Escolar Documentos
Profissional Documentos
Cultura Documentos
ENGINEERING
This is a series of Pergamon scientific reference works, each volume providing comprehensive,
self-contained and up-to-date coverage of a selected area in the field of materials science and
engineering. T h e series is being developed primarily from the highly acclaimed Encyclopedia
of Materials Science and Engineering, published in 1986. Other titles in the series are listed
below.
B E V E R t (ed.)
Concise Encyclopedia
of Materials
Economics,
B R O O K (ed.)
Concise Encyclopedia of Advanced
C A R R & H E R Z (eds.)
Concise Encyclopedia of Mineral
Policy &
Ceramic
Management
Materials
Resources
C O R I S H (ed.)
Concise Encyclopedia
of Polymer Processing
&
Applications
E V E T T S (ed.)
Concise Encyclopedia
of Magnetic
& Superconducting
Materials
K E L L Y (ed.)
Concise Encyclopedia
of Composite
Materials
M A H A J A N & K I M E R L I N G (eds.)
Concise Encyclopedia
of Semiconducting
Materials
& Related
Technologies
M O A V E N Z A D E H (ed.)
Concise Encyclopedia
Materials
S C H N I E W I N D (ed.)
Concise Encyclopedia
W I L L I A M S (ed.)
Concise Encyclopedia
of Medical
& Dental
Materials
Materials
NOTICE TO READERS
Dear Reader
If your library is not already a standing order/continuation order customer to the series
A d v a n c e s in M a t e r i a l s Science a n d E n g i n e e r i n g , m a y w e r e c o m m e n d that you place a
standing/continuation order to receive immediately upon publication all new volumes. Should
you find that these volumes no longer serve your needs, your order can be cancelled at any time
without notice.
B E V E R t (ed.)
Concise Encyclopedia
of Materials
Economics,
B R O O K (ed.)
Concise Encyclopedia of Advanced
C A R R & H E R Z (eds.)
Concise Encyclopedia of Mineral
Policy &
Ceramic
Management
Materials
Resources
C O R I S H (ed.)
Concise Encyclopedia
of Polymer Processing
&
Applications
E V E T T S (ed.)
Concise Encyclopedia
of Magnetic
& Superconducting
Materials
K E L L Y (ed.)
Concise Encyclopedia
of Composite
Materials
M A H A J A N & K I M E R L I N G (eds.)
Concise Encyclopedia
of Semiconducting
Materials
& Related
Technologies
M O A V E N Z A D E H (ed.)
Concise Encyclopedia
Materials
S C H N I E W I N D (ed.)
Concise Encyclopedia
W I L L I A M S (ed.)
Concise Encyclopedia
of Medical
& Dental
Materials
Materials
NOTICE TO READERS
Dear Reader
If your library is not already a standing order/continuation order customer to the series
A d v a n c e s in M a t e r i a l s Science a n d E n g i n e e r i n g , m a y w e r e c o m m e n d that you place a
standing/continuation order to receive immediately upon publication all new volumes. Should
you find that these volumes no longer serve your needs, your order can be cancelled at any time
without notice.
CONCISE ENCYCLOPEDIA OF
MATERIALS CHARACTERIZATION
Editors
of Cambridge,
UK
ERIC LIFSHIN
General
Electric
Development,
UK
MICHAEL BEVER*
MIT, Cambridge, MA, USA
PERGAMON PRESS
OXFORD NEW YORK SEOUL TOKYO
UK
USA
KOREA
JAPAN
(~) The paper used in this publication meets the minimum requirements of the
American National Standard for Information S c i e n c e s P e r m a n e n c e of Paper for
Printed Library Materials, A N S I Z 3 9 . 4 8 - 1 9 8 4 .
Printed and bound in Great Britain by Butler & Tanner Ltd, Frome
Chairman
Walter S Owen
MIT, Cambridge,
MA, USA
MIT, Cambridge,
Kent Bowen
MIT, Cambridge,
Gilbert Y
Jack W Christian F R S
MA, USA
Chin
AT&T Bell
Laboratories
Murray Hill, NJ, USA
vi
MA, USA
University
of Oxford,
UK
Derek Hull F R S
University
of Cambridge,
University
of Oxford,
Anthony Kelly C B E
UK
UK
FRS
University of Surrey
Guildford, UK
Chairman,
Walter S Owen
Honorary
Editorial
Advisory
Board
Robert W Cahn
Executive
Editor
Publishing
Director,
Peter Shepherd
Pergamon
Press
vii
FOREWORD
Honorary
Editorial
Chairman
Advisory
Board
ix
EDITORS' PREFACE
T h e Concise Encyclopedia
of Materials
Characterization
is f o u n d e d o n t h e l a r g e g r o u p
of articles on c h a r a c t e r i z a t i o n a n d i n v e s t i g a t i o n of m a t e r i a l s in t h e o r i g i n a l
Encyclopedia
of Materials
Science and Engineering,
p u b l i s h e d in 1 9 8 6 , for w h i c h E r i c L i f s h i n w a s
r e s p o n s i b l e at t h e t i m e . T h e s e a r t i c l e s w e r e s u p p l e m e n t e d w i t h a n u m b e r of a d d i t i o n a l
o n e s w h i c h h a d b e e n c o m m i s s i o n e d b y R o b e r t C a h n for Supplementary
Volume 1 a n d
Supplementary
Volume 2 , p u b l i s h e d in 1988 a n d 1 9 9 0 r e s p e c t i v e l y , w i t h f u r t h e r a r t i c l e s
that w e r e s p e c i f i c a l l y c o m m i s s i o n e d b y b o t h of u s for t h e p r e s e n t v o l u m e . W e b e l i e v e
that t h i s g r a d u a l a c c r e t i o n of e s s a y s o n w h a t h a s e v e n t u a l l y b e c o m e an e x t r e m e l y w i d e
r a n g e of t e c h n i q u e s h a s p r o v e d to b e an e f f e c t i v e w a y of c o v e r i n g t h i s e n o r m o u s field.
T h e t e x t b e g i n s w i t h an i n t r o d u c t i o n to t h e w h o l e field, w r i t t e n b y E r i c L i f s h i n . T h e
m a j o r i t y of t h e 116 a l p h a b e t i c a l a r t i c l e s c o v e r a r a n g e of t e c h n i q u e s of c h a r a c t e r i z a t i o n
w h i c h a r e n o t s p e c i f i c t o a n y o n e g r o u p of m a t e r i a l s , a l t h o u g h n o f e w e r t h a n 12 are
specific to p o l y m e r s a n d s e v e r a l m o r e are specific to m e t a l s , c e r a m i c s o r s e m i c o n d u c t o r s .
A g a i n , a m a j o r i t y of t h e t e c h n i q u e s c o v e r e d a r e i n t r i n s i c a l l y b u l k m e t h o d s , b u t a
s u b s t a n t i a l m i n o r i t y a r e s p e c i f i c to t h e s t u d y of t h e t o p o g r a p h y a n d c o m p o s i t i o n of
surfaces and near-surface regions. S o m e are venerable techniques (though even these
a r e r e g u l a r l y m o d e r n i z e d ) a n d o t h e r s a r e of v e r y r e c e n t v i n t a g e : t h i s l a t t e r i n c l u d e s , by
w a y of e x a m p l e , articles such as Atomic Force Microscopy,
Confocal Optical
Microscopy,
Gamma-Ray
Diffrac tome try; Thermal Wave Imaging;
a n d X-Ray Diffraction,
TimeResolved.
T h e a r t i c l e t i t l e s g u i d e t h e r e a d e r to a r t i c l e s c o v e r i n g s p e c i f i c t e c h n i q u e s ,
b u t as t e c h n i q u e s m a y b e d i s c u s s e d e l s e w h e r e o t h e r t h a n in an a r t i c l e d e v o t e d to t h e m ,
t h e d e t a i l e d i n d e x w i l l aid t h e r e a d e r t o find all t h e v a r i o u s p l a c e s w h e r e a p a r t i c u l a r
t o p i c is t r e a t e d .
L i k e all e d i t o r s , w e h a v e b e e n c o n s t r a i n e d b y t h e a v a i l a b l e s p a c e to m a k e s o m e
difficult c h o i c e s c o n c e r n i n g w h a t t o i n c l u d e a n d w h a t to l e a v e o u t . In p a r t i c u l a r , t h e
shadowy borderland between characterization and nondestructive evaluation posed
s o m e p r o b l e m s : in g e n e r a l , w e o m i t t e d t e c h n i q u e s w h i c h are c l o s e r to t h e w o r l d of
i n s p e c t i o n t h a n to t h a t of r e s e a r c h .
W e w i s h to e x p r e s s o u r g r a t i t u d e for t h e h a r d w o r k , a n d f o r b e a r a n c e , of t h e m a n y
a u t h o r s w h o h a v e w r i t t e n a r t i c l e s for u s , s o m e t i m e s a g a i n s t d e m a n d i n g d e a d l i n e s . W e
a r e a l s o g r e a t l y i n d e b t e d t o t h e p r o f e s s i o n a l s at P e r g a m o n P r e s s i n p a r t i c u l a r , P e t e r
F r a n k a n d H e l e n M c P h e r s o n f o r all t h e y h a v e d o n e to b r i n g this v o l u m e i n t o e x i s t e n c e .
Robert W Cahn
Eric Lifshin
Editors
T h i s C o n c i s e E n c y c l o p e d i a is a c o m p r e h e n s i v e
r e f e r e n c e w o r k c o v e r i n g all a s p e c t s of m a t e r i a l s
c h a r a c t e r i z a t i o n . I n f o r m a t i o n is p r e s e n t e d in
a s e r i e s of a l p h a b e t i c a l l y a r r a n g e d a r t i c l e s
w h i c h d e a l c o n c i s e l y w i t h i n d i v i d u a l t o p i c s in a
self-contained manner. This guide outlines the
main
features
and
organization
of
the
E n c y c l o p e d i a , a n d is i n t e n d e d to h e l p t h e r e a d e r
to l o c a t e t h e m a x i m u m a m o u n t of i n f o r m a t i o n
on a g i v e n t o p i c .
A c c e s s i b i l i t y of m a t e r i a l is of vital i m p o r t a n c e in
a r e f e r e n c e w o r k of t h i s k i n d a n d a r t i c l e titles h a v e
t h e r e f o r e b e e n s e l e c t e d not o n l y o n t h e b a s i s of
article c o n t e n t b u t a l s o w i t h t h e m o s t p r o b a b l e n e e d s
of the r e a d e r in m i n d . A n a l p h a b e t i c a l list of all t h e
articles c o n t a i n e d in t h i s E n c y c l o p e d i a is to b e f o u n d
on p p . xvii a n d x v i i i .
Articles are linked by an e x t e n s i v e cross-referencing
s y s t e m . C r o s s - r e f e r e n c e s t o o t h e r a r t i c l e s in t h e
E n c y c l o p e d i a a r e of t w o t y p e s : in t e x t a n d e n d of
text. T h o s e in t h e b o d y of t h e text are d e s i g n e d t o
refer t h e r e a d e r to a r t i c l e s that p r e s e n t in g r e a t e r
detail m a t e r i a l o n t h e s p e c i f i c t o p i c u n d e r d i s c u s s i o n
at that point. T h e y g e n e r a l l y take o n e of the f o l l o w i n g
forms:
...which is fully described in the article Field-Ion
Microscopy:
Observation
of Radiation
Effects.
...other applications of this technique (see
Sampling
Inductively
Coupled
Plasma
Spectrometry).
Laser
Mass
T h e c r o s s - r e f e r e n c e s listed at t h e e n d of an a r t i c l e
s e r v e to identify b r o a d b a c k g r o u n d r e a d i n g a n d to
direct the r e a d e r to articles that c o v e r different a s p e c t s
of t h e s a m e t o p i c .
T h e n a t u r e of an e n c y c l o p e d i a d e m a n d s a h i g h e r
d e g r e e of u n i f o r m i t y in t e r m i n o l o g y a n d n o t a t i o n
than many other scientific works. The widespread
u s e of t h e SI s y s t e m of u n i t s h a s d e t e r m i n e d that
s u c h u n i t s b e u s e d in t h i s E n c y c l o p e d i a . It h a s b e e n
r e c o g n i z e d , h o w e v e r , that in s o m e fields I m p e r i a l
u n i t s a r e m o r e g e n e r a l l y u s e d . W h e r e this is the
c a s e , I m p e r i a l u n i t s are g i v e n with their SI e q u i v a l e n t
q u a n t i t y a n d u n i t f o l l o w i n g in p a r e n t h e s e s . W h e r e
p o s s i b l e , t h e s y m b o l s d e f i n e d in Quantities,
Units,
and Symbols,
p u b l i s h e d b y t h e R o y a l S o c i e t y of
London, have been used.
A l l a r t i c l e s in t h e E n c y c l o p e d i a i n c l u d e a
b i b l i o g r a p h y g i v i n g s o u r c e s of further i n f o r m a t i o n .
E a c h b i b l i o g r a p h y consists of general i t e m s for further
r e a d i n g and/or references w h i c h c o v e r specific aspects
of t h e t e x t . W h e r e a p p r o p r i a t e , a u t h o r s are c i t e d in
t h e t e x t u s i n g a n a m e / d a t e s y s t e m as f o l l o w s :
...as was recently reported (Smith 1988).
Jones (1984) describes...
T h e c o n t r i b u t o r s ' n a m e s a n d t h e o r g a n i z a t i o n s to
w h i c h t h e y a r e affiliated a p p e a r at t h e e n d of all
articles.
A l l c o n t r i b u t o r s c a n b e f o u n d in t h e
a l p h a b e t i c a l L i s t of C o n t r i b u t o r s , a l o n g w i t h t h e i r
full p o s t a l a d d r e s s e s a n d t h e titles of t h e a r t i c l e s of
w h i c h t h e y are a u t h o r s or c o a u t h o r s .
T h e a r t i c l e An Introduction
to Investigation
and
Characterization
of Materials
p r o v i d e s an o v e r v i e w
of t h e s u b j e c t a r e a a n d d i s c u s s e s in b r i e f t h e i s s u e s
c o v e r e d in d e t a i l b y t h e a r t i c l e s in t h e b o d y of the
work.
T h e m o s t i m p o r t a n t i n f o r m a t i o n s o u r c e for locating
a p a r t i c u l a r topic in the E n c y c l o p e d i a is the multilevel
S u b j e c t I n d e x , w h i c h h a s b e e n m a d e as c o m p l e t e
a n d fully s e l f - c o n s i s t e n t as p o s s i b l e .
xv
Acoustic Emission
Acoustic Microscopy
A d h e s i v e s : T e s t s for M e c h a n i c a l P r o p e r t i e s
Anodization Spectroscopy
Art F o r g e r i e s : Scientific D e t e c t i o n
Atomic Force Microscopy
Auger Electron Spectroscopy
Auger Microscopy, Angular Distribution
Ceramic Materials: Cathodoluminescence Analysis
Ceramic Powders: Packing Characterization
Channelling-Enhanced Microanalysis
C h e m i c a l A n a l y s i s of Solid Surfaces
Composite Materials: Nondestructive Evaluation
Compton Scattering
Confocal O p t i c a l M i c r o s c o p y
Corrosion and Oxidation Study Techniques
Corrosion: Test Methods
D e p t h Profiling
Diffusion: N o v e l M e a s u r e m e n t M e t h o d s
Elastomers: Spectroscopic Characterization
E l a s t o m e r s : T e s t s for M e c h a n i c a l P r o p e r t i e s
E l e c t r o n Diffraction
E l e c t r o n Diffraction, L o w - E n e r g y
Electron Energy-Loss Spectrometry
Electron Microprobe Analysis
E l e c t r o n M i c r o s c o p e A n a l y s i s of Defect C l u s t e r s ,
Voids and Bubbles
Electron Microscopy, Analytical
Electron Microscopy, High-Resolution
Electron Microscopy, High-Voltage
E l e c t r o n S p e c t r o s c o p y for C h e m i c a l A n a l y s i s
E l e c t r o n Spin R e s o n a n c e
Electron Tunnelling Spectroscopy
Field-Ion Microscopy: Atom-Probe Microanalysis
F i e l d - I o n M i c r o s c o p y : O b s e r v a t i o n of R a d i a t i o n
Effects
Fractals
Gamma Radiography
G a m m a - R a y Diffractometry
G a s and L i q u i d C h r o m a t o g r a p h y
Gas Sensors, Solid-State
Grain S i z e : N o n d e s t r u c t i v e E v a l u a t i o n
Hardness Characterization
H y d r o g e n as a M e t a l l u r g i c a l P r o b e
Infrared S p e c t r o s c o p y
Ion B a c k s c a t t e r i n g A n a l y s i s
Junction Transient Spectroscopy
Laser Microprobe Mass Spectrometry
Laser Sampling Inductively Coupled Plasma Mass
Spectrometry
Liquid Chromatography Mass Spectroscopy
Magnetic Materials: Measurements
Mechanical Properties Microprobe
M i c r o e n g i n e e r i n g of M a t e r i a l s : C h a r a c t e r i z a t i o n
Alphabetical
xviii
List of
Articles
Characteristics
X - R a y A b s o r p t i o n S p e c t r o s c o p y : E X A F S and
XANES Techniques
X - R a y a n d N e u t r o n Diffraction S t u d i e s of
Amorphous Solids
X - R a y a n d N e u t r o n Diffuse S c a t t e r i n g of R a d i a t i o n Induced Defects
X - R a y Diffraction, T i m e - R e s o l v e d
X-Ray Fluorescence Spectrometry
X-Ray Microanalysis, Quantitative
X - R a y P o w d e r Diffraction
AN INTRODUCTION TO INVESTIGATION
AND CHARACTERIZATION OF MATERIALS
by Eric Lifshin
P r e s e n t - d a y m a t e r i a l s science d e p e n d s heavily o n
u n d e r s t a n d i n g h o w t h e p r o p e r t i e s of a m a t e r i a l relate
to its c o m p o s i t i o n a n d m i c r o s t r u c t u r e . H o w e v e r , this
a p p r o a c h is relatively recent a n d for centuries before
B o h r ' s m o d e l of t h e a t o m , skilled craftsmen a n d
builders p r o d u c e d m a n y objects of r e m a r k a b l e utility
a n d b e a u t y w i t h o u t a n y k n o w l e d g e of w h a t is n o w
considered basic c h e m i s t r y o r m e t a l l u r g y . T h e y
started with m a t e r i a l s f o u n d in their native s t a t e o r
those r e q u i r i n g m i n i m a l processing. D e s i r e d p r o p e r
ties were achieved b y trial a n d e r r o r e x p e r i m e n t a t i o n
or the utilization of experience p a s s e d d o w n t h r o u g h
generations.
F o r t h o u s a n d s of y e a r s certain m e t a l s were
extracted from their ores b y smelting, with v a r i a t i o n s
in the resulting p r o p e r t i e s often being a t t r i b u t e d t o
s u p e r n a t u r a l i n t e r v e n t i o n r a t h e r t h a n t o subtle dif
ferences in t h e m a t e r i a l s o r processes used. A s time
passed a n d p r i n t i n g d e v e l o p e d , practical experience
w a s written d o w n . F o r e x a m p l e , in the sixteenth
c e n t u r y A g r i c o l a ' s De re metallica described m a n y of
the m e t h o d s used for t h e e x t r a c t i o n , m e a s u r e m e n t
a n d classification of m e t a l s . A t a b o u t t h e s a m e t i m e
empirical k n o w l e d g e existed of h o w t o use distillation
to p r e p a r e a variety of simple c o m p o u n d s including
v a r i o u s a l c o h o l s a n d oils.
U n t i l t h e e i g h t e e n t h c e n t u r y only a small n u m b e r of
elements were k n o w n , a n d physical a t t r i b u t e s like
density, c o l o r a n d h a r d n e s s were sufficient t o tell o n e
from a n o t h e r . A s c h e m i s t r y a n d physics d e v e l o p e d in
the n i n e t e e n t h c e n t u r y , t h e g r o w t h of m o r e basic
u n d e r s t a n d i n g led t o t h e discovery of a n u m b e r of
elements a n d t h e e x t r a c t i o n o r synthesis of t h o u s a n d s
of c o m p o u n d s . T h e s e n e w s u b s t a n c e s were a p p l i e d
to m a n y a r e a s i n c l u d i n g m e d i c i n e , c o n s t r u c t i o n ,
t r a n s p o r t a t i o n , w e a p o n r y a n d a g r i c u l t u r e . By t h e
m i d - n i n e t e e n t h c e n t u r y t h e a m o u n t of scientific infor
m a t i o n available h a d g r o w n so large t h a t v a r i o u s
scientific disciplines b e g a n t o split i n t o specialties. I n
chemistry, general chemists w e r e r e p l a c e d b y o r g a n i c ,
i n o r g a n i c , physical, physiological, a g r i c u l t u r a l a n d
analytical chemists. I n 1848 F r e s e n i u s f o u n d e d t h e
first analytical l a b o r a t o r y w h i c h , in a d d i t i o n t o teach
ing, p r o v i d e d g o v e r n m e n t agencies a n d i n d u s t r y w i t h
checks o n m a t e r i a l specifications a n d t h e analysis of
water, food a n d physiological specimens. T h e idea
c a u g h t o n a n d t o d a y t h e r e a r e h u n d r e d s of i n d e p e n
d e n t analytical l a b o r a t o r i e s , as well a s t h o s e associ
ated with h o s p i t a l s , i n d u s t r i a l c o n c e r n s , universities
a n d g o v e r n m e n t agencies. F o l l o w i n g t h e specializa
tion of analytical c h e m i s t r y t h e r e h a s r e m a i n e d a
s t r o n g interplay b e t w e e n t h e analysis a n d d e v e l o p
m e n t of m a t e r i a l s . Better analytical m e t h o d s lead t o a
1. Historical
Background
xix
Introduction
because of difficulty in m e a s u r i n g r e a c t i o n e n d p o i n t s ,
b u t as m o r e i n d i c a t o r s b e c a m e available t h e m e t h o d
grew in p o p u l a r i t y . A t h i r d t e c h n i q u e , k n o w n as
c o l o r i m e t r y , w a s also k n o w n in t h e n i n e t e e n t h cen
tury. Selected r e a c t i o n s a r e p e r f o r m e d t o p r o d u c e
colored c o m p o u n d s c o n t a i n i n g t h e e l e m e n t of inter
est. C o l o r intensity is t h e n m e a s u r e d , relative t o
s t a n d a r d s o l u t i o n s , t o e s t i m a t e t h e a m o u n t of t h a t
element present. A l t h o u g h this a p p r o a c h w a s initially
limited t o a few elements a n d q u a n t i t a t i v e analysis
w a s fairly subjective, its use increased as m o r e c o l o n metric reagents were identified a n d i n s t r u m e n t a t i o n
was developed to m a k e measurements m o r e accurate.
T h e n i n e t e e n t h c e n t u r y also saw t h e initial d e v e l o p
m e n t of electroanalytical c h e m i s t r y a n d t h e use of
polarized light t o discriminate b e t w e e n m a t e r i a l s , b u t
t h e m o s t significant i n s t r u m e n t a l m e t h o d d e v e l o p e d
w a s t h e s p e c t r o s c o p e . Its o p e r a t i o n is b a s e d o n t h e
ability of a p r i s m t o disperse w h i t e light i n t o its
v a r i o u s c o n s t i t u e n t s , a fact d e m o n s t r a t e d b y N e w t o n
in the seventeenth c e n t u r y . I n 1814 F r a u n h o f e r , a lens
m a n u f a c t u r e r , recognized t h a t a n u m b e r of b o t h
bright a n d d a r k lines c o u l d b e o b s e r v e d in b o t h
sunlight a n d t h e flames p r o d u c e d b y b u r n i n g different
fuels. T h e idea of using a b s o r p t i o n spectra for m o r e
general chemical analysis w a s p r o p o s e d b y Brewster a
few years later. I n t h e 1850s B u n s e n a n d Kirchhoff
developed a s p e c t r o s c o p e w i t h a n i m p r o v e d s o u r c e
a n d viewing optics which is t h e f o r e r u n n e r of instru
m e n t s used t o d a y . W i t h it they discovered b o t h t h e
elements cesium a n d r u b i d i u m .
A t t h e beginning of t h e n i n e t e e n t h c e n t u r y only
a b o u t 30 elements were k n o w n ; b y t h e e n d this
n u m b e r h a d m o r e t h a n d o u b l e d . D u r i n g this p e r i o d it
also b e c a m e a p p a r e n t t h a t s o m e t y p e of systematic
classification of t h e elements w a s n e e d e d . T h e c o n c e p t
of t h e periodic table w a s i n d e p e n d e n t l y d e v e l o p e d b y
M e n d e l e e v in R u s s i a a n d M e y e r in G e r m a n y using
schemes b a s e d o n a t o m i c weights a n d v a r i o u s o t h e r
physical p r o p e r t i e s . A l t h o u g h o r d e r i n g of t h e ele
m e n t s is n o w related t o a t o m i c n u m b e r a n d t h e
electronic s t r u c t u r e of t h e elements, m o s t of t h e
c h a n g e s m a d e over t h e years h a v e b e e n t o a d d n e w
elements r a t h e r t h a n t o r e o r d e r k n o w n elements.
A t the e n d of t h e n i n e t e e n t h c e n t u r y a n d t h e
beginning of t h e twentieth c e n t u r y a series of m a j o r
events t o o k place w h i c h revolutionized u n d e r s t a n d i n g
of b o t h t h e a t o m a n d t h e e l e t r o m a g n e t i c r a d i a t i o n .
Studies of t h e electrical c o n d u c t i v i t y of gases a t
r e d u c e d pressure led t o t h e discovery of c a t h o d e r a y s
by H i t t o r f in 1869, confirmed by G o l d s t e i n in 1876.
A l t h o u g h initially t h e n a t u r e of these rays w a s
unclear, w o r k b y T h o m s o n , p u b l i s h e d in 1897,
s h o w e d t h a t they consisted of negatively c h a r g e d
particles, from their deflection in m a g n e t i c a n d
electrostatic fields. H e also d e m o n s t r a t e d t h a t these
particles (later called electrons) h a d t h e s a m e c h a r g e t o - m a s s r a t i o as t h o s e given off from h o t filaments o r
released d u r i n g t h e e x p o s u r e of certain m e t a l s t o
xx
e l e c t r o m a g n e t i c r a d i a t i o n (the p h o t o e l e c t r i c effect,
discovered b y H e r t z in 1887). T h u s they a p p e a r e d t o
b e a key c o m p o n e n t of all m a t t e r , a n d w h e n r e m o v e d
w o u l d leave a t o m s as positive ions.
T h e n a t u r e of this positive ion c o r e w a s studied in
t h e first d e c a d e of t h e t w e n t i e t h c e n t u r y b y R u t h e r
ford, w h o e x p e r i m e n t e d o n t h e scattering of p a r t i
cles from thin m e t a l foils. F r o m this w o r k c a m e a
m o d e l of t h e a t o m in w h i c h electrons revolve a r o u n d
a positively c h a r g e d n u c l e u s . A l t h o u g h this m o d e l w a s
consistent w i t h his o b s e r v a t i o n s , it w a s u n a c c e p t a b l e
from t h e p o i n t of view of classical physics, since t h e
electrons w o u l d c o n t i n u o u s l y r a d i a t e energy a n d
s h o u l d , therefore, spiral i n t o t h e nucleus. H o w e v e r ,
this d i l e m m a w a s s o o n reconciled by B o h r , w h o
p o s t u l a t e d t h a t t h e electron o r b i t s c o r r e s p o n d e d t o
discrete energy states a n d as l o n g as a n electron
r e m a i n e d in its o r b i t n o r a d i a t i o n w o u l d occur. T h e
idea of discrete energy states w a s b a s e d o n t h e p r i n
ciples of q u a n t u m m e c h a n i c s i n t r o d u c e d b y P l a n c k in
1900 t o describe r a d i a t i o n e m i t t e d from a black b o d y .
U s i n g these states, B o h r w a s able t o describe correctly
t h e line s p e c t r a of h y d r o g e n o b s e r v e d in t h e 1880s b y
B a l m e r a n d m a t h e m a t i c a l l y f o r m u l a t e d by R y d b e r g
in 1890. A l t h o u g h t h e B o h r m o d e l w a s significantly
modified b y S o m m e r f e l d a n d S c h r o d i n g e r t o describe
m u l t i e l e c t r o n a t o m s m o r e accurately, t h e c o n c e p t of
electron t r a n s i t i o n s b e t w e e n discrete levels a n d t h e
a c c o m p a n y i n g release o r a b s o r p t i o n of energy is of
central i m p o r t a n c e t o m a n y of t h e different types of
p h o t o n a n d electron s p e c t r o m e t r i e s used t o d a y .
T h o m p s o n ' s use of m a g n e t i c a n d electric fields t o
d e t e r m i n e c h a r g e - t o - m a s s r a t i o s w a s also applied t o
t h e c h a r a c t e r i z a t i o n of positive ion b e a m s (called
K a n a l s t r a h l e n b y G o l d s t e i n ) , w h i c h were also k n o w n
t o exist a l o n g with c a t h o d e r a y s , as s h o w n in
e x p e r i m e n t s o n t h e electrical c o n d u c t i v i t y of gases.
T h o m s o n ' s apparatus, k n o w n as a parabolic mass
s p e c t r o m e t e r , p r o d u c e d a series of p h o t o g r a p h i c a l l y
r e c o r d e d p a r a b o l a s , o n e for e a c h c h a r g e - t o - m a s s
r a t i o . T h e system lacked m a s s r e s o l u t i o n , h o w e v e r ,
because it h a d n o energy selectivity. This difficulty
w a s o v e r c o m e several years later (1919) w h e n A s t o n
d e v e l o p e d a velocity focusing i n s t r u m e n t w h i c h
s h o w e d t h a t t h e s p e c t r u m of n e o n actually c o n t a i n e d
t w p p e a k s , o n e a t m a s s 20 a n d t h e o t h e r a t m a s s 22.
T h i s d e m o n s t r a t e d t h a t a n e l e m e n t of a given n u m b e r
c a n h a v e m o r e t h a n o n e f o r m (isotopes) a n d t h u s
revealed t h e p o w e r of t h e m a s s s p e c t r o m e t e r as a n
i m p o r t a n t analytical i n s t r u m e n t . I n t h e d e c a d e s t h a t
followed, r e s o l u t i o n a n d sensitivity c o n t i n u e d t o im
p r o v e as a result of t h e efforts of D e m p s t e r , M a t t a u c h
and Herzog, and Nier and Johnson. Some commer
cially available i n s t r u m e n t s t o d a y h a v e m a s s resolu
tions of 1 p a r t in 100 000, c o m p a r e d w i t h t h e 1 p a r t in
12 of t h e first p a r a b o l i c s p e c t r o m e t e r s .
E x p e r i m e n t s o n t h e electrical c o n d u c t i v i t y of gases
also led t o t h e accidental discovery of r a y s b y
R o e n t g e n in 1896. H e recognized t h a t their u n u s u a l
Introduction
p e n e t r a t i n g p o w e r w a s influenced by t h e t u b e o p e r a t
ing voltage as well as by t h e thickness a n d t y p e of
a b s o r b e r s used. Since r a y s were n o t deflected b y
m a g n e t i c o r electrostatic fields, it w a s believed t h a t
they were p a r t of t h e e l e c t r o m a g n e t i c s p e c t r u m , b u t
t h a t they m u s t h a v e a very s h o r t w a v e l e n g t h . D e t e r
m i n i n g their w a v e l e n g t h d i s t r i b u t i o n p r e s e n t e d s o m e
thing of a p r o b l e m , b e c a u s e a l t h o u g h diffraction
gratings h a d previously b e e n d e v e l o p e d for dispersing
visible spectra, they were n o t fine e n o u g h t o s e p a r a t e
rays. T h e s o l u t i o n w a s p r o p o s e d b y L a u e in 1912,
w h o believed t h a t t h e i n t e r a t o m i c s p a c i n g of crystals
should be of t h e right o r d e r of m a g n i t u d e t o act a s
suitable diffraction g r a t i n g s . H e p r o v e d this h y p o t h e
sis by p a s s i n g a b e a m of r a y s t h r o u g h a crystal of
zinc sulfide a n d o b t a i n i n g a p a t t e r n of s p o t s o n a
photographic plate.
This w o r k s t i m u l a t e d further studies b y W . H .
Bragg a n d W . L. B r a g g (father a n d s o n ) , w h o built t h e
first crystal diffraction s p e c t r o m e t e r . U s i n g a crystal
of r o c k salt with a k n o w n i n t e r p l a n a r spacing, t h e y
were able t o c h a r a c t e r i z e t h e spectral d i s t r i b u t i o n of a
p l a t i n u m x-ray t a r g e t a n d also d e v e l o p t h e simple
e q u a t i o n w h i c h relates i n t e r p l a n a r spacing, x-ray
wavelength a n d diffraction angle. T h e s p e c t r a t h e y
observed consisted of b o t h a b r o a d b a n d of general
r a d i a t i o n (the x-ray c o n t i n u u m ) a n d discrete lines
characteristic of t h e t u b e a n o d e . I n v e s t i g a t i o n s b y
Moseley described in 1913 s h o w e d t h a t t h e r e also
existed a simple r e l a t i o n s h i p b e t w e e n t h e w a v e l e n g t h s
of the characteristic lines e m i t t e d from a n e l e m e n t a n d
its a t o m i c n u m b e r . T h i s u n i q u e r e l a t i o n s h i p f o r m s t h e
basis for e l e m e n t a l analysis by a variety of x-ray,
electron a n d i o n - i n d u c e d x-ray spectroscopies. T h e
w o r k of t h e B r a g g s also p r o v i d e d t h e key t o crystal
s t r u c t u r e d e t e r m i n a t i o n b y u s i n g a selected c h a r a c t e r
istic x-ray w a v e l e n g t h t o d e t e r m i n e a set of i n t e r p l a
n a r spacings for a single crystal.
T h e n u m e r o u s scientific discoveries t h a t t o o k place
at the b e g i n n i n g of t h e t w e n t i e t h c e n t u r y p r o v i d e d t h e
physical f o u n d a t i o n for t h e h u n d r e d s of i n s t r u m e n
t a l o r i e n t e d analytical m e t h o d s w h i c h a r e widely
used t o d a y . It is a s t o n i s h i n g t h a t m o s t of w h a t we n o w
consider s t a n d a r d l a b o r a t o r y i n s t r u m e n t s were d e
veloped after 1930. T h e following t e c h n i q u e s a n d key
contributors are examples:
transmission electron microscopy, Ruska (1934)
scanning electron microscopy, von Ardenne (1938)
liquid chromatography, Martin and Synge (1941)
carbon-14 dating, Libby (1946)
nuclear magnetic resonance, Block and Purcell (1946)
electron microprobe analysis, Castaing (1951)
gas chromatography, Martin and James (1952)
secondary-ion mass spectrometry, Castaing and Slodzian
(1960)
T h e n a m e s , events a n d d a t e s m e n t i o n e d so far tell
only a small p a r t of t h e c h r o n o l o g i c a l d e v e l o p m e n t of
s o m e of t h e m e t h o d s described. Practical refinement
of m a n y of these i n s t r u m e n t a l m e t h o d s often t o o k
m a n y y e a r s a n d c o n s i d e r a b l e ingenuity o n t h e p a r t of
o t h e r key c o n t r i b u t o r s . F o r e x a m p l e , t h e first c o m
mercially available s c a n n i n g electron m i s c r o s c o p e did
n o t a p p e a r until 27 years (1965) after v o n A r d e n n e ' s
first i n s t r u m e n t , a n d it h a s b e e n only d u r i n g t h e last
few y e a r s t h a t relatively easy-to-use c o m p u t e r i z e d
complete
single-crystal
structure
determination
e q u i p m e n t h a s been readily available. A t p r e s e n t o n e
of t h e m o s t active a r e a s of analysis is t h e s t u d y of
surfaces b y x-ray p h o t o e l e c t r o n s p e c t r o s c o p y b u t , as
m e n t i o n e d previously, t h e p h o t o e l e c t r i c effect w a s
k n o w n before t h e e n d of t h e n i n e t e e n t h c e n t u r y .
Relatively recent d e v e l o p m e n t s in electronics, c o m
p u t e r s a n d h i g h - v a c u u m systems h a v e all h a d a n
e n o r m o u s i m p a c t o n analytical i n s t r u m e n t a t i o n in
t e r m s of ease of o p e r a t i o n , s o p h i s t i c a t i o n of the
analysis, q u a l i t y of results a n d speed. I n d u s t r i a l l a b o r
a t o r i e s n o w r o u t i n e l y u n d e r t a k e types of analysis t h a t
w o u l d formerly h a v e r e q u i r e d t h e effort for a P h . D .
thesis.
W i t h t h e great diversity of i n s t r u m e n t a t i o n avail
able, t h e role of t h e t r a d i t i o n a l analytical l a b o r a t o r y
h a s n o w b e e n e x p a n d e d t o include d e t e r m i n a t i o n s of
morphology, microstructure, crystallography and a
variety of physical p r o p e r t i e s . T h e t e r m often associ
a t e d with t h e c o m b i n a t i o n of analytical chemistry a n d
these o t h e r m e t h o d s of analysis is m a t e r i a l s c h a r a c t e r
ization. T h e c o n c e p t of a m a t e r i a l s c h a r a c t e r i z a t i o n
g r o u p goes h a n d in h a n d with t h e e v o l u t i o n of
interdisciplinary m a t e r i a l s science a n d engineering
centers w h i c h b r i n g t o g e t h e r e x p e r t s in such a r e a s as
m e t a l l u r g y , electronic m a t e r i a l s , ceramics, solid-state
physics, p o l y m e r s a n d surface chemistry. N o t only
h a v e t h e variety of m a t e r i a l s a n d t h e types of instru
m e n t a t i o n available increased, b u t t h e r e a s o n s for
l o o k i n g a t these m a t e r i a l s h a v e also multiplied.
M a t e r i a l s c h a r a c t e r i z a t i o n specialists m u s t n o w be
c o n c e r n e d with basic research, p r o d u c t a n d process
d e v e l o p m e n t , failure analysis, r e g u l a t o r y c o m p l i a n c e ,
p a t e n t issues, q u a l i t y c o n t r o l , m a n u f a c t u r i n g p r o d u c
tivity a n d t h e e x a m i n a t i o n of c o m p e t i t i v e p r o d u c t s .
It is also i m p o r t a n t t o recognize t h e degree of
analytical specialization w h i c h h a s b e e n t a k i n g place.
I n d i v i d u a l s w h o a r e e x p e r t s in n u c l e a r m a g n e t i c reso
n a n c e s p e c t r o s c o p y m a y n o t h a v e expertise in singlecrystal x-ray s t r u c t u r e d e t e r m i n a t i o n , even t h o u g h
i n f o r m a t i o n gained b y t h e t w o t e c h n i q u e s m a y be
highly c o m p l e m e n t a r y a n d i m p o r t a n t t o a p o l y m e r
chemist. A n e x p e r t in t r a n s m i s s i o n electron m i c r o
s c o p y m a y h a v e only a n incidental k n o w l e d g e of
s e c o n d a r y - i o n m a s s s p e c t r o m e t r y , even t h o u g h b o t h
chemical a n d s t r u c t u r a l i n f o r m a t i o n m a y be t h e
key t o u n d e r s t a n d i n g t h e b e h a v i o u r of a n electronic
device. A s t h e d e m a n d for m a t e r i a l s with u n i q u e
p r o p e r t i e s g r o w s , so also d o e s t h e c o m p l e x i t y of t h e
m a t e r i a l s themselves a n d t h e m e t h o d s n e e d e d t o a n a
lyze t h e m . E x a m p l e s a r e t h e chemical identification of
s u b m i c r o m e t e r s e c o n d - p h a s e particles w h i c h c a n sig-
xxi
Introduction
DPS
Ions
^/^r
Electrons
Electrons
N
Photons
N ^ P h o t o n s
Photons
Electrons
^^^^^^Photons
X - r a y fluorescence (XRF)
Figure 1
Analytical methods: probes and responses
nificantly influence t h e p r o p e r t i e s of h i g h - t e m p e r a t u r e
alloys, t h e d e t e r m i n a t i o n of p o l l u t a n t s a t t h e p a r t s p e r
billion level a n d t h e c h a r a c t e r i z a t i o n of a few a t o m i c
layers o n the surface of a catalyst. Clearly, scientists
a n d engineers h a v e e n o u g h difficulty in k e e p i n g u p
with a d v a n c e s in their o w n fields w i t h o u t h a v i n g t o be
materials c h a r a c t e r i z a t i o n experts. H o w e v e r , it is es
sential t o h a v e e n o u g h basic u n d e r s t a n d i n g of cur
rently used analytical m e t h o d s t o be able t o i n t e r a c t
effectively with such experts.
Materials
mass spectrometry
gas and liquid chromatography
scanning and transmission electron microscopy
nuclear magnetic resonance spectrometry
optical emission and absorption spectrometry
x-ray diffraction and fluorescence spectrometry
Auger and x-ray photoelectron spectrometry
scanning tunnelling and scanning force microscopy
O t h e r t e c h n i q u e s e m p l o y i n g c o m m e r c i a l l y available
e q u i p m e n t w h i c h a r e s o m e w h a t less c o m m o n l y used
a l t h o u g h often i m p o r t a n t include:
low-energy electron diffraction
secondary-ion mass spectrometry
Raman spectrometry
low-energy ion scattering spectrometry
field-ion microscopy and atom-probe analysis
electron spin resonance spectrometry
Mossbauer spectrometry
laser microprobe analysis
acoustic microscopy
quantititave image analysis
W h a t m u s t be recognized also is t h a t even if a welle q u i p p e d analytical l a b o r a t o r y h a s all t h e specialties
listed in t h e first c a t e g o r y , e a c h of t h e m e t h o d s c a n b e
substantially s u b d i v i d e d , r e q u i r i n g s e p a r a t e instru
m e n t s a n d often s e p a r a t e skills. T a k i n g x-ray diffrac
tion as a n e x a m p l e , t h e following subdivision c a n
easily b e m a d e :
conventional diffractometry
high- and low-temperature diffractometry
back-reflection and transmission Laue photography
residual stress measurement
single-crystal structure determination
pole figure determination
double-crystal diffractometry
microdiffraction
Debye-Scherrer and Guinier powder photography
Berg-Barrett and Lang topography measurements
Services n o t readily available i n - h o u s e c a n often b e
p u r c h a s e d externally from general analytical l a b o r a
tories o r specialists in s o m e of t h e a b o v e m e t h o d s .
Introduction
This a p p r o a c h is p a r t i c u l a r l y useful w h e n t h e n u m b e r
of samples d o e s n o t justify setting u p a n i n - h o u s e
facility o r if i n - h o u s e facilities a r e severely over
loaded. N o single l a b o r a t o r y c a n possess e v e r y t h i n g
a n d the use of external a n a l y s t s often p r o v i d e s a n
effective w a y of p r o v i d i n g n e e d e d resources. I n s o m e
cases, t h e use of e x t e r n a l l a b o r a t o r i e s is t h e only
a p p r o a c h w h e n t h e i n s t r u m e n t a t i o n r e q u i r e d is in t h e
multimillion d o l l a r price r a n g e a n d large s u p p o r t
staffs a r e needed. E x a m p l e s of such specialized facili
ties include:
extended x-ray absorption fine structure measurements
(using synchrotron radiation)
neutron activation analysis
carbon-14 dating
picosecond laser fluorescence spectrometry
neutron activation spectrometry
high-voltage transmission electron microscopy
Rutherford backscattering and ion-channelling spec
trometry
proton-excited x-ray fluorescence
T h e r e a r e o t h e r factors in a d d i t i o n t o cost a n d
speed of analysis t h a t s h o u l d b e c o n s i d e r e d in t h e
decision t o use i n - h o u s e o r external facilities. I n a n
industrial e n v i r o n m e n t , p r o p r i e t a r y c o n c e r n s often
limit s a m p l e d i s t r i b u t i o n . A n o t h e r i m p o r t a n t factor is
the n a t u r e of t h e i n t e r a c t i o n b e t w e e n t h e a n a l y s t a n d
the research scientist o r engineer. I n t h o s e cases w h e r e
the specific t y p e of analysis n e e d e d is k n o w n a n d t h e
right s a m p l e h a s been selected, it m a y be q u i t e satis
factory t o send a s a m p l e several t h o u s a n d k i l o m e t e r s
a n d receive t h e results in a few weeks. H o w e v e r , in
o t h e r cases a m u c h h i g h e r degree of i n t e r a c t i o n m a y
lead m o r e r a p i d l y t o m e a n i n g f u l results. T h i s is p a r
ticularly t r u e if t h e t e c h n i q u e o r t h e s a m p l e selected
h a s t o be c h a n g e d b e c a u s e t h e initial a p p r o a c h is
unsuccessful. It c a n also b e t r u e if detailed d a t a
i n t e r p r e t a t i o n relative t o t h e objectives of t h e overall
investigation is r e q u i r e d .
S o m e t i m e s t h e q u e s t i o n of w h o s h o u l d d o t h e
analysis b e c o m e s a n i n t e r n a l o n e . S h o u l d scientists o r
engineers h a v e their o w n c h a r a c t e r i z a t i o n tools o r
s h o u l d they use a centralized service? W h i l e t h e r e is n o
single a n s w e r t o this q u e s t i o n , it is clearly a n issue of
optimizing t h e utilization of resources. It is n o t
u n c o m m o n for every chemist in a l a b o r a t o r y t o h a v e
his o w n gas o r liquid c h r o m a t o g r a p h a n d every
metallurgist t o h a v e his o w n light optical m i c r o s c o p e .
In such cases a n i n v e s t m e n t of a few t h o u s a n d d o l l a r s
could i m p r o v e research p r o d u c t i v i t y b y p r o v i d i n g
quick a n s w e r s expediting t h e next e x p e r i m e n t . It is
highly unlikely, h o w e v e r , t h a t e a c h chemist w o u l d
have a p r i v a t e n u c l e a r m a g n e t i c r e s o n a n c e spec
t r o m e t e r a n d e a c h metallurgist a s e p a r a t e t r a n s m i s
sion electron m i c r o s c o p e . T h e s e r e q u i r e very large
initial capital as well as t h e e x p e n d i t u r e of b o t h
m o n e y a n d time t o a c q u i r e t h e n e e d e d expertise a n d
to m a i n t a i n a piece of e q u i p m e n t t h a t m a y n o t even
h a v e a l o n g - t e r m use. O b v i o u s l y t h e overall i m p a c t
3. Interaction
with the
Analyst
G i v e n h u n d r e d s of analytical m e t h o d s , it is o b v i o u s t o
a s k h o w is a n a p p r o p r i a t e m e t h o d selected for solving
a given p r o b l e m ? Before t h e recent proliferation of so
m a n y n e w types of analytical i n s t r u m e n t s , a scientist
o r engineer w o u l d g o t o a d e s i g n a t e d analytical
chemist in his o r g a n i z a t i o n a n d describe the i n f o r m a
tion n e e d e d . T h e analytical chemist w o u l d either g o t o
suitable references o r k n o w i m m e d i a t e l y from per
s o n a l experience w h i c h t e c h n i q u e t o use. T o d a y this
d i a l o g u e c o u l d be c o n s i d e r a b l y e x t e n d e d a n d w o u l d
u n d o u b t e d l y involve experts in several fields. T h e
scientist o r engineer initiating t h e s t u d y s h o u l d b e
p r e p a r e d t o a n s w e r a n u m b e r of q u e s t i o n s which will
aid in establishing t h e m e t h o d o r m e t h o d s m o s t
suitable for solving t h e p r o b l e m . T h e following is a
list of representative q u e s t i o n s frequently a s k e d ,
s e p a r a t e d i n t o t h r e e general categories. I n a d d i t i o n
s o m e c o m m e n t s a r e a d d e d which s h o u l d h e l p t o
u n d e r s t a n d t h e role of these categories in establishing
a n analytical strategy. If t h e scientist o r engineer a n d
t h e m a t e r i a l s a n a l y s t a r e , in fact, t h e s a m e p e r s o n , the
discussion is replaced b y i n t r o s p e c t i o n b u t t h e q u e s
tions remain the same.
(a)
Q u e s t i o n s relating t o t h e t y p e a n d detail of
information sought:
Is t h e r e a need t o k n o w w h a t elements a r e p r e s e n t
a n d / o r h o w m u c h of each?
Is t h e r e a need t o k n o w all the elements o r only
s o m e of t h e m ?
D o w n t o w h a t level?
W h a t degree of a c c u r a c y is r e q u i r e d in the
results?
Is crystal s t r u c t u r e o r m i c r o s t r u c t u r a l i n f o r m a
tion n e e d e d ?
xxiii
Introduction
(b)
Q u e s t i o n s relating t o w h a t is a l r e a d y k n o w n
a b o u t the s a m p l e :
W h a t is the physical state of the sample?
Is the s a m p l e a m e t a l , c e r a m i c , s e m i c o n d u c t o r ,
chemical c o m p o u n d s o r p o l y m e r ?
D o e s t h e s a m p l e consist of o n e o r m o r e t h a n o n e
phase?
Is the s a m p l e a m o r p h o u s o r crystalline?
Is s a m p l e h a n d l i n g of t h e s a m p l e r e q u i r e d , either
because of toxicity o r because t h e s a m p l e m i g h t
t r a n s f o r m t o s o m e t h i n g different before o r d u r
ing analysis?
W a s t h e s a m p l e (or its source) e x p o s e d t o a n y
u n u s u a l physical o r chemical c o n d i t i o n s w h i c h
m i g h t h a v e altered its c o m p o s i t i o n o r m i c r o structure?
D o e s t h e s a m p l e consist of layers a n d , if it d o e s ,
h o w m a n y a r e there a n d h o w thick a r e they?
H o w m u c h of each s a m p l e is t h e r e a n d h o w m a n y
samples a r e t o be r u n ?
(c)
Q u e s t i o n s relating t o the w o r k i n g r e l a t i o n s h i p
between t h e analyst a n d t h e scientist o r engineer:
H o w s o o n a r e results needed?
H o w m u c h c a n be spent t o o b t a i n t h e results?
Is y o u r presence n e e d e d d u r i n g the analysis?
Is a detailed r e p o r t o n t h e results needed?
A r e the samples p r o p r i e t a r y ?
(ii)
xxiv
a Sample
and a
Method
T h e q u a l i t y of a n analysis c a n be n o b e t t e r t h a n t h a t
d e t e r m i n e d b y t h e s a m p l e o n w h i c h t h e analysis is
p e r f o r m e d . I n t r a c e level d e t e r m i n a t i o n , a s a m p l e c a n
easily b e c o n t a m i n a t e d b y h a n d l i n g o r b y t h e use of
u n c l e a n glassware o r o t h e r l a b o r a t o r y supplies. S a m
ples c a n also b e affected b y e x p o s u r e t o t h e a t m o s
p h e r e , a s in t h e case of h y g r o s c o p i c m a t e r i a l s o r
h y d r o c a r b o n b u i l d u p o n a s a m p l e t o be studied b y
surface analysis t e c h n i q u e s . M a t e r i a l s a r e also n o t
always as h o m o g e n e o u s as expected. If a m e t h o d is
used with a precision of 1 % b u t the c o m p o s i t i o n
of a r a n d o m l y picked s a m p l e varies b y 1 0 % ,
obviously t h e s a m p l i n g e r r o r will d o m i n a t e . T h i s
effect c a n t a k e place a t either the m a c r o s c a l e o r t h e
microscale. I n o t h e r w o r d s , a 1 k g s a m p l e t a k e n from
a single l o c a t i o n in a t a n k c a r c a n lead t o t h e s a m e
m a g n i t u d e of e r r o r in assessing t h e overall c o n t e n t s of
t h e c a r as using a 1 n g m i c r o p r o b e m e a s u r e m e n t t o
d e t e r m i n e t h e c o m p o s i t i o n of a highly segregated
alloy ingot.
Collecting s a m p l e s from e n o u g h regions of t h e
m a t e r i a l t o be a n a l y z e d t o d e t e r m i n e its h o m o g e n e i t y
a n d / o r a v e r a g e c o m p o s i t i o n is a n essential p a r t of
c h a r a c t e r i z a t i o n m e a s u r e m e n t s . If t h e m e t h o d of
Introduction
analysis t o b e used in a p a r t i c u l a r p r o b l e m is k n o w n
in a d v a n c e , as in t h e case of a research e x p e r i m e n t ,
samples s h o u l d b e p r e p a r e d so t h a t t h e y a r e truly
representative of t h e p r o b l e m a n d also of t h e p r o p e r
size a n d g e o m e t r y t o b e c o m p a t i b l e w i t h t h e m e t h o d
to b e used. F o r m o s t m e t h o d s t h e r e is s o m e c o r r e l a
tion b e t w e e n s a m p l e size, sensitivity, a c c u r a c y a n d
precision. S i t u a t i o n s w h e r e t h e a m o u n t of s a m p l e is
limited a r e frequently e n c o u n t e r e d , h o w e v e r , a n d in
these cases t h e q u a n t i t y of s a m p l e m a y strongly
influence t h e analytical m e t h o d selected a n d m i n i
m u m detectability limits. C o n s i d e r t h e following:
a geologist working in an inaccessible location gathering
samples to map out its mineral content
a forensic scientist working with only a small piece of
evidence
a metallurgical failure analysis expert working with a
fragment of a broken device
a research chemist or metallurgist developing a new
material in which it is important to explore hundreds of
variations of composition and/or phase distribution
T h e r e a r e also times w h e n a n a b u n d a n t a m o u n t of
s a m p l e is available b u t either t h e c o n c e n t r a t i o n levels
sought by a particular instrumental method are too
low t o detect b e c a u s e of m a x i m u m a c c e p t a b l e s a m p l e
size limitations, o r interferences from o t h e r c o n s t i
t u e n t s c a n i n t r o d u c e serious e r r o r s in t h e analysis. I n
such s i t u a t i o n s , d e t e r m i n i n g w h e t h e r t h e c o m p o n e n t
of interest ( p h a s e o r e l e m e n t ) is dispersed h o m o g e
neously t h r o u g h o u t t h e s a m p l e o r is n o n u n i f o r m l y
d i s t r i b u t e d is i m p o r t a n t n o t o n l y from t h e s a m p l i n g
p o i n t of view b u t also a s a m e a n s of selecting a
t e c h n i q u e t o give e n h a n c e d localized analysis for
i n h o m o g e n e o u s s a m p l e s . Being able t o detect 1 n g of
m a t e r i a l in a 1 g s a m p l e is a real challenge for a n y
b u l k analysis t e c h n i q u e b u t is very simple b y electron
m i c r o p r o b e analysis if t h e relevant l o c a t i o n is k n o w n .
In t h e case of solids, this c a n often b e d o n e b y
m i c r o s c o p i c e x a m i n a t i o n of t h e s a m p l e either a s it is
o r specially p r e p a r e d t o e n h a n c e p h a s e differences.
W h e n possible, c o n v e n t i o n a l light m i c r o s c o p y s h o u l d
always b e tried first. L o w - m a g n i f i c a t i o n o b s e r v a t i o n
of a n unmodified s a m p l e often reveals w h e t h e r a
s a m p l e is n o n u n i f o r m . If t h e s a m p l e consists of p a r t i
cles o b s e r v a b l e u n d e r a l o w - p o w e r b i n o c u l a r m i c r o
scope, they c a n often b e s e p a r a t e d for easier analysis
by a variety of m e t h o d s i n c l u d i n g s e d i m e n t a t i o n ,
m a g n e t i c s e p a r a t i o n o r even h a n d selection w i t h
tweezers.
If magnifications a b o v e ~ 100 a r e n e e d e d a n d t h e
s a m p l e consists of discrete particles, s c a n n i n g electron
m i c r o s c o p y is usually a b e t t e r a p p r o a c h . H o w e v e r ,
since t h e a t t r i b u t e of c o l o r is n o t available, differences
between particles t e n d t o b e b a s e d o n m o r p h o l o g y
a n d , in s o m e cases, o n a t o m i c - n u m b e r - d e p e n d e n t
electron b a c k s c a t t e r i n g . F u r t h e r m o r e , since particles
smaller t h a n a few tens of 1 a r e difficult t o h a n d l e ,
the analysis m a y h a v e t o be d o n e in situ u s i n g energydispersive x-ray s p e c t r o s c o p y . T h i s m e t h o d p r i m a r i l y
p r o v i d e s q u a l i t i t a v e elemental analysis a n d c a n be
a p p l i e d t o p a r t i c u l a t e s u s i n g magnifications u p t o
a b o u t 5000 if t h e particles a r e well s e p a r a t e d . Light
m i c r o s c o p y is used in t h e magnification r a n g e of
~ 100-2000 x p r i m a r i l y t o e x a m i n e polished sections
b y reflection for o p a q u e m a t e r i a l s o r t r a n s m i s s i o n for
transparent materials.
W h i l e s o m e chemical i n f o r m a t i o n is o b t a i n a b l e b y
p o l a r i z e d light a n d refractive index m e a s u r e m e n t s , the
presence of multiple p h a s e s m a y indicate t h a t t h e
s a m p l e s h o u l d be a n a l y z e d either b y a high-spatialr e s o l u t i o n i n s t r u m e n t a l m e t h o d , like electron m i c r o p r o b e analysis, o r infrared m i c r o s c o p y . Alternatively,
it m a y be necessary t o dissolve t h e s a m p l e m a t r i x so as
t o isolate s e c o n d - p h a s e particles for analysis b y o t h e r
t e c h n i q u e s . T h e t r a n s m i s s i o n electron m i c r o s c o p e
e x t e n d s t h e ability t o p e r f o r m c o m b i n e d m i c r o s t r u c t u r a l a n d m i c r o c h e m i c a l analysis t o magnifications
well a b o v e 5000 , b u t t h e complexities of specimen
p r e p a r a t i o n a n d t h e relatively high cost a n d inaccessi
bility o f this m e t h o d in m o s t l a b o r a t o r i e s , c o m p a r e d
with light a n d s c a n n i n g electron m i c r o s c o p y , t e n d t o
m a k e it a m e t h o d w h i c h is c h o s e n only w h e n the o t h e r
m e t h o d s a r e unsuccessful.
If b y m i c r o s c o p i c e x a m i n a t i o n t h e s a m p l e a p p e a r s
t o b e fairly h o m o g e n e o u s , t h e a d v a n t a g e s associated
with t h e spatial selectivity of m i c r o a n a l y s i s c a n n o t be
realized a n d v a r i o u s m e t h o d s of b u l k analysis a r e
p r o b a b l y m o r e suitable. I n a d d i t i o n t o t r a d i t i o n a l wet
c h e m i c a l analysis, these m e t h o d s i n c l u d e s p a r k - s o u r c e
m a s s s p e c t r o m e t r y , optical emission a n d a b s o r p t i o n
s p e c t r o m e t r y a n d x-ray fluorescence spectroscopy.
E a c h h a s a sensitivity e x t e n d i n g d o w n t o t h e p a r t s p e r
million level a n d , in s o m e cases, well below. In
a d d i t i o n , t h e optical a n d x-ray t e c h n i q u e s c a n b o t h be
m a d e q u a n t i t a t i v e w i t h relative ease. T h e s e techniques
c a n often be applied t o i n h o m o g e n e o u s samples,
p r o v i d e d t h a t n o b r e a k d o w n b y p h a s e s is r e q u i r e d .
F i g u r e s 2, 3 a n d 4 give a n a p p r o x i m a t e s u m m a r y of
t h e p e r f o r m a n c e of s o m e of t h e m e t h o d s described,
with r e g a r d t o their ability t o d e t e r m i n e p h a s e m o r
p h o l o g y , crystal s t r u c t u r e a n d elemental c o m p o s i t i o n ,
respectively.
T h e preceding comments about determining sam
ple h o m o g e n e i t y refer principally t o solid i n o r g a n i c
s a m p l e s , a l t h o u g h all t h e t e c h n i q u e s m e n t i o n e d c a n
b e used o n p o l y m e r s as well, w i t h i n certain limitations
associated with v a c u u m a n d electron b e a m c o m p a t i
bility r e q u i r e m e n t s o f t h e electron m i c r o s c o p i c m e t h
o d s . F u r t h e r m o r e , x-ray fluorescence m e a s u r e m e n t s
a r e p r i m a r i l y c o n c e r n e d with elemental analysis
r a t h e r t h a n c o m p o u n d identification. Since c a r b o n ,
h y d r o g e n , n i t r o g e n a n d oxygen a r e u b i q u i t o u s in
o r g a n i c m a t e r i a l s , q u a l i t a t i v e e l e m e n t a l analysis by xr a y t e c h n i q u e s ( h y d r o g e n is u n d e t e c t a b l e by these
m e t h o d s ) d o e s little t o aid in t h e identification of t h e
m a t e r i a l o t h e r t h a n t o s h o w t h a t it is o r g a n i c . D e t e r
m i n i n g w h e t h e r a n o r g a n i c s a m p l e consists o f o n e o r
m o r e p h a s e s o r c o m p o u n d s is also a n i m p o r t a n t issue,
XXV
introduction
XRF
100 /xm
+3
">
g>
IR
xray
SEM
XRD~|
EPM
I
QL
LM
AEM
&
AEM
||
/iRBS
RBS
RBS
SIMS
STM/AFM
S T M / A F M "! A E S
0.1 n m '
10 n m
I \
100 \
Lateral resolution
I cm
0.1 n m
ESCA
10 n m
I /xm
100 ,
Lateral resolution
Figure 2
Lateral and depth resolution comparison for the methods
indicated in Fig. 1 used for studying morphology
Figure 4
Lateral and depth resolution comparison for the methods
indicated in Fig. 1 used for elemental analysis
however, b u t t h e types of s a m p l e s , t h e s e p a r a t i o n
techniques used a n d t h e k i n d s of i n f o r m a t i o n r e q u i r e d
c a n differ c o n s i d e r a b l y from t h o s e associated with t h e
e x a m i n a t i o n of i n o r g a n i c samples. First of all, m o s t
samples a r e either s u b m i t t e d as s o l u t i o n s o r a r e t a k e n
u p i n t o s o l u t i o n before analysis. S e p a r a t i o n s a r e
usually achieved b y s o l u t i o n chemistry, solvent
extraction o r c h r o m a t o g r a p h y (gas o r liquid). Separ
ated fractions a r e either a n a l y z e d b y direct i n t r o d u c
tion i n t o a physically c o u p l e d i n s t r u m e n t like a m a s s
o r infrared s p e c t r o m e t e r o r a r e collected a n d t r a n s
ferred t o a n o t h e r location for analysis. If t h e s a m p l e is
a p o l y m e r of only o n e type, t h e i n f o r m a t i o n s o u g h t
m a y be m o l e c u l a r weight d i s t r i b u t i o n a n d c h r o m a t o
g r a p h y (gel p e r m e a t i o n ) m a y be all t h a t is required. I n
o t h e r cases t h e i n f o r m a t i o n n e e d e d is t h e s t r u c t u r a l
f o r m u l a . T h i s c o u l d be d e t e r m i n e d from i n f o r m a t i o n
o b t a i n e d b y a variety of m e t h o d s including m a s s
s p e c t r o m e t r y , infrared s p e c t r o s c o p y a n d n u c l e a r m a g
netic r e s o n a n c e , as well as b y t r a d i t i o n a l c a r b o n ,
h y d r o g e n a n d o x y g e n analysis b a s e d o n c o m b u s t i o n
a n d gas a b s o r p t i o n . T h e s a m p l e size a n d c o n c e n t r a
tion r e q u i r e d a g a i n b e c o m e a n issue, b e c a u s e t h e
characteristics of t h e v a r i o u s t e c h n i q u e s differ
b r o a d l y . W h i l e n u c l e a r m a g n e t i c r e s o n a n c e is excel
lent for s t r u c t u r e d e t e r m i n a t i o n , it requires larger
samples than the other methods mentioned and can
rarely detect c o m p o u n d s o r functional g r o u p s a t a
c o n c e n t r a t i o n level less t h a n 0 . 1 % . O r g a n i c m a s s
s p e c t r o m e t r y , o n t h e o t h e r h a n d , c a n w o r k with m u c h
smaller s a m p l e s a n d detect c o m p o u n d s even below
t h e p a r t s p e r billion level in a well-separated s a m p l e .
S t r u c t u r a l i n f o r m a t i o n is h a r d e r t o o b t a i n , h o w e v e r ,
a n d c o m p o u n d s w i t h h i g h m o l e c u l a r weights ( > 2000)
a r e difficult t o a n a l y z e b y c o n v e n t i o n a l m e a n s . W i t h
systems of sufficiently high r e s o l u t i o n a n d soft ioniza
tion sources, it is possible t o o b t a i n m o l e c u l a r i o n s
a n d d e t e r m i n e s t o i c h i o m e t r y b a s e d o n direct p a c k i n g
fraction m e a s u r e m e n t s . I n s o m e cases, s t r u c t u r e c a n
also b e d e t e r m i n e d using c o n v e n t i o n a l electron
impact ionization and comparing fragmentation pat
tern spectra with t h o s e of k n o w n c o m p o u n d s .
Infrared s p e c t r o s c o p y c a n also h a v e relatively high
sensitivity t o specific functional g r o u p s a n d c a n b e
used t o e x a m i n e relatively small s a m p l e s , a l t h o u g h
larger o n e s a r e preferred for higher sensitivity. It is
used m o r e effectively in relating t h e s p e c t r u m of a n
u n k n o w n s a m p l e t o a reference s p e c t r u m r a t h e r t h a n
as a m e a n s of d e t e r m i n i n g t h e s t r u c t u r e of a c o m p l e t e
u n k n o w n . O f p a r t i c u l a r value is t h e fact t h a t it c a n be
r o u t i n e l y used t o e x a m i n e solid s a m p l e s s u c h a s
crosslinked insoluble p o l y m e r s .
XRD
100
SEM
\ |
XRD
AEM
RBS
I LEED
STM/AFM
0.1 n m
10 n m
I ,
100
I cm
Lateral resolution
Figure 3
Lateral and depth resolution comparison for the methods
indicated in Fig. 1 used for obtaining crystal structure
information
xxvi
Introduction
5. Cost and
Complexity
T h e r e c a n b e a n e n o r m o u s r a n g e in t h e costs associ
ated with m a t e r i a l s c h a r a c t e r i z a t i o n , d e p e n d i n g o n
the complexity of t h e p r o b l e m , t h e a m o u n t of infor
m a t i o n s o u g h t , t h e n u m b e r of s a m p l e s t o b e r u n , h o w
quickly t h e analysis h a s t o b e d o n e a n d t h e i n v e s t m e n t
in e q u i p m e n t a n d m a n p o w e r . M u l t i e l e m e n t analysis
for large n u m b e r s of r o u t i n e s a m p l e s c a n b e effected
for less t h a n U S $ 2 5 p e r s a m p l e , while c o m p l e x surface
analysis c a n exceed U S $ 1 0 0 0 p e r s a m p l e . Access t o a
p a r t i c u l a r t y p e of i n s t r u m e n t a t i o n of t h e types d e
scribed so far d o e s n o t p r o v i d e all t h e i n f o r m a t i o n
needed a b o u t w h e t h e r a given t e c h n i q u e will h a v e t h e
sensitivity, r e s o l u t i o n o r s a m p l e h a n d l i n g c a p a b i l i t y
t o d o a given j o b . It is possible t o p u r c h a s e c o m p l e t e
m a s s s p e c t r o m e t e r systems for u n d e r U S $ 5 0 0 0 o r
over U S $ 5 0 0 000. W h i l e t h e f o r m e r m a y b e perfectly
a d e q u a t e as a residual g a s a n a l y z e r w h e r e u n i t m a s s
resolution is sufficient, it w o u l d b e totally unsatisfac
t o r y for t h e analysis of h i g h - m o l e c u l a r - w e i g h t o r g a n i c
c o m p o u n d s . E v e n if t h e larger s u m of m o n e y w e r e
available, a h i g h - r e s o l u t i o n m a s s s p e c t r o m e t e r for
isotopic analysis w o u l d b e decidedly different from
o n e used for c o m b i n e d gas c h r o m a t o g r a p h y m a s s
spectrometry.
T h e trade-off b e t w e e n cost a n d p e r f o r m a n c e
features is characteristic of all m a j o r pieces of a n a l y t i
cal i n s t r u m e n t a t i o n . T o deal effectively w i t h this issue
w h e n selecting a n i n s t r u m e n t t o p u r c h a s e o r use for a
given a p p l i c a t i o n r e q u i r e s t h e d e v e l o p m e n t of a speci
fication
for i n s t r u m e n t p e r f o r m a n c e relative t o
i n t e n d e d use. A g a i n t a k i n g m a s s s p e c t r o m e t r y a s a n
e x a m p l e , if t h e need is for high-sensitivity, h i g h resolution analysis of g a s c h r o m a t o g r a p h effluents, a n
i n s t r u m e n t m i g h t b e specified w i t h a highly efficient
electron i m p a c t s o u r c e c o u p l e d t o a fast-switching,
double-focusing a n a l y z e r w i t h high-sensitivity electri
cal detection. F u r t h e r m o r e , it s h o u l d also b e possible
t o specify a generally a c c e p t e d p e r f o r m a n c e s t a n d a r d .
F o r e x a m p l e , t h e i n s t r u m e n t s h o u l d be able t o detect
9
1 0 ~ C of i o n p e r g of m e t h y l s t e a r a t e a t a m a s s
resolution of 1 p a r t in 10 000 a n d a s o u r c e v o l t a g e of
8 k V . G e n e r a l l y , w h e n selecting a n i n s t r u m e n t of a n y
type, cost rises w i t h p e r f o r m a n c e . It is therefore
i n c u m b e n t o n t h e b u y e r t o b e realistic a b o u t h o w
m a n y special features a n d w h a t level of p e r f o r m a n c e
are n e e d e d for a given r a n g e of a p p l i c a t i o n s . It m a k e s
little sense t o p a y t h e a d d e d cost for a s c a n n i n g
electron m i c r o s c o p e c a p a b l e of 1 0 0 0 0 0 magnifica
tion relative t o a lower r e s o l u t i o n m o d e l if t h e details
of interest a r e clearly o b s e r v a b l e a t 5000 o r if t h e
n a t u r e of t h e s a m p l e is such t h a t p i c t u r e s a t h i g h e r
magnifications a r e n o t possible.
6.
Trends
T h e m a j o r i m p a c t of c o m p u t e r s a n d m i c r o e l e c t r o n i c s
on materials characterization techniques, already
a l l u d e d t o , will u n d o u b t e d l y c o n t i n u e for a n u m b e r of
years. I n a d d i t i o n t o i n s t r u m e n t c o n t r o l , d a t a collec
t i o n a n d t h e p r o c e s s i n g of results, c o m p u t e r s will p l a y
a m o r e i m p o r t a n t role in m e t h o d selection a n d the
m a n a g e m e n t of l a b o r a t o r y i n f o r m a t i o n . It c a n be
expected t h a t m o r e general spectral d a t a b a s e s a n d
efficient m e a n s for s e a r c h i n g t h e m will lead b o t h t o
faster a n d t o m o r e c o m p l e t e results. Since specimen
p r e p a r a t i o n is often a rate-limiting step in m a n y
f o r m s of analysis, l a b o r a t o r y r o b o t s a r e n o w being
used m o r e extensively t o also i m p r o v e q u a l i t y a n d
productivity.
I n very general t e r m s , m o s t analytical i n s t r u m e n t s
c a n b e t h o u g h t of as consisting of a source, a n
a n a l y z e r a n d a d e t e c t o r . A s w a s s h o w n in Fig. 1, the
s o u r c e c a n b e used o n t h e i n t e r a c t i o n of the s a m p l e
w i t h p r o b i n g r a d i a t i o n of a n y w a v e l e n g t h o r particles
of different types a n d energies. It m a y even be the
specimen itself, as in t h e case of the analysis of
r a d i o a c t i v e s a m p l e s . T h e a n a l y z e r serves as a m e a n s
of s e p a r a t i n g t h e signals e m i t t e d o r scattered b y t h e
s a m p l e , b a s e d o n differences in their physical o r
chemical p r o p e r t i e s , a n d finally t h e d e t e c t o r c o n v e r t s
t h e s e p a r a t e d signals i n t o a c o m p r e h e n s i b l e form. A
m a j o r t r e n d , w h i c h e m e r g e d d u r i n g t h e 1980s, is t o try
all m a n n e r of c o m b i n a t i o n s of sources, analyzers a n d
d e t e c t o r s a n d t h e r e b y c r e a t e i n s t r u m e n t s which a r e
o p t i m i z e d for p a r t i c u l a r a p p l i c a t i o n s . I n o r g a n i c m a s s
s p e c t r o m e t r y , for e x a m p l e , ion sources a r e b a s e d o n
e l e c t r o n i m p a c t , field i o n i z a t i o n , field d e s o r p t i o n ,
laser i o n i z a t i o n a n d b o t h ion a n d n e u t r a l particle
b e a m s . I n gas c h r o m a t o g r a p h y , d e t e c t o r s include
flame i o n i z a t i o n , electron c a p t u r e , t h e r m a l c o n d u c
tivity a n d infrared s p e c t r o m e t r y .
If t h e s a m p l e is o n l y p a r t l y c o n s u m e d o r n o t
c o n s u m e d a t all b y a given d e t e c t i o n process, multiple
d e t e c t o r s c a n b e u s e d in series t o p r o v i d e c o m p l e m e n
t a r y i n f o r m a t i o n . T h i s h a s b e e n d o n e in b o t h gas a n d
liquid c h r o m a t o g r a p h y . S o m e t i m e s t h e d e t e c t o r is
itself a s p e c t r o m e t e r a n d t h u s allows s e p a r a t e d species
t o b e c h a r a c t e r i z e d m o r e fully. E x a m p l e s include gas
a n d liquid c h r o m a t o g r a p h y - m a s s s p e c t r o m e t r y a n d
b o t h g a s a n d liquid c h r o m a t o g r a p h y - i n f r a r e d spec
t r o m e t r y . A n i m p o r t a n t c h a r a c t e r i s t i c of s p e c t r o m e t r i c d e t e c t o r s used in c o m b i n a t i o n m e t h o d s is t h a t
they m u s t either b e very fast o r function in a parallel
d e t e c t i o n m o d e . T h u s , in t h e e x a m p l e s j u s t m e n
t i o n e d , a m a s s s p e c t r o m e t e r c a p a b l e of s c a n n i n g its
c o m p l e t e m a s s r a n g e in a few s e c o n d s is used in o n e
case a n d F o u r i e r t r a n s f o r m infrared s p e c t r o m e t r y in
t h e o t h e r . If s e p a r a t i o n t e c h n i q u e s a r e t o b e used with
a t o m i c emission t e c h n i q u e s , s o m e of t h e newly
d e v e l o p e d types of parallel d e t e c t i o n optical spec
t r o m e t e r s will p r o v e very v a l u a b l e . I n o t h e r analytical
s i t u a t i o n s , several d e t e c t o r s c a p a b l e of m o n i t o r i n g a
variety of signals a r e used a t t h e s a m e time. F o r
e x a m p l e , s i m u l t a n e o u s x-ray a n d electron d e t e c t i o n in
s c a n n i n g electron m i c r o s c o p e s a n d analytical t r a n s
mission electron m i c r o s c o p e s m a k e s it possible t o
xxvii
Introduction
relate chemical t o m i c r o s t r u c t u r a l i n f o r m a t i o n easily.
It is always difficult t o predict w h e r e a n y field will
go in t h e future, b u t clearly defined needs c o u p l e d
with active technologies c a n p r o v i d e s o m e h i n t s . All
analytical m e t h o d s s h a r e the c o m m o n goals of h i g h e r
speed, lower cost, g r e a t e r sensitivity, m o r e flexibility
a n d increased a c c u r a c y . Since t h e early 1970s, re
m a r k a b l e p r o g r e s s h a s b e e n m a d e in a d v a n c i n g loca
lized elemental analysis capability t o t h e limit of
single-atom detection by a t o m - m i c r o p r o b e analysis
a n d u l t r a h i g h - r e s o l u t i o n s c a n n i n g t r a n s m i s s i o n elec
t r o n m i c r o s c o p y , a l t h o u g h only limited k i n d s of s a m
ple are suitable for these m e t h o d s . A t o m i c r e s o l u t i o n
c h a r a c t e r i z a t i o n of surfaces is n o w possible as a result
of recent d e v e l o p m e n t of t h e s c a n n i n g tunnelling a n d
s c a n n i n g force m i c r o s c o p e s ( S T M a n d A F M ) . T h e s e
i n s t r u m e n t s p r o v i d e a relatively low-cost w a y of
i m a g i n g m a n y surfaces directly with a t o m i c resolu
tion. U n l i k e electron m i c r o s c o p e s they utilize very
fine physical p r o b e s a n d d o n o t need t o o p e r a t e
in a v a c u u m e n v i r o n m e n t . I n a d d i t i o n t o surface
m o r p h o l o g y c h a r a c t e r i z a t i o n , v a r i a t i o n s of t h e tech
n i q u e offer p r o m i s e in t h e m e a s u r e m e n t of localized
physical a n d chemical p r o p e r t i e s . T h e p o s i t i o n of
S T M / A F M t e c h n i q u e s in t h e lower left of Figs. 2 - 4 is
indicative of their high p o t e n t i a l t o e x p a n d t h e fron
tiers of m a t e r i a l s c h a r a c t e r i z a t o n . T h e r e is still a need,
however, for higher spatial resolution t e c h n i q u e s t h a t
can identify c o m p o u n d s , p a r t i c u l a r l y o r g a n i c s , since a
k n o w l e d g e of elemental c o n s t i t u e n t s is usually of little
value in distinguishing o n e m a t e r i a l from a n o t h e r .
Selected a r e a diffraction a n d , m o r e recently, m i c r o diffraction a r e routinely used t o identify i n o r g a n i c
c o m p o u n d s in t r a n s m i s s i o n electron m i c r o s c o p e s .
T h e newer m e t h o d h a s even given results from a r e a s
less t h a t 5 n m in d i a m e t e r . H o w e v e r , these a p p r o a c h e s
are of very limited value in t h e e x a m i n a t i o n of o r g a n i c
materials, because of electron b e a m d a m a g e a n d the
fact t h a t m a n y o r g a n i c s of interest a r e in a n o n c r y s t a l
line form.
T h e full c h a r a c t e r i z a t i o n of thin o r g a n i c films even
w h e n lateral spatial r e s o l u t i o n is n o t a n issue is
c o m p l i c a t e d for o t h e r r e a s o n s . X - r a y p h o t o e l e c t r o n
xxviii
s p e c t r o s c o p y h a s a l r e a d y p r o v e d itself t o b e a p o w e r
ful t o o l , b u t t h e chemical shift i n f o r m a t i o n c o n t a i n e d
in a s p e c t r u m is often difficult t o e x t r a c t b e c a u s e of
t h e i n h e r e n t energy r e s o l u t i o n limits of t h e t e c h n i q u e .
P e r h a p s o n e of t h e m o s t interesting a n d challenging
p r o b l e m s is t h e a t o m i c level c h a r a c t e r i z a t i o n of inter
faces w i t h i n m a t e r i a l s , w h e r e a n y a t t e m p t t o r e a c h
t h e interfaces by m a t e r i a l r e m o v a l , as is d o n e in
s e c o n d a r y - i o n m a s s s p e c t r o m e t r y a n d A u g e r electron
analysis, so alters t h e m as t o m a k e t h e i n f o r m a t i o n
o b t a i n e d useless. F o r these k i n d s of p r o b l e m s , n o n
destructive t e c h n i q u e s like solid-state n u c l e a r m a g
netic r e s o n a n c e a n d s o m e f o r m s of laser s p e c t r o s c o p y
may provide valuable solutions.
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Casper L A, Powell C J (eds.) 1982 Industrial Applications of
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Czandema A W (ed.) 1975 Methods of Surface Analysis.
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A
Acoustic Emission
A c o u s t i c emission ( A E ) is t h e t r a n s i e n t m e c h a n i c a l
v i b r a t i o n a c c o m p a n y i n g a s u d d e n release of s t o r e d
elastic energy o r chemical free energy. It o c c u r s a s a
c o n s e q u e n c e of t h e i m p o s i t i o n of e n v i r o n m e n t a l stress
o n m a t e r i a l s . T h e A E r e s p o n s e of a large n u m b e r of
m a t e r i a l s h a s been studied as a function of m e c h
anically, t h e r m a l l y o r chemically i n d u c e d stresses.
D e t e c t i o n , analysis a n d i n t e r p r e t a t i o n of A E from
m a t e r i a l s , p a r t s a n d s t r u c t u r e s forms t h e basis of
this n o n d e s t r u c t i v e e v a l u a t i o n ( N D E ) m e t h o d .
A E originates from a variety of s o u r c e s in m a t e r
ials. T h e s e include localized, r a p i d m o v e m e n t s of
m a t e r i a l , such a s initiation a n d p r o p a g a t i o n of c r a c k s ,
twinning, slip, m a r t e n s i t i c p h a s e t r a n s f o r m a t i o n s a n d
void coalescence. A n y similar d y n a m i c a n d localized
m o v e m e n t of m a t e r i a l will also act a s a n A E s o u r c e .
Processes t h a t o c c u r via a t o m - b y - a t o m diffusion a r e
n o t u s a b l e A E s o u r c e s . D i s l o c a t i o n m o t i o n s , except
for c o o p e r a t i v e m o t i o n of m a n y d i s l o c a t i o n s , a r e n o t
usable A E sources. M a t r i x c r a z i n g , fiber-matrix disb o n d i n g , fiber fracture a n d d e l a m i n a t i o n a r e sources
of A E in fiber c o m p o s i t e s .
A E sources t e n d t o be localized events in m a t e r i a l s .
A E precedes gross failure of t h e m a t e r i a l w h e n it is
used in a p a r t , c o m p o n e n t o r s t r u c t u r e a n d t h u s A E
c a n be a n effective N D E t o o l w h e n p r o p e r l y detected
and analyzed.
1. General
Features
of AE
Signals
A E signals a r e s t i m u l a t e d in m a t e r i a l s b y m e c h a n i c a l ,
t h e r m a l o r chemically i n d u c e d stresses. E a c h m a t e r i a l
exhibits its o w n u n i q u e A E r e s p o n s e characteristics.
H o w e v e r , t w o b r o a d types of A E r e s p o n s e c a n b e
described w h i c h serve as useful q u a l i t a t i v e descrip
tions: c o n t i n u o u s A E a n d b u r s t A E . C o n t i n u o u s A E
h a s w a v e f o r m s similar t o G a u s s i a n noise a n d is
generally associated w i t h t h e m o r e ductile m a t e r i a l s .
It c h a n g e s in a v e r a g e a m p l i t u d e , b u t n o t in general
a p p e a r a n c e , as t h e s t i m u l a t i o n p a r a m e t e r s of t h e
w o r k p i e c e being studied a r e c h a n g e d . It t e n d s t o s h o w
a large increase in a v e r a g e a m p l i t u d e w h e n a m a t e r i a l
yields, either locally o r in a gross fashion. C o n t i n u o u s
A E is believed t o b e m a d e u p of a large n u m b e r of
very small v i b r a t o r y t r a n s i e n t s , r a n d o m l y d i s t r i b u t e d
in time. B u r s t A E h a s larger a m p l i t u d e s a n d t h e b u r s t
events a r e sufficiently s e p a r a t e d in time t h a t they
a p p e a r t o b e discrete events. B u r s t A E is usually
observed w h e n brittle m a t e r i a l s o r m a t e r i a l s w i t h
brittle c o m p o n e n t s a r e b e i n g s t u d i e d . Stable c r a c k
g r o w t h in h i g h - s t r e n g t h steel a n d fiber fracture in
c o m p o s i t e s g e n e r a t e b u r s t A E . B u r s t A E is t h e m o r e
useful t y p e for N D E a p p l i c a t i o n s because it is m o r e
closely associated with processes t h a t c a n lead t o local
o r c a t a s t r o p h i c failure.
M a t e r i a l s in t h e m i d - r a n g e of ductility frequently
s h o w p r e d o m i n a n t l y c o n t i n u o u s A E a t low values of
s t i m u l a t i o n , t h e n b u r s t A E a p p e a r s as t h e s t i m u l a t i o n
increases a n d failure of t h e w o r k p i e c e a p p r o a c h e s .
M a t r i x crazing in c o m p o s i t e s frequently h a s the
a p p e a r a n c e of c o n t i n u o u s A E , w h e r e a s fiber fracture
produces burst A E .
2. Unique Features
of Acoustic-Emission
NDE
M o s t N D E m e t h o d s d e p e n d o n injecting a directed
b e a m of energy i n t o a m a t e r i a l . T h i s is t h e case, for
e x a m p l e , in t h e x-ray, u l t r a s o n i c , e d d y - c u r r e n t a n d
m i c r o w a v e m e t h o d s . A n analysis of t h e scattering,
a t t e n u a t i o n o r a b s o r p t i o n of t h e injected b e a m as it
interacts with a d i s c o n t i n u i t y in t h e m a t e r i a l is t h e n
r e q u i r e d in o r d e r t o describe t h e discontinuity, the
o u t p u t b e a m b e i n g received b y a n a p p r o p r i a t e sensor.
T h e m a t e r i a l of t h e w o r k p i e c e being studied plays a n
entirely passive role in this process, a l t h o u g h the
m a t e r i a l a n d its characteristic defect d i s t r i b u t i o n sig
nificantly influence t h e choice of N D E m e t h o d . T h e
s a m e f o r m of energy is received in e a c h of these cases
as is injected.
A E is s t i m u l a t e d by a n entirely different form of
energy t h a n is received a t t h e sensor for analysis. T h e
w o r k p i e c e m u s t h a v e m e c h a n i c a l stresses i n d u c e d i n t o
it either by m e c h a n i c a l , t h e r m a l o r chemical m e a n s .
A E , a n a c o u s t i c (usually u l t r a s o n i c ) t r a n s i e n t vibra
tion, is g e n e r a t e d w h e n a d i s c o n t i n u i t y s u d d e n l y re
leases all o r a p o r t i o n of t h e stress i n d u c e d i n t o it. T h e
m a t e r i a l , its d i s c o n t i n u i t y a n d t h e w o r k p i e c e geo
m e t r y d e t e r m i n e w h a t t h e o u t p u t signal will be. T h e
A E generated by a particular discontinuity under a
given set of s t i m u l a t i o n c o n d i t i o n s c o n t a i n s u n i q u e
information concerning the changes that occurred at
t h e d i s c o n t i n u i t y . N o t e t h a t it is only c h a n g e s t h a t c a n
be discerned with A E , t h u s it is a d y n a m i c N D E
m e t h o d , as well as being a m e t h o d t h a t is intensively
related t o t h e specific m a t e r i a l being tested.
A E h a s serious d i s a d v a n t a g e s as well as distinct
advantages when compared with other N D E meth
o d s . It c a n only detect discontinuities t h a t cause
a b r u p t c h a n g e s in their s u r r o u n d i n g stress fields as a
result of s t i m u l a t i o n . T h e s e discontinuities a r e very
likely t o be t h e m o s t serious o n e s in a p a r t i c u l a r
w o r k p i e c e , b u t large discontinuities t h a t a r e n o t
revealed b y a n A E test need t o be considered ser
iously, especially in t h e case of fatigue service. T h e
1
Acoustic
Emission
s t i m u l a t i o n r e q u i r e d m u s t be g r e a t e r t h a n t h a t
expected in service, t o e n s u r e t h a t existing disconti
nuities a r e n o t serious, even for static service. If
m e c h a n i c a l l o a d i n g is t h e s t i m u l a t i o n , for e x a m p l e ,
e q u i p m e n t foreign t o , a n d s o m e t i m e s u n a v a i l a b l e t o
N D E g r o u p s will b e r e q u i r e d . F u r t h e r m o r e , A E is
inferior t o o t h e r N D E m e t h o d s in its ability t o
describe t h e size a n d s h a p e of a discontinuity; x-ray
and ultrasonic methods are superior. However, A E
has the advantage that a discontinuity can be located
by using multiple sensors (as described in Sect. 4)
w i t h o u t a long, detailed a n d expensive search, if t h e
discontinuity is a n A E s o u r c e . A E c a n also detect
discontinuities t h a t a r e below t h e d e t e c t i o n limit of
o t h e r N D E m e t h o d s b y a t least a n o r d e r of m a g n i
t u d e ; a n e x a m p l e is t h e f o r m a t i o n of a c r a c k e m b r y o
d u e t o a b r e a k a w a y of a dislocation p i l e u p .
3. Analog-Instrumentation
Methods
4. Digital-Instrumentation
Methods
Acoustic
5. Unique Capabilities
Method
of the
Acoustic-Emission
A E inspection m e t h o d s c a n b e used in a n u m b e r of
situations w h e r e o t h e r N D E m e t h o d s w o u l d be p r o h i
bitively expensive o r totally impossible. I n these in
spection a p p l i c a t i o n s , t h e i n f o r m a t i o n w h i c h c a n b e
a c q u i r e d is n o t likely t o fulfill r e q u i r e m e n t s of existing
codes. In s o m e cases, n o such g u i d a n c e exists for a n y
N D E inspection m e t h o d . T h u s , n e w goals need t o be
set for t h e inspection a n d n e w p r o c e d u r e s need t o b e
established for i n t e r p r e t i n g t h e d a t a in m a n y cases.
A E c a n b e used t o m o n i t o r s t r u c t u r e s a n d m a c h i n e s
c o n t i n u o u s l y while they a r e in o p e r a t i o n a sig
nificant a d v a n t a g e for N D E . E x a m p l e s a r e s t e a m
turbines, electric g e n e r a t o r s , circulating p u m p s , p i p e
lines, valves, chemical p l a n t s , aircraft a n d offshore
p l a t f o r m s . Studies a r e in p r o g r e s s t o define p r o
cedures for c o m p r e h e n s i v e m o n i t o r i n g of n u c l e a r
reactors.
In-process m o n i t o r i n g of welds h a s also been per
fected as a n inspection m e t h o d . Electric-resistance,
percussion a n d t u b i n g - p i n c h welds c a n be q u a l i t y
assured a s they a r e m a d e . L a s e r welds c a n b e success
fully inspected as they a r e m a d e , a n d t h e t e c h n i q u e is
highly d e v e l o p e d for welding cables t o c o n n e c t o r s .
Successful m e t h o d s h a v e been d e v e l o p e d for inprocess inspection of welds in heavy-section steel,
w h e r e multiple passes of weld m a t e r i a l a r e laid d o w n .
T h e r e is a large cost a d v a n t a g e in detecting a b a d weld
u n d e r these c o n d i t i o n s , since t h e cost of r e m o v i n g
large a m o u n t s of m a t e r i a l t o r e p a i r t h e b a d weld p a s s
is saved.
In-process inspection of o t h e r m a n u f a c t u r i n g p r o
cesses, such as p u n c h i n g , m e t a l f o r m i n g a n d casting,
is u n d e r d e v e l o p m e n t .
Acknowledgement
T h e w o r k of t h e a u t h o r is p e r f o r m e d u n d e r t h e
auspices of t h e U S D e p a r t m e n t of E n e r g y , C o n t r a c t
No. W-7405-ENG-48.
See also: Wood: Acoustic Emission and Acousto-Ultrasonic
Characteristics
Emission
Bibliography
American Society for Testing and Materials 1981 Standard
definition of terms relating to acoustic emission, E610-77.
1981 Annual Book of AST Standards, Pt. 11: Metallo
graphy; Nondestructive Testing. ASTM, Philadelphia,
PA, pp. 603-5
American Society for Testing and Materials 1981 Standard
practice for acoustic emission monitoring during continu
ous welding, E749-80. 1981 Annual Book of ASTM Stan
dards, Pt. 11: Metallography; Nondestructive Testing,
ASTM, Philadelphia, PA, pp. 698-704
American Society for Testing and Materials 1981 Standard
practice for acoustic emission monitoring during resist
ance spot welding, E751-80. 1981 Annual Book of ASTM
Standards, Pt. 11: Metallography; Nondestructive Testing.
ASTM, Philadelphia, PA, pp. 716-24
American Society for Testing and Materials 1981 Standard
practice for measuring the operating characteristics of
acoustic emission instrumentation, E750-80. 1981 Annual
Book of ASTM Standards, Pt. 11: Metallography; Non
destructive Testing. ASTM, Philadelphia, PA, pp. 705-15
American Society for Testing and Materials 1981 Standard
practice for mounting piezoelectric acoustic emission con
tact sensors, E650-78. 1981 Annual Book of ASTM Stan
dards, Pt. 11: Metallography; Nondestructive Testing.
ASTM, Philadelphia, PA, pp. 606-8
American Society for Testing and Materials 1981 Standard
recommended practice for acoustic emission monitoring
of structures during controlled stimulation, E569-76.
1981 Annual Book of ASTM Standards, Pt. 11: Metallo
graphy; Nondestructive Testing. ASTM, Philadelphia,
PA, pp. 5 5 1 ^
Drouillard F, Laner F J 1979 Acoustic Emission: A
Bibliography with Abstracts. IFI Plenum Data Company,
New York
Dunegan L, Hartman W F (eds.) 1981 Advances in
Acoustic Emission. Dunhart, Knoxville, TN
Dunegan L, Tatro C A 1971 Acoustic emission effects
during mechanical deformation. In: Bunshah R F (ed.)
1981 Techniques of Metals Research, Vol. 5, Pt. 2. Interscience, New York, pp. 273-312
Hartman W F, McElroy J W (eds.) 1979 Acoustic Emission
Monitoring of Pressurized Systems, ASTM Special Tech
nical Publication 697. American Society for Testing and
Materials, Philadelphia, PA
Liptai R G, Harris D O, Tatro C A (eds.) 1972 Acoustic
Emission, ASTM Special Technical Publication 505. Am
erican Society for Testing and Materials, Philadelphia,
PA
Liptai R G, Tatro C A 1976 Acoustic emission inspection.
Metals Handbook, 8th edn., Vol. 11. ASM International,
Materials Park, OH
Nichols R W (ed.) 1976 Acoustic Emission. Applied Science,
Barking, UK
Spanner J C 1974 Acoustic Emission Techniques and Applica
tions. Intex, Evanston, IL
Spanner J C, McElroy J W (eds.) 1975 Monitoring Structural
Integrity by Acoustic Emission, ASTM Special Technical
Publication 571. American Society for Testing and
Materials, Philadelphia, PA
C. A . T a t r o
[Lawrence Livermore Laboratory,
L i v e r m o r e , California, U S A ]
Acoustic
Microscopy
Acoustic Microscopy
I n acoustic m i c r o s c o p y , magnified a c o u s t i c i m a g e s of
t h e elastic s t r u c t u r e of t h e surface o r interior of a solid
a r e p r o d u c e d b y p a s s i n g high-frequency focused
acoustic pulses t h r o u g h t h e m a t e r i a l a n d displaying
the received signals in i m a g e f o r m as s h a d e s of gray.
Usually, m u c h higher frequencies a r e used t h a n in
o t h e r k i n d s of a c o u s t i c i m a g i n g . T h e a c o u s t i c pulses
are focused directly, o r t h e energy used t o p r o d u c e t h e
pulses is focused i n t o a very small region. W h e n a
small a r e a of a specimen is s c a n n e d with a series of
focused pulses a n d t h e t r a n s m i t t e d o r reflected signals
are viewed o n a n i m a g i n g system (a television p i c t u r e
t u b e , a gray-scale r e c o r d e r o r s o m e o t h e r s c a n n e d
display), t h e magnification of t h e resulting i m a g e is
e q u a l t o t h e r a t i o of t h e d i a m e t e r of t h e display t o t h e
d i a m e t e r of t h e a r e a s c a n n e d . T h i s p r o c e d u r e is also
used in electron m i c r o s c o p y a n d s c a n n i n g electron
m i c r o s c o p y t o p r o d u c e magnified i m a g e s by s c a n n i n g
a finely focused b e a m of electrons.
A c o u s t i c m i c r o s c o p y h a s b e e n used successfully in
materials c h a r a c t e r i z a t i o n a n d d e v e l o p m e n t a s well as
in b i o m e d i c a l a p p l i c a t i o n s ( L e m o n s a n d Q u a t e 1979).
Because t h e d i s p l a c e m e n t a m p l i t u d e associated w i t h
p r o p a g a t i o n of high-frequency s o u n d waves is a t m o s t
a fraction of a n a n g s t r o m , a p o o r chemical b o n d
between t w o m a t e r i a l s is readily detected b y m o n i t o r
ing the reflectivity o r t r a n s m i s s i o n of signals a t t h e
interface. T h e cleanliness of h o m o g e n e o u s m a t e r i a l s ,
the integrity of large-scale i n t e g r a t e d circuits, t h e
a t t a c h m e n t of very t h i n films t o s u p p o r t i n g s u b
strates, a n d t h e integrity of s e m i c o n d u c t o r - h e a t - s i n k
b o n d s a r e also being e v a l u a t e d w i t h b o t h reflection
a n d t r a n s m i s s i o n acoustic m i c r o g r a p h s . A c o u s t i c sur
face w a v e interference i m a g e s a r e u s e d t o e x a m i n e
surface d e f o r m a t i o n c a u s e d , for e x a m p l e , b y a b r a
sion, w e a r a n d m a c h i n i n g a s well a s t h e g r a i n size of
m a t e r i a l s t h a t a r e difficult t o e x a m i n e optically. T h e
capability of a c o u s t i c m i c r o s c o p y t o i m a g e small
regions in w h i c h near-surface residual stresses h a v e
c h a n g e d t h e elastic p r o p e r t i e s of m a t e r i a l s h a s led t o
w o r k o n visualizing microstress fields. Because t h e
acoustic c o n t r a s t in biological specimens is often far
greater t h a n t h e optical c o n t r a s t , a c o n s i d e r a b l e b o d y
of w o r k h a s been directed t o w a r d t h e i m a g i n g of
cellular s t r u c t u r e , collagen a n d o t h e r biological
materials.
A t present, a c o u s t i c m i c r o s c o p y includes several
m e t h o d s for t h e f o r m a t i o n of magnified a c o u s t i c
images. T h e four discussed here a r e s c a n n i n g a c o u s t i c
m i c r o s c o p y , p h o t o a c o u s t i c m i c r o s c o p y , electron
acoustic m i c r o s c o p y a n d s c a n n i n g laser a c o u s t i c
microscopy.
1.
Background
I n 1936, t h e R u s s i a n physicist S o k o l o v i n t r o d u c e d a n
acoustic i m a g i n g device (the S o k o l o v t u b e ) w h i c h
2. Scanning
Acoustic
Microscopy
Acoustic
Sapphire
transmitter x
lens
Oscil lator
Microscopy
* +
,
Ps P uo tr smP | e
Receiving
transducer
Synchronization
(b)
Figure 1
Scanning acoustic microscopes: (a) pulse transmission and
(b) pulse-echo modes (courtesy of C. Quate and L. Lam,
Stanford University)
t r a n s d u c e r s h o r t e r a n d closer t o g e t h e r t h a n t h e lines
t h a t m a k e u p t h e i m a g e . C o n s i d e r , for e x a m p l e , a
1 m m x 1 m m a r e a t h a t is s c a n n e d b y m o v i n g a c o m
bined acoustic s o u r c e a n d receiver, e a c h focused t o
2 in d i a m e t e r over 500 lines t h a t a r e 1 m m l o n g
a n d spaced 2 a p a r t . W h e n t h e received sonic
signal is displayed in 500 equally spaced lines o n a
100 c m x 100 c m i m a g i n g screen, the result is a n
acoustic m i c r o g r a p h with a magnification of 1000 x .
A 5 cm x 5 c m s c a n n e d a r e a displayed o n the s a m e
100 c m x 100 c m screen generates a n acoustic m i c r o
g r a p h with a magnification of 20 x .
T h e p r i m a r y s t r e n g t h of t h e s c a n n i n g a c o u s t i c
m i c r o s c o p e design is its r e m a r k a b l e versatility. M i c r o
scopes c a n be c o n s t r u c t e d for use at a wide r a n g e of
frequencies for s c a n n i n g objects over a wide r a n g e of
sizes. A c o u s t i c images g e n e r a t e d by focused pulses
from 1 G H z t o 3 G H z typically scan a specimen a r e a
of 0.25 m m x 0.25 m m . T h e y p e n e t r a t e n o d e e p e r
t h a n 150 a n d t h e typical magnification is a p p r o x
imately 1000 x . F o r industrial acoustic images, it is
n o t u n u s u a l t o scan a n a r e a 15 c m x 15 c m with
10 M H z focused pulses, p e n e t r a t i n g t o a d e p t h of
5 cm o r m o r e a n d displaying t h e received signals a t
magnifications of 2 - 3 x .
Since the mid-1970s, m o s t of t h e S t a n f o r d w o r k h a s
been directed a t frequencies b e t w e e n 1 G H z a n d
Figure 2
Images of grain structure in Inconel: (a) optical image,
(b) optical image etched, and (c) 2.7 GHz acoustic image
of the same region (courtesy of L. Lam, Stanford
University)
Acoustic
Microscopy
Sample
Mechanical
scan
Scan-control
and CRT-drive
circuitry
Synchronization
(a)
Figure 3
Longitudinal acoustic wave (50 MHz) image of Lincoln's
head on the obverse surface of a US penny (courtesy of
E. Lynk, General Electric Company)
F i g u r e 2 s h o w s etched a n d u n e t c h e d optical i m a g e s
a n d a n u n e t c h e d 2.7 G H z acoustic surface w a v e inter
ference i m a g e of I n c o n e l g r a i n s . Because surface
waves p e n e t r a t e at m o s t 1-2 i n t o t h e specimen a t
these frequencies, essentially t h e s a m e m a t e r i a l is
s h o w n in all t h r e e images.
F i g u r e 3 s h o w s a 50 M H z p u l s e - e c h o i m a g e of the
Lincoln h e a d (obverse) surface of a p e n n y viewed
from t h e reverse side of t h e c o i n . T h e reverse side h a s
been l a p p e d s m o o t h t o p r o v i d e a distortion-free e n t r y
surface for the focused acoustic b e a m .
3. Photoacoustic
Microscopy
Figure 4
Schematic diagrams of photoacoustic microscope systems:
(a) after C. C. Williams, Stanford University; (b) after Y.
Martins and E. A. Ash, University College London
e x p a n s i o n causes a n u p w a r d d i s p l a c e m e n t of t h e
surface a n d a d o w n w a r d - p r o p a g a t i n g acoustic pulse.
T h e size of t h e h e a t e d s p o t t h a t c o n t r o l s t h e p h o t o
acoustic i m a g e r e s o l u t i o n is directly p r o p o r t i o n a l t o
the size of t h e light s p o t , t h e d u r a t i o n of the light pulse
a n d the specimen t h e r m a l diffusion (i.e., the r a t e at
which h e a t s p r e a d s t h r o u g h o u t the m a t e r i a l ) . T h e
distinguishing features of t h e p h o t o a c o u s t i c m i c r o
scopes discussed in this section a r e the m e t h o d s of
detecting acoustic pulse a m p l i t u d e s a n d the s c a n n i n g
m e t h o d s used t o c h a n g e the p o s i t i o n of t h e pulses in
the specimen.
T h e p h o t o a c o u s t i c m i c r o s c o p e system s h o w n in
Fig. 4a o r i g i n a t e d a t S t a n f o r d University ( W i c k r a m a s i n g h e et al. 1978) a n d utilizes the S t a n f o r d scan
ning acoustic m i c r o s c o p e t o receive a n d display the
signals a n d scan the specimen, b u t replaces t h e t r a n s
m i t t i n g t r a n s d u c e r with a n a r g o n laser m o d u l a t e d a t
940 M H z . T h i s system generates a t h e r m a l s p o t a b o u t
8 in d i a m e t e r . F i g u r e 5a s h o w s a n optical i m a g e
a n d Fig. 5b s h o w s a p h o t o a c o u s t i c i m a g e , p r o d u c e d
by t h e S t a n f o r d system, of a p a t t e r n e d gold film o n
Acoustic
Microscopy
Modified
scanning
electron microscope
Piezoelectric
transducer
receiver
Figure 6
Schematic diagram of an electron acoustic microscope
(after Cargill 1980)
this system h a s been a c c u r a t e l y n a m e d a " p h o t o d i s p l a c e m e n t m i c r o s c o p e . " A t h i r d type of p h o t o a c o u s t i c system utilizes a configuration similar t o the
electron acoustic system s h o w n in Fig. 6, with a
s c a n n e d laser in place of t h e s c a n n e d electron b e a m .
4. Electron
Figure 5
Images of gold foil attached to a glass substrate:
(a) optical image and (b) acoustic image with a resolution
size of about 8 (courtesy of C. C. Williams, Stanford
University)
glass. T h e sensitivity of p h o t o a c o u s t i c m i c r o s c o p y t o
the a d h e s i o n of films t o u n d e r l y i n g s u b s t r a t e s is
d e m o n s t r a t e d b y t h e c o n t r a s t o f t h e b u b b l e s in t h e
p h o t o a c o u s t i c i m a g e even t h o u g h the 8 focal s p o t
d e g r a d e s t h e r e s o l u t i o n slightly.
T h e alternative configuration (Fig. 4b) uses a
second laser t o m e a s u r e t h e u p w a r d surface displace
m e n t c a u s e d b y t h e h e a t i n g laser. Originally i n t r o
duced by researchers at U n i v e r s i t y College L o n d o n ,
u n d e r the direction of A s h ( M a r t i n s a n d A s h 1982),
Acoustic
Microscopy
S o m e t i m e s c o n s i d e r e d to be a n o t h e r device for p h o t o
a c o u s t i c m i c r o s c o p y , a n electron acoustic m i c r o s c o p e
differs in t h a t it uses a pulsed electron b e a m , usually
p r o v i d e d by a modified s c a n n i n g electron m i c r o s c o p e
t o p r o d u c e the ( t h e r m a l l y i n d u c e d ) s o u n d pulses. F o r
the electron b e a m t o be o p e r a t i v e , however, the
s a m p l e m u s t be in a high v a c u u m . T h e typical c o n
figuration
this system t a k e s is s h o w n in Fig. 6. T h e
s a m p l e is a t t a c h e d t o a stage by a n o n v o l a t i l e fluid
such as v a c u u m grease o r silicone oil. T h e stage is in
t u r n a t t a c h e d t o a piezoelectric t r a n s d u c e r configured
to receive all the pulses from the specimen a r e a at
a p p r o x i m a t e l y e q u a l sensitivity.
A l t h o u g h a typical focused s p o t d i a m e t e r for the
electron b e a m is a b o u t 0.1 , o r five times smaller
t h a n the smallest laser s p o t d i a m e t e r , until recently
the lateral r e s o l u t i o n of electron a c o u s t i c m i c r o s c o p e s
h a s n o t been a p p r e c i a b l y b e t t e r t h a n t h a t of the laserdriven m i c r o s c o p e s b e c a u s e of t h e d o m i n a n c e of the
t h e r m a l diffusivity of t h e i m a g e d m a t e r i a l . B o t h sys
t e m s seem t o p r o d u c e h e a t e d s p o t sizes b e t w e e n 5
a n d 10 , d e p e n d i n g o n the t h e r m a l diffusivity.
H o w e v e r , careful c o n t r o l of the p r i m a r y electron
Acoustic
Microscopy
5. Scanning
Laser
Acoustic
Microscopy
Scan - control
and
CRT-drive
circuitry
Piezoelectric
transducer
I n c i d e n t sound
Figure 7
Schematic diagram of a scanning laser acoustic
microscope (courtesy of L. W. Kessler, Sonoscan)
Figure 8
Scanning laser acoustic microscope transmission images at
100 MHz of ribbon leads on a metallized A1 20 3 substrate.
The bonded region, circled, has an area of 125 2
(courtesy of L. W. Kessler, Sonoscan)
Adhesives:
6. Future
Developments
Acoustic m i c r o s c o p y c o n t i n u e s t o h o l d c o n s i d e r a b l e
p r o m i s e for m a t e r i a l s c h a r a c t e r i z a t i o n a n d q u a l i t y
a s s u r a n c e in research a n d i n d u s t r y . T h e future direc
tions for a c o u s t i c m i c r o s c o p y a r e a l m o s t w i t h o u t
limit. A t S t a n f o r d , s c a n n i n g a c o u s t i c m i c r o s c o p y is
n o w being d o n e in cryogenic e n v i r o n m e n t s . A t liquidhelium t e m p e r a t u r e s , w a v e l e n g t h s as s h o r t as 80 n m
h a v e been p r o d u c e d . Extensive m a t e r i a l s c h a r a c t e r i
zation w o r k is u n d e r w a y at O x f o r d , U n i v e r s i t y
College L o n d o n , S t a n f o r d , C a r n e g i e M e l l o n a n d else
where. In i n d u s t r y , H u g h e s Aircraft, G e n e r a l Electric,
I n t e r n a t i o n a l Business M a c h i n e s , Bell L a b o r a t o r i e s ,
S o n o s c a n , Leitz a n d O l y m p u s a r e using a c o u s t i c
m i c r o s c o p y for m a t e r i a l s c h a r a c t e r i z a t i o n a n d p r o
duct testing. T h e last three firms a r e m a r k e t i n g a c o u s
tic m i c r o s c o p e s .
Bibliography
Ash A (ed.) 1980 Scanned Image Microscopy. Academic
Press, London
Balk L J, Kultscher 1983 Scanning electron acoustic
microscopy. Beitr.
Elektronemikroskop.
Direktabb.
Oberfl. BEDO-16
Briggs G A D 1992 Acoustic Microscopy. Oxford University
Press, Oxford
Cargill G S 1980 Electron acoustic microscopy. In: Ash
1980, pp. 319-31
Chou C H, Khuri-Yakub , Kino G S 1980 Transmission
imaging: forward scattering and scatter reconstruction.
In: Wang Y (ed.) 1980 Acoustical Imaging: Visualiza
tion and Characterization, Vol. 9. Plenum, New York,
pp. 357-77
Korpel A, Kessler L W, Palermo R 1971 Acoustic
microscope operating at 100 MHz. Nature (London) 232:
110-11
Lemons R A, Quate C F 1974 Acoustic microscope: scan
ning version. Appl. Phys. Lett. 24: 163-5
Lemons R A, Quate C F 1979 Acoustic microscopy. In:
Mason W P, Thurston R (eds.) 1979 Physical Acous
tics: Principles and Methods, Vol. 14. Academic Press,
London, pp. 1-92
Martins Y, Ash A 1982 Photodisplacement microscopy
using a semiconductor laser. Electron. Lett. 18: 763-4
Weglin R D 1979 A model for predicting acoustic material
signatures. Appl. Phys. Lett. 34: 179-81
Wickramasinghe , Bray R C, Jipson V, Quate C F,
Sakedo J R 1978 Photoacoustics on a microscopic scale.
Appl. Phys. Lett. 33: 923-5
R. G i l m o r e
[General Electric C o r p o r a t e R e s e a r c h
and Development, Schenectady,
New York, USA]
Properties
1. Adhesive
Characterization
T h e c o m p l e t e c h a r a c t e r i z a t i o n of a n adhesive re
quires t h a t its r e s p o n s e t o v a r i o u s l o a d , time a n d
e n v i r o n m e n t a l c o n d i t i o n s be a s c e r t a i n e d . T h e specific
a d h e s i v e - p r o p e r t y d a t a r e q u i r e d t o predict the re-
Adhesives:
Properties
o b t a i n fatigue a n d viscoelastic p r o p e r t i e s of t h e
adhesive. A brief s u m m a r y of their i m p o r t a n c e in
t h e design process follows.
(a)
shear a n d tensile m o d u l i ;
(b)
u l t i m a t e shear, tensile a n d c o m b i n e d s h e a r a n d
tensile strength;
(c)
u l t i m a t e s h e a r a n d tensile strain;
3. Fatigue
(d)
c r e e p - c o m p l i a n c e m a s t e r curves in s h e a r
tension;
(e)
(f)
(g)
coefficients of t h e r m a l a n d h y g r o s c o p i c e x p a n
sion.
and
2. Criteria
for
Test-Specimen
Evaluation
T h e specimen l o a d i n g m o d e m u s t be d o m i n a n t
a n d c o n t r o l l a b l e t e n s i o n a n d shear m o d e s
s h o u l d be s e p a r a b l e a n d their m a g n i t u d e easily
controlled. A biaxial o r triaxial stress state
s h o u l d be p r e s e n t in the adhesive.
(b)
T h e specimen m u s t be c a p a b l e of p r o v i d i n g
quantitative resultsmodulus and strength data
in representative e n v i r o n m e n t s s h o u l d be o b t a i n
able.
(c)
T h e test specimen m u s t be r e p r e s e n t a t i v e of
m a t e r i a l s a n d processing in p r o d u c t i o n i t
s h o u l d reflect the chemical, physical a n d m e c h a
nical r e s p o n s e of a n adhesive b o n d e d b e t w e e n
t w o relatively rigid a d h e r e n d s .
(d)
(e)
Multiple-specimen p r e p a r a t i o n s h o u l d be rela
tively easy a n d of n o m i n a l c o s t u n i f o r m c o n
trol of a d h e s i v e - b o n d l i n e thickness is necessary
for p r o p e r t e s t - d a t a i n t e r p r e t a t i o n .
(f)
(g)
O t h e r c o n s i d e r a t i o n s i n a d d i t i o n t o the a b o v e
criteria, t h e specimen s h o u l d be readily usable t o
10
4.
Response
Viscoelastic
Response
5. Candidate
Test
Specimens
A s u m m a r y of the v a r i o u s candidate-test-specimen
geometries a l r e a d y in existence versus t h e e v a l u a t i o n
criteria is given in T a b l e 1. F r o m this table c a n be
o b t a i n e d t h e list of test specimens best suited t o
o b t a i n desired adhesive m e c h a n i c a l p r o p e r t i e s s h o w n
in T a b l e 2.
6. Single
Lap
Joint
It is u n f o r t u n a t e t h a t t h e p r i m a r y s t a n d a r d for a d
hesive s t r e n g t h is t h e A S T M Test
Standard
D 1 0 0 2 - 7 2 , " S t r e n g t h P r o p e r t i e s of Adhesives in S h e a r
T e n s i o n L o a d i n g . " T h e specimen is a single l a p j o i n t
(see Fig. 1), c o m p r i s e d of t w o t h i n a d h e r e n d s , usually
steel o r a l u m i n u m , b o n d e d t o g e t h e r b y a n adhesive
layer. T h e specimen is pulled in tension a n d the m e a n
value of s h e a r s t r e n g t h is c o m p u t e d t o be the m a x i
m u m tensile l o a d divided by t h e shear a r e a
(L x unit width).
Because of t h e thin a d h e r e n d s , t h e tensile in-plane
l o a d causes c o n s i d e r a b l e b e n d i n g in the j o i n t , as seen
in Fig. 1. T h i s results in shear-stress p e a k s n e a r the
Adhesives:
Properties
Table 1
Candidate test specimens
Evaluation criteria
Loading mode
Specimen can provide
quantitative results
Representative of real
strutural
applications
Biaxial or triaxial
stress state in
adhesive
Specimen analysis
performed
Adhesive thickness
controllable
measurable
Specimen fabrication
ease of replicating
specimen
relative cost
NDE inspectability
Thickadherend
specimen
Scarf
joint
Butt
joint
tension
tension, shear
tension
static
static
static
visoelastic
viscoelastic viscoelastic
fatigue
fatigue
fatigue
shear
none
Napkin-ring
specimen
Iosipescu
specimen
tension, shear
shear
static
static
viscoelastic viscoelastic
fatigue
Double
lap joint
Peel
specimen
shear
none
tension
none
yes
yes
yes
yes
no
yes
yes
yes
yes
yes
yes
yes
yes
yes
yes
yes
yes
yes
yes
yes
no
yes
yes
no
easy
difficult
easy
easy
easy
yes
modestly
difficult
yes
yes
yes
yes
easy
easy
easy
easy
low
low
low
low
easy
difficult
modestly
difficult
modestly
expensive
modestly
difficult
easy
easy
yes
e n d s of t h e o v e r l a p , w h i c h g o t o z e r o a t t h e free
surfaces. It is also n o t e d t h a t the n o r m a l o r peel
stresses p e a k at t h e e n d s a n d a r e compressive over a
sizeable region in t h e j o i n t interior.
T h e adhesive shear stress of the A S T M test speci
m e n is far from c o n s t a n t , t h u s n e g a t i n g t h e d e t e r m i
n a t i o n of a t r u e s h e a r s t r e n g t h . E v e n w o r s e is t h e fact
t h a t t h e m a x i m u m tensile o r peel stress in the adhesive
c a n be g r e a t e r t h a n t h e m a x i m u m s h e a r stress. S o ,
failure m a y o c c u r in tensile r u p t u r e r a t h e r t h a n in
shear. T h u s , t h e specimen is n o t r e c o m m e n d e d for
d e t e r m i n i n g adhesive m e c h a n i c a l p r o p e r t i e s .
Table 2
Test specimens suited to obtain desired adhesive properties
Specimen
Type load
Thick-adherend lap
joint
Butt joint napkin ring
shear
Scarf joint
Single
lap joint
tension
tension plus
shear
Mechanical properties
obtainable
static, viscoelastic,
fatigue
static, viscoelastic,
fatigue
static, viscoelastic,
fatigue
modestly
modestly
difficult
difficult
yes
yesone side
only
easy
difficult
low
high
easy
modestly
difficult
modestly
difficult
modestly
expensive
modestly
difficult
7. Thick-Adherend
Symmetric
Lap
Joint
T h e t h i c k - a d h e r e n d s y m m e t r i c l a p j o i n t (see Fig. 2)
h a s been p r o p o s e d ( R e n t o n 1976, 1978) as a viable
specimen with w h i c h t o o b t a i n t h e effective thin-filmadhesive s h e a r m o d u l u s , p r o p o r t i o n a l limit stress a n d
u l t i m a t e s h e a r s t r e n g t h , as well as viscoelastic a n d
fatigue s h e a r p r o p e r t i e s . A d h e s i v e p r o p e r t i e s from
this specimen p r o v i d e d a t a readily u s a b l e in t h e
n u m e r o u s m e t h o d s of analysis c u r r e n t l y in use for
d e t e r m i n i n g stresses a n d d e f o r m a t i o n s in b o t h the
adhesive a n d t h e a d h e r e n d s . A d d i t i o n a l l y , it c a n be
used t o d e t e r m i n e t h e effect of adhesive thickness,
surface r o u g h n e s s , t e m p e r a t u r e , strain r a t e , residual
strains, c o r r o s i v e e n v i r o n m e n t a n d cyclic loading.
A c c u r a t e m e a s u r e m e n t of adhesive d e f o r m a t i o n is a
challenge w h i c h c a n be m e t b y a t t a c h i n g a m e a s u r e
m e n t device a t t h e adhesive b o n d l i n e ( H u g h e s a n d
R u t h e r f o r d 1968, R e n t o n 1976, 1978). T h e cost of
specimen fabrication a n d testing is q u i t e r e a s o n a b l e .
Figure 1
Deflections induced in a thin adherend lap joint
11
Adhesives:
Properties
- 0 . 9 c m j lT~
'
Adherends
LG
h2--
h2/2
,/2 -
Optimum
/2
dimensions:
Figure 2
Geometry of thick adherend optimum adhesive test
specimen
>
A t t a c h m e n t point
for strain
measurement
hi
> 8
1-2 ~
8. Butt
Joint
9. Scarf
Joint
12
Figure 3
Geometry of tensile specimen optimum adhesive test
specimen
n e u t r o n r a d i o g r a p h y offers a realistic a p p r o a c h t o
resolving this p r o b l e m . T h e s e specimens c a n also p o s e
b o n d l i n e thickness c o n t r o l a n d a l i g n m e n t p r o b l e m s .
Analytical a n d p h o t o e l a s t i c studies ( R e n t o n 1978)
h a v e s h o w n t h a t t h e stress in the m i d d l e p l a n e of t h e
specimen is triaxial, with a s u p e r i m p o s e d shear stress.
In s u m m a r y , by careful selection of t h e testspecimen g e o m e t r y , o n e c a n o b t a i n a n e a r - u n i f o r m
triaxial tensile-stress s t a t e a n d i m p a r t t o t h e adhesive
a c o n t r o l l e d s h e a r stress. A n aspect r a t i o of 40 ( u p t o
100 if the P o i s s o n ' s r a t i o of the adhesive is
0.480) is
suggested to k e e p the edge effect to within o n e o r t w o
adhesive thicknesses of t h e b o n d edge. A s t h e m e c h a
nical p r o p e r t i e s o b t a i n e d a r e a v e r a g e p r o p e r t i e s of the
adhesive c o n s t r a i n e d between the m u c h stiffer elastic
a d h e r e n d s , this m i n o r edge effect s h o u l d n o t a p p r e c i a
bly affect the test results. T h u s , the uniformity of the
Figure 4
Scarf joint
Adhesives:
Adhesive
bondline
specimen
Figure 5
Napkin-ring test specimen
10. Napkin-Ring
Specimen
M a n y of t h e i n s t r u m e n t e d adhesive c h a r a c t e r i z a t i o n
tests p e r f o r m e d t o d a t e h a v e used t h e n a p k i n - r i n g
specimen (see Fig. 5). O n e of its p r i n c i p a l a t t r i b u t e s is
t h a t it c a n be used t o d e t e r m i n e t h e s t r e s s - s t r a i n
response of a n adhesive m a t e r i a l in shear, tension o r a
c o m b i n a t i o n thereof, for static, fatigue a n d viscoelastic l o a d s . T h e use of t h e n a p k i n - r i n g test piece c a n
p r o v i d e a d h e s i v e - s h e a r - p r o p e r t y d a t a for typical
b o n d e d - j o i n t thicknesses, b u t requires e x t r e m e c a r e in
l o a d i n g t o e n s u r e p u r e t o r q u e . A d d i t i o n a l l y , the cost
per test item is q u i t e high a n d the specimen configur
a t i o n is n o t a b l y different from t h e g e o m e t r i c a l c o n
figuration
( H u g h e s a n d R u t h e r f o r d 1968) in w h i c h
structural adhesives a r e n o r m a l l y used. A n a c c u r a t e
analysis of the stress (strain) d i s t r i b u t i o n in the a d
hesive of this specimen h a s n o t been r e p o r t e d ; it is
believed t o be biaxial o r triaxial.
Load transfer
rod
(typical)
Properties
11.
Napkin-ring
Iosipescu
Specimen
12.
Other
Specimens
In principle, t h e b a l a n c e d d o u b l e lap j o i n t c o u l d be
used in a s h e a r m o d e with m o d e s t l y thick a d h e r e n d s ,
b u t w i t h relatively high fabrication a n d N D E inspec
tion costs. T h e selection of t h e g e o m e t r y of t h e j o i n t
w o u l d be extremely i m p o r t a n t in o b t a i n i n g a u n i f o r m shear-stress c o n d i t i o n .
Several o t h e r test specimens t o c h a r a c t e r i z e the
s t r u c t u r a l r e s p o n s e of adhesives a r e available. T h e
i n a d e q u a c i e s of t h e b l o c k s h e a r ( A S T M - D 9 0 5 ) , cross
t a b t e n s i o n a n d glueline cleavage tests h a v e been
r e p o r t e d ( R e n t o n 1978). It is i m p o r t a n t t o n o t e t h a t
t h e v a r i o u s peel tests t h a t presently exist a r e represen
tative of gross c o m b i n a t i o n s of s h e a r a n d tension. T h e
m a i n difficulty w i t h these peel tests is t h a t the adhesive
p r o p e r t i e s u n d e r shear p l u s t e n s i o n a r e grossly affec
ted by t h e a d h e r e n d . T h i s factor m a k e s the p r e s e n t
peel tests u n u s a b l e from the s t a n d p o i n t of o b t a i n i n g
precise q u a n t i t a t i v e m e c h a n i c a l - p r o p e r t y d a t a appli
cable t o b o n d e d - j o i n t analysis.
////////////////
/#/////////////\
-
(TV-
13.
Figure 6
Iosipescu shear-test specimen
Test-Methodology
Criteria
13
Adhesives:
Properties
14.
Test-Data
Reporting
A m a j o r deficiency in adhesive c h a r a c t e r i z a t i o n re
sults from the a r b i t r a r y test a n d r e p o r t p r o c e d u r e s
followed by m a n y investigators. I n c o m p l e t e i n f o r m a
tion m a k e s d a t a difficult to interpret a n d d a t a c o m
p a r i s o n s impossible. T h i s m a y be d u e in p a r t to the
lack of A S T M test specifications in this a r e a .
75. Adhesive
Deformation
Measurement
Anodization Spectroscopy
A n o d i z a t i o n s p e c t r o m e t r y is a d e p t h profiling tech
n i q u e which c a n p r o v i d e i n f o r m a t i o n a b o u t the c h e m
ical c o m p o s i t i o n a n d m i c r o s t r u c t u r e of a thin-film
specimen by r e c o r d i n g the voltage required t o m a i n
tain a c o n s t a n t c u r r e n t d u r i n g the electrolytic g r o w t h
of a n oxide film o n its surface. T h e t e c h n i q u e relies o n
the difference in the rates of oxide g r o w t h a n d varia
tions in ionic mobility between m a t e r i a l s ; these dif
ferences result in a characteristic r a t e of voltage rise
(dV/dt) with time for each element or c o m p o u n d .
C o n s e q u e n t l y , c h a n g e s in dV/dt c a n be a t t r i b u t e d t o
s t r u c t u r a l c h a n g e s in the specimen a n d the voltage a t
which they o c c u r t o the thickness of the preceding
layer. A n o d i z a t i o n s p e c t r o s c o p y h a s been applied t o a
variety of m a t e r i a l s a n d h a s been d e m o n s t r a t e d t o
h a v e very high resolution.
1.
Bibliography
Brown R 1986 Adhesion corrosion and staining. Physical
Testing of Rubber, 2nd edn. Elsevier, Amsterdam, Chap.
18
Hughes J, Rutherford J L 1968 Study of Micromechanical
Properties of Adhesive Bonded Joints, Technical Report
No. 3744. General Precision, Little Falls, NJ
Kutscha D, Hofer Jr 1969 Feasibility of Joining
Advanced Composite Flight Vehicles, Report AFML-TR68-391. US Air Force Materials Laboratory, Dayton, OH
Lehman G M, Hawley A V 1969 Investigation of Joints in
Advanced Fibrous Composites for Aircraft Structures, Vol.
1, AFFDL Report No. TR-69-43. US Air Force Flight
Dynamics Laboratory, Wright-Patterson Air Force Base,
Dayton, OH
14
Theory
A l t h o u g h t h e t h e o r y of the g r o w t h of a n o d i c oxides is
n o t completely clarified, all m o d e l s include s o m e
a s s u m p t i o n of t h e r m a l l y activated ionic h o p p i n g c o n
d u c t i o n . T h i s leads t o the a n o d i z a t i o n c u r r e n t density
J being g o v e r n e d by a r e l a t i o n s h i p of the form
J = A cxp(BE) in which the electric field E, is the
d o m i n a n t driving force a n d A a n d a r e c o n s t a n t s .
T h i s e q u a t i o n therefore predicts a linear r e l a t i o n s h i p
between voltage a n d oxide thickness. P r o v i d e d t h a t
the oxide is h o m o g e n e o u s this also leads t o a direct
p r o p o r t i o n a l i t y between thickness of c o n s u m e d speci
m e n m a t e r i a l a n d m o n i t o r e d voltage V; so t h a t
V=Rt
(1)
w h e r e t is the thickness of m a t e r i a l c o n s u m e d a n d R is
a material-dependent constant.
Anodization
Spectroscopy
Electrolyte
Specimen
Figure 1
Schematic diagram of the anodization system: the defined
anodization area is normally smaller than the electrolyte
drop
2. Sample
Preparation
and
Time (scaled)
Measurement
Procedure
Since q u a n t i t a t i v e c o m p o s i t i o n i n f o r m a t i o n c a n only
be extracted from t h e voltage u n d e r c o n s t a n t c u r r e n t
density c o n d i t i o n s , t h e p r i m a r y r e q u i r e m e n t in s a m p l e
p r e p a r a t i o n is t h a t t h e a r e a of t h e specimen e x p o s e d
t o the a n o d i z a t i o n cell s h o u l d r e m a i n c o n s t a n t
t h r o u g h o u t t h e m e a s u r e m e n t . If this a r e a varies t h e n
n o t only will t h e c u r r e n t density be altered, t h u s
modifying the p r o p o r t i o n a l i t y b e t w e e n thickness a n d
voltage, b u t c o n s i d e r a b l e noise c a n be g e n e r a t e d even
by very small increases in a n o d i z a t i o n a r e a . T h e
s t a n d a r d s a m p l e p r e p a r a t i o n t e c h n i q u e is t h e p a t t e r n
ing of a small w i n d o w in a resistant, electrically
insulating layer c o v e r i n g t h e surface of t h e specimen.
A Z p h o t o r e s i s t o r i n o r g a n i c resists, such as v a p o r deposited S i 0 2 , are the usual m a s k i n g m a t e r i a l s .
A typical e x p e r i m e n t a l a r r a n g e m e n t is illustrated in
Fig. 1. A d r o p of electrolyte is placed over t h e e x p o s e d
a n o d i z a t i o n region a n d electrical c o n t a c t is m a d e t o
the specimen in a region n o t e x p o s e d t o electrolyte,
usually by m e a n s of a s p r i n g p r o b e . A p l a t i n u m o r
gold c a t h o d e is c o n v e n t i o n a l l y e m p l o y e d . T h e s t a n
d a r d electrolyte for metallic specimens is a 0.4
solution of a m m o n i u m p e n t a b o r a t e in a 3:2 ethylene
g l y c o l - w a t e r m i x t u r e . A n o d i z a t i o n s p e c t r o s c o p y in
G a A s a n d o t h e r I I I - V s e m i c o n d u c t o r s h a s been
achieved using a q u e o u s 3 % ( + )-tartaric acid in a 1:2
v o l u m e r a t i o with ethylene glycol.
T h e voltage thickness c o n s t a n t R for e a c h element
(see E q n . (1)) m u s t generally be c a l i b r a t e d from a
series of m e a s u r e m e n t s . G i v e n a k n o w l e d g e of t h e
v o l u m e e x p a n s i o n coefficient of t h e oxide, a m e a s u r e
m e n t of t h e increase in thickness p o s t a n o d i z a t i o n will
p r o v i d e t h e r e q u i r e d i n f o r m a t i o n . If this factor is n o t
k n o w n t h e n o n e of t w o o t h e r t e c h n i q u e s m u s t be
e m p l o y e d : c o m p l e t e a n o d i z a t i o n of a film w h o s e
thickness is k n o w n or which c a n be m e a s u r e d , o r by
Figure 2
Anodization plots of (110) niobium-tantalum multilayers
showing (a) the differential voltage and (b) the direct
voltage vs time. Multilayer wavelength = 7.5 nm (1) and
= 3.4 nm (2). Atomic layers are represented by the ripple
structure on the dV/dt plots
3.
Applications
15
Anodization
Spectroscopy
A n o d i z a t i o n s p e c t r o s c o p y h a s been successfully
d e m o n s t r a t e d o n a n u m b e r of systems. A p p l i c a t i o n s
of the t e c h n i q u e fall n a t u r a l l y i n t o t w o classes, which
will n o w be discussed.
3.1 Structure
Determination
A n o d i z a t i o n s p e c t r o s c o p y is of p a r t i c u l a r relevance t o
m a t e r i a l s which c o n t a i n a thin b u r i e d layer w h o s e
d e p t h from the surface is critical t o a n aspect of
s u b s e q u e n t device processing. A s a n e x a m p l e , a n o d i
z a t i o n s p e c t r o s c o p y h a s been used t o d e t e r m i n e the
s e p a r a t i o n of A 1 2 0 3 t u n n e l b a r r i e r s in n i o b i u m super
c o n d u c t i n g devices as a stage in their processing i n t o
three t e r m i n a l devices a n d for the direct m e a s u r e m e n t
of 1-2 n m A 1 0 x t u n n e l b a r r i e r thicknesses. T h i s p r o
filing t e c h n i q u e is p a r t i c u l a r l y a t t r a c t i v e in t h a t it c a n
be achieved as p a r t of a p r o c e s s i n g stage in its o w n
right, a n d the r o u t i n e m e a s u r e m e n t of a l u m i n u m
layer thicknesses in N b - A l O ^ - N b t u n n e l j u n c t i o n
structures is n o w s t a n d a r d in m a n y l a b o r a t o r i e s .
3.2 Layer
Uniformity
Measurement
T h e c h a r a c t e r i z a t i o n of highly r e g u l a r m u l t i l a y e r
s t r u c t u r e s is of p a r t i c u l a r interest, in t h a t m a n y of the
results o b t a i n e d from such s t r u c t u r e s d e p e n d o n the
regularity a n d s h a r p n e s s of t h e interfaces b e t w e e n
layers. C o m p l e m e n t a r y d a t a o n these aspects c a n be
o b t a i n e d from x-ray diffraction a n d A u g e r electron
s p e c t r o s c o p y ( A E S ) . K a d i n et al. (1986) a r g u e t h a t the
resolution o b t a i n a b l e from a n o d i z a t i o n s p e c t r o s c o p y
is higher t h a n t h a t o b t a i n a b l e from m o s t o t h e r d e p t h
profiling t e c h n i q u e s .
4. Comparison
with Other
Depth
Profiling
Techniques
Bibliography
16
M . G. Blamire
[University of C a m b r i d g e ,
Cambridge, U K ]
Art Forgeries:
Scientific
Detection
o n t h e accepted m a r k e t p r o m i s e t o refund m o n e y s
gained by e r r o n e o u s a t t r i b u t i o n , t h a t h a v e been the
s t i m u l u s for a c u r r e n t g r o w t h in the involvement of
science in a r t analysis. T h a t i n v o l v e m e n t is n o t always
p a r t i c u l a r l y d e e p p e r h a p s j u s t the identification of a
m o d e r n industrial c o m p o n e n t in the p a p e r of a n
illuminated m a n u s c r i p t , o r of a resin vehicle in the
false p a t i n a t i o n o n a b r o n z e . O t h e r times, however,
t h e analytical a p p r o a c h h a s been m o r e sophisticated,
t a p p i n g resources of m o d e r n t e c h n o l o g y t h a t , in
m a n y instances, a r e scarcely a d e c a d e old.
T h e sheer diversity of m e d i a used in a r t over the
p a s t c o u p l e of millennia h a s e n s u r e d t h a t the field of
scientific fake detection is a very active o n e , t h o u g h
there a r e several m a t e r i a l s ( n o t a b l y Classical gold
jewelry a n d m a r b l e sculpture) t h a t still defy reliable
m e t h o d s of a u t h e n t i c i t y analysis. H o w e v e r , four areas
of forgery r e s e a r c h t h e d a t i n g of the clay fabric of
c e r a m i c s , the i n t e r p r e t a t i o n of the v a r i o u s s t r u c t u r a l
c o m p o n e n t s of p a i n t i n g s a n d the alloy analysis of
coins a n d of m e t a l s t a t u a r y h a v e each p r o d u c e d a n
extensive " r o g u e s ' g a l l e r y , " t o g e t h e r with a very ex
tensive ( s o m e t i m e s c o n t r o v e r s i a l ) literature. T h e case
histories included in the following general discussion
d r a w o n t h a t literature a n d typify the k i n d s of p r o b
lems t h a t a r t forgery h a s p o s e d a n d their technical
solution.
1.
Ceramics
17
Art Forgeries:
Scientific
Detection
Figure 1
The Ambush of Troilus and Polyxena, a detail from a fake painting on terracotta in the Etruscan style (courtesy of
S. J. Fleming)
18
T h e r a w m a t e r i a l s of t h e t e r r a c o t t a will h a v e s t o r e d
a great deal of T L energy d u r i n g their geological
history, b u t all t h a t energy will h a v e been erased by
kiln firing a t 700 C o r m o r e d u r i n g its m a n u f a c t u r e .
In o t h e r w o r d s , a time-zero is set for further T L
energy a c c u m u l a t i o n d u r i n g archaeological time. T h e
T L intensity m e a s u r e d t o d a y p r o v i d e s a n e s t i m a t e of
the t o t a l r a d i a t i o n d o s a g e received by the t e r r a c o t t a ,
a n d t h a t d o s a g e reflects t h e age of t h e t e r r a c o t t a . A
forgery will h a v e a relatively low d o s a g e c o m p a r e d
with its a n c i e n t c o u n t e r p a r t .
T h e t e r r a c o t t a w a l l - p a i n t i n g illustrated in Fig. 1,
depicting t h e m y t h i c a l t h e m e of The Ambush of Troi
lus and Polyxena, is o n e of a g r o u p of such artifacts
w h i c h a p p e a r e d in M u n i c h s o m e t i m e after 1963. It
w a s s u p p o s e d l y from a wall-niche in a n illicitly
o p e n e d t o m b which h a d been lavishly d e c o r a t e d in
h o n o r of a deceased E t r u s c a n n o b l e s o m e 2500 years
a g o . H o w e v e r , T L d a t a revealed t h a t it h a d been
Art Forgeries:
2.
Paintings
Scientific
Detection
Table 1
A comparison between the main colors of the traditional
artist's palette and those introduced in the wake of the
eighteenth century chemical revolution: the data for the first
use of each new color in European oil painting is given in
parentheses
Traditional
Artificial
lead white
vermilion
red/brown ocher
red lead
madder
yellow ocher
litharge
Naples yellow
verdigris
malachite
green earth
19
Art Forgeries:
Scientific
Detection
Figure 2
Detail from Still Life in the style of the Spanish master, Francisco de Zurbaran: it is now recognized as a post-1830 work,
because cadmium yellow was used to paint the skin of the lemons (courtesy of the St. Louis Art Museum: inv. 114.42)
20
R e m b r a n d t ) r a n schools of p a i n t i n g , p r o d u c t s of
which often beg for higher a t t r i b u t i o n t h a n " a p u p i l
of
" S o m e of t h o s e schools c o n t i n u e d t o flourish
m a n y d e c a d e s after t h e o r i g i n a t o r h a d died. P i g m e n t
analysis, a n d indeed m a n y of t h e n e w e r t e c h n i q u e s
b e g i n n i n g t o be applied t o a u t h e n t i c i t y analysis of
p a i n t i n g s (lead i s o t o p e analysis, a u t o r a d i o g r a p h y ,
infrared reflectometry, etc.) lack t h e t e m p o r a l resolu
tion r e q u i r e d t o u n r a v e l t h e scope of w o r k s h o p activi
ties of this k i n d .
3. Counterfeiting
of Silver
Coinage
Art Forgeries:
Scientific
Detection
Figure 3
A debased Mexican 8 real piece (obverse and reverse) recovered from the wreck of the American China Trader Rapid
(courtesy of I. MacLeod)
4. Bronze
Statuary
21
Art Forgeries:
Scientific
Detection
Hazards
Figure 4
Bodhisattva, a fake casting in the style of pre-Khmer
(c. seventh century) bronze statutary from the Thai
temple site of Pra Kon Chai (courtesy of S. J. Fleming)
22
Atomic
Force
Microscopy
s a m p l e is s c a n n e d using piezoelectric t r a n s d u c e r s .
M u c h of the t e c h n o l o g y used in the A F M h a s been
derived from the s c a n n i n g tunnelling m i c r o s c o p e
( S T M ) . A n i m p o r t a n t feature of the A F M is its ability
to i m a g e n o n c o n d u c t i n g surfaces, w h e r e a s the S T M
requires a c o n d u c t i n g surface c a p a b l e of sustaining a
stable tunnelling c u r r e n t . Several c o m m e r c i a l instru
m e n t s p r o v i d e b o t h S T M a n d A F M capabilities by
simply switching types of surface detector.
3
T h e useful magnification r a n g e is from 10 to
7
g r e a t e r t h a n 10 . A t o m i c resolution, of the o r d e r of
0.1-0.2 n m , h a s been achieved o n s m o o t h surfaces.
E q u a l l y i m p o r t a n t , vertical distances can be m e a s u r e d
to a resolution of less t h a n 1 n m . T h e i n s t r u m e n t
typically o p e r a t e s in air, b u t c a n easily be set u p with
the tip a n d specimen s u r r o u n d e d by a liquid. O p e r a
tion in a v a c u u m is possible b u t n o t c o m m o n . T h e
A F M is n o t well suited t o e x a m i n i n g r o u g h surfaces
o r surfaces inclined with respect to the tip.
T h e i n f o r m a t i o n collected d u r i n g a scan of the
surface is q u a n t i t a t i v e in three d i m e n s i o n s . W h e n
p r e s e n t e d as a t o p o g r a p h i c i m a g e , the elevation of
e a c h p o i n t in t h e p i c t u r e is e n c o d e d a c c o r d i n g to a
g r a y scale o r a false c o l o r scale. T h i s is a n a l o g o u s t o a
t o p o g r a p h i c m a p of a piece of l a n d . By g e n e r a t i n g a
r e n d e r e d t h r e e - d i m e n s i o n a l perspective, it is possible
t o r e c o n s t r u c t a n i m a g e of the surface features from
different v i e w p o i n t s . Profiles, o r cross sections,
t h r o u g h the surface c a n be p l o t t e d a n d q u a n t i t a t i v e
h o r i z o n t a l a n d vertical distances m e a s u r e d . R o o t m e a n - s q u a r e surface r o u g h n e s s c a n be c o m p u t e d
a l o n g lines o r over p l a n e s .
A p p l i c a t i o n s of the A F M to m a t e r i a l s science are
g r o w i n g very rapidly. It is well suited t o e x a m i n i n g
s m o o t h surfaces which c o n t a i n features o r defects less
t h a n 1 in size. O n surfaces which a r e atomically
s m o o t h , it is frequently possible t o observe a t o m
l o c a t i o n s . A t o m i c r e s o l u t i o n h a s been achieved for
m a t e r i a l s such as gold, N a C l , mica a n d T e S e 2 . Ledges,
g r o w t h steps a n d spiral features e m a n a t i n g from
screw dislocations h a v e been observed. Cleaved sur
faces of single crystals c a n be i m a g i n e d . O n a polished
a n d etched cross section of a m e t a l o r ceramic, grain
b o u n d a r i e s , precipitates, inclusions, voids a n d o t h e r
features a r e visible. Because the A F M h a s very g o o d
vertical r e s o l u t i o n , relief polishing will delineate
p h a s e s with even slight differences in a b r a s i o n resist
a n c e . Scratches a n d w e a r m a r k s h a v e been observed
a n d m e a s u r e d . P o l y m e r surfaces c a n be imaged,
a l t h o u g h very soft p h a s e s c a n interact with the tip to
p r o d u c e artifacts.
/.
Measurement
of Surface
Forces
23
Atomic
Force
Microscopy
2. Scanning
the
Surface
M e c h a n i c a l s c a n n i n g is a c c o m p l i s h e d by using a
piezoelectric t r a n s d u c e r . If fabricated in t h e f o r m of a
hollow cylinder with o n e electrode o n t h e interior wall
a n d four s e p a r a t e electrodes o n each q u a d r a n t of t h e
exterior wall, m o t i o n in three d i m e n s i o n s c a n be
achieved. O n e e n d of t h e cylinder is fixed to t h e
24
Figure 1
Surface scanning: small vertical displacements of the
specimen surface will cause a deflection of the laser beam
as it reflects off the cantilever surface. Displacements less
than 1 nm can be detected in the A-B signal. If negative
feedback is used to couple the detector signal to the
displacement of the piezoscanner, then a greater range
in specimen height can be measured
m i c r o s c o p e b a s e a n d t h e specimen is m o u n t e d o n t h e
o p p o s i t e e n d . A voltage applied b e t w e e n t h e interior
electrode a n d all of t h e o u t e r electrodes will c a u s e a
d i m e n s i o n a l c h a n g e a l o n g t h e axis of t h e cylinder, o r
direction. P o t e n t i a l s applied b e t w e e n o p p o s i t e q u a d
r a n t s of the o u t e r electrodes will cause b e n d i n g of t h e
t u b e a n d s u b s e q u e n t deflection of t h e free e n d of t h e
t u b e in t h e o r y direction. Typical r a n g e s a r e 10
in a n d 100 in a n d y. F o r a t o m i c resolution,
a c t u a t o r s with smaller r a n g e s in a n d y a r e preferred,
b e c a u s e the scan m a y cover only a few n a n o m e t e r s .
A critical p r o c e d u r e in a c t u a l o p e r a t i o n is t h e
a p p r o a c h of t h e tip t o t h e specimen. W i t h the aid of a
light m i c r o s c o p e , t h e t i p - s p e c i m e n s e p a r a t i o n is
mechanically r e d u c e d t o a few m i c r o m e t e r s a n d t h e
specimen is t h e n a d v a n c e d using the p i e z o a c t u a t o r
m o t i o n until c o n t a c t is m a d e . In Fig. 1, t h e specimen
is in c o n t a c t with the tip in the repulsive force m o d e
a n d is held a t a p o s i t i o n w h e r e the reflected light from
t h e laser is evenly split b e t w e e n segments A a n d of
t h e position-sensitive d e t e c t o r . If the specimen is
t r a n s l a t e d so t h a t a higher region p u s h e s t h e c a n t i
lever slightly u p w a r d s , t h e n m o r e of the light will fall
o n d e t e c t o r A a n d the A - B signal will increase. T h u s ,
t h e d e t e c t o r o u t p u t signal is a m e a s u r e of specimen
height a n d c a n be sensitive t o d i s p l a c e m e n t s of less
than 1 nm.
W h i l e this d e t e c t o r a r r a n g e m e n t is very sensitive, it
h a s a r a n g e limited by t h e physical p r o p e r t i e s of t h e
cantilever as well as by t h e p h o t o d e t e c t o r . If t h e
circuit is switched t o a negative feedback m o d e , with a
Atomic
Force
Microscopy
Computer
Control
signal
output
Data
signal
input
Laser and
photodetector
Cantilever
Specimen
position
y scan
Piezotube
scanner
Figure 2
The essential components for computer control and data
collection in a surface force microscope
3. Images
Displaying
Qualitative
Information
T h e processing a n d p r e s e n t a t i o n of t h e t o p o g r a p h i c
i n f o r m a t i o n in t h e f o r m of a n i m a g e requires a
c o m p u t e r . A single line of d a t a c a n be p l o t t e d as
height vs distance, depicting t h e elevation a l o n g t h a t
line. Early i m a g e s were f o r m e d by p l o t t i n g all the
lines of d a t a with a slight vertical a n d h o r i z o n t a l
offset for successive lines, in o r d e r to give a c r u d e
t h r e e - d i m e n s i o n a l aspect t o the display. W i t h c o m
p u t e r s a n d m o n i t o r s c a p a b l e of displaying s h a d e s of
gray o r a m u l t i t u d e of c o l o r s , it is possible t o g e n e r a t e
m u c h better i m a g e s . T h e basic p r o b l e m is t o t a k e the
t h r e e - d i m e n s i o n a l i n f o r m a t i o n describing p o i n t s o n a
surface a n d project t h e m o n t o a t w o - d i m e n s i o n a l
p l a n e for viewing.
T h e t o p view, o r gray-scale i m a g e , is a n a l o g o u s t o a
t o p o g r a p h i c m a p , with a view l o o k i n g directly d o w n
o n t o the surface. F i g u r e 3 is t h e surface of a c o m p a c t
disk, w h e r e t h e m o l d e d d e p r e s s i o n s c o n t a i n i n g the
Figure 3
The surface topography of a compact disk obtained with
an AFM. The molded depressions used to digitally encode
the signal are clearly visible. The black regions can be
thought of as being at "sea level" and the gray level of
other regions represent their height above sea level. The
gray-level bar to the right of the image calibrates the
height scale
25
Atomic
Force
Microscopy
Figure 4
The data used in Fig. 3 can also be displayed in a
three-dimensional rendered image. The shape of the
depressions can be clearly seen at the edge of the image
4. Extracting
Quantitative
Information
26
5.
Limitations
Atomic
6. Applications
to Materials
Force
Science
Microscopy
and
Engineering
A p p l i c a t i o n s of the A F M a r e rapidly g r o w i n g in the
field of m a t e r i a l s science a n d engineering. A t the
a t o m i c level, it is useful for o b s e r v i n g surface v a c a n
cies, s u b s t i t u t i o n a l impurities a n d a d a t o m s . T h e re
c o n s t r u c t i o n of clean surfaces, a n d c h a n g e s o c c u r r i n g
d u r i n g a d s o r p t i o n , c a n be studied. W i t h liquid o r
electrochemical cells, r e a c t i o n s at the solid-liquid
interface c a n be followed in detail. I m a g e s for these
a p p l i c a t i o n s a r e t a k e n a t very high magnifications,
typically a r o u n d 20 000 000.
3
6
A t lower magnifications ( 10 to 10 ) the c a p a
bility of the A F M for q u a n t i t a t i v e t o p o g r a p h i c
m e a s u r e m e n t s c o m p l e m e n t s the capabilities of o t h e r
microscopies very well. F o r e x a m p l e , a light m i c r o
scope e q u i p p e d for N o r m a r s k i differential interfer
ence c o n t r a s t is highly sensitive for detecting small
c h a n g e s in surface elevation (a few n a n o m e t e r s ) .
H o w e v e r , lateral r e s o l u t i o n is limited by the wave
length of light t o several h u n d r e d n a n o m e t e r s a n d
differences in height c a n n o t be m e a s u r e d q u a n t i t a t i
vely. If it is first used t o rapidly e x a m i n e a specimen in
o r d e r t o identify a n d locate features of interest, then
the specimen c a n be transferred t o a n A F M for m o r e
detailed a n d q u a n t i t a t i v e m e a s u r e m e n t s of the
features.
A metallurgical a p p l i c a t i o n is the e x a m i n a t i o n of
the surface of a polished ball b e a r i n g . T h e d i a m e t e r is
a b o u t 5 m m , so t h a t surface c u r v a t u r e limits the use of
a n optical m i c r o s c o p e . T h e S E M c a n i m a g e p h a s e s in
the m i c r o s t r u c t u r e as well as use energy dispersive
analysis to m e a s u r e their chemical c o m p o s i t i o n , b u t
its large d e p t h of field p r o v i d e s relatively p o o r d e p t h
p e r c e p t i o n . T h e A F M c a n a d e q u a t e l y c o m p e n s a t e for
the c u r v a t u r e w h e n used in the feedback m o d e a n d
gives a d d i t i o n a l i n f o r m a t i o n a b o u t surface finish.
F i g u r e 5 illustrates the surface of a ball b e a r i n g , with
the i m a g e processed to r e m o v e surface c u r v a t u r e . T h e
surface is quite s m o o t h , with a m e a s u r e d r m s r o u g h
ness of 12 n m . T h e lighter s h a d e of t h e M 6 C carbides
indicates relief polishing; because they are h a r d e r t h a n
t h e s u r r o u n d i n g steel m a t r i x , they polish less rapidly
a n d p r o t r u d e a b o v e the surface by a b o u t 20 n m .
T h e surfaces of m e t a l s a n d alloys a r e frequently
etched to reveal m i c r o s t r u c t u r e w h e n using light
m i c r o s c o p y . T h e precipitate size in m a n y m o d e r n
alloys is s u b m i c r o m e t e r , r e q u i r i n g magnifications
higher t h a n t h o s e achievable in the light m i c r o s c o p e .
T h e etched surface of a nickel-base superalloy (N-18)
is s h o w n in Fig. 6. T h e m a t r i x h a s been etched t o
r e m o v e a b o u t 30 n m , leaving t h e y particles s t a n d i n g
in relief.
In general, fracture surfaces a r e t o o irregular t o be
i m a g e d with the A F M . H o w e v e r , brittle m a t e r i a l s
m a y cleave a l o n g well-defined
crystallographic
p l a n e s , giving a suitable surface. E x a m i n a t i o n of a
cleaved surface of calcite d e m o n s t r a t e s t h a t the c r a c k
27
Atomic
Force
Microscopy
7. Future
Figure 5
Surface of a ball bearing made from tool steel. The
surface has been flattened electronically to remove the
curvature. The large particles are M 6C carbides which rise
about 20 nm above the surrounding matrix. The average
rms surface roughness is 12nm
Developments
Bibliography
Altshuler L 1991 Atomic-scale materials characterization.
Adv. Mater. Process. 140(3): 18
Binnig G, Quate C F, Gerber Ch 1986 Atomic force
microscope. Phys. Rev. Lett. 56: 930-3
Journal of Vacuum Science and Technology 9(2) 1991 Pro
ceedings of the Fifth International Conference on Scan
ning Tunnelling Microscopy/Spectroscopy
Sarid D 1991 Scanning Force Microscopy with Applications
to Electric, Magnetic and Atomic Forces. Oxford Univer
sity Press, New York
W. G. Morris
[General Electric C o r p o r a t e R e s e a r c h
a n d D e v e l o p m e n t , Schenectady,
New York, USA]
Figure 6
Etched surface of a nickel-base superalloy. The etchant
has preferentially attacked the matrix, leaving ' particles
clearly visible
28
Auger
1. Probability
of an Auger
Decay
Process
shell
electron
Spectroscopy
Figure 2
X-ray yield as a function of atomic number
Auger
electron
2. Escape
\
v.
Primary
electron
Electron
\
\
Figure 1
Schematic showing the competitive processes of x-ray and
Auger electron emission. The measured energy of the
emitted Auger electron is given by EKLL = EK(Z) - EL
( + ) - , where is the atomic number, EK(Z) is
the binding energy of the K-level electron, EL(Z) is the
binding energy of the L-level electron, E(Z + ) is
the binding energy of the L-level electron in the singly
ionized atom ( is a correction factor to account for the
ionized state of the atom and is approximately 0.5-0.75),
and is the work function of the analyzer
Depth
T h e factor t h a t is m o s t i m p o r t a n t in A E S , a n d which
m a k e s it a n i m p o r t a n t e x p e r i m e n t a l m e t h o d for sur
face c h a r a c t e r i z a t i o n , is t h e escape d e p t h of the
A u g e r electrons from the solid. T h e escape d e p t h is
the characteristic distance below the surface from
which the A u g e r electron c a n reach the surface with
o u t h a v i n g a n inelastic i n t e r a c t i o n with the m a t r i x .
F i g u r e 4 s h o w s the escape d e p t h as a function of the
electron kinetic energy. F o r 2 0 - 1 0 0 0 eV electrons the
escape d e p t h is less t h a n 2.0 n m , falling as low as
a b o u t 0.5 n m in t h e 5 0 - 2 0 0 eV energy r a n g e . T h e
escape d e p t h is defined as t h e distance from the
surface t h a t t h e electron c a n originate at a n d still h a v e
a p r o b a b i l i t y of 1/e (i.e., 0.37) of escaping w i t h o u t a n
inelastic i n t e r a c t i o n with the m a t r i x . T h e n u m b e r of
A u g e r electrons TV t h a t reach t h e surface from a d e p t h
below the surface w h e r e N0 electrons originate is
z/S
given by = N0e~ . T h i s s h o w s t h a t the majority of
the A u g e r electrons o r i g i n a t e m u c h closer t o the
surface t h a n the characteristic escape d e p t h , a n d t h a t
a large n u m b e r also o r i g i n a t e below the escape d e p t h .
A c o m p a r i s o n b e t w e e n A E S a n d electron m i c r o p r o b e
29
Auger
Electron
Spectroscopy
Pi
Th
Ac ,U
Fr
A l Rn
Po
Bi
m.
Tl
|H
Au
lr
Pi
0*
""Mi
T. "
Hf
Lu
Yh
Tm
im
Ho
M
n
Tb
Gd
Eu
m
VINTVI
$
""
Pr
La
Cs
P
Ce
Bi
X.
T*
"
A9
Rh
Tc
Pri
Ru
M
Nh
l
Y 7r
Sc
r
Rh
Vli
I
MM
Br
Kr
Se
As
P..
Lu
2n
Ni
Fe
r
Mil
v
;
'
a C
U ftr
PI
c
VI 1
-r\LL-
*S
'
Ma
a
F
N
"
L
li
0
r
R.
"
' Urn
U
-H
Figure 3
Characteristic Auger electron energies: dots indicate the electron energies of the principal Auger peaks for each element;
large dots represent predominant peaks for each element
Ag
Au
Mo
SocE^
Ag
Fe
Ag
Mo
W
-
^.
Ag
Mo
Ag
3. Auger
Electron energy (eV)
Figure 4
Escape depth as a function of the Auger electron energy
30
Signal
M a n y factors a r e involved in d e t e r m i n i n g t h e A u g e r
c u r r e n t from a given t r a n s i t i o n . F o r t h e /th t r a n s i t i o n
the A u g e r c u r r e n t /, c a n be given b y
Auger
Electron
Spectroscopy
Figure 5
Schematic of ionization cross section (arbitrary units) as a
function of the ratio of the primary energy to the
ionization energy
/, =
^^^
(1)
4. Ionization
and Backscattering
Cross
Sections
5. Auger
Peak
6. Measurement
of Auger
Electron
Energy
Exit s l i t
: =
^ - ( I n n e r cylinder)
C M A symmetry
axis \
Scanning
Specimen\ -n/f
C M A / v >
focal'
point
electron gun
Electron
multiplier
Exit
aperture
Widths
T h e H e i s e n b e r g u n c e r t a i n t y principle c a n
be
expressed as AEAt ^ h/2n, w h e r e h is P l a n c k ' s c o n
1 5
1 6
stant ( ~ 4 x l ( T e V s ) a n d At^z^ ( ~ 1 0 ~ S ) is t h e
half-life of t h e initial i o n i z a t i o n state. T h e r e f o r e ,
Cathode
Vm (Outer cylinder)
Figure 6
Schematic of a cylindrical mirror analyzer
31
Auger
Electron
Spectroscopy
200
400
600
E0
800
1000
(eV)
Figure 7
AES spectrum of silver: (a) derivative mode, (b) energy
distribution mode
7. Chemical
Effects
in
AES
8. Quantitative
Auger
Analysis
9. AES
Depth
Profiling
32
250
Electron energy (eV)
Figure 8
Characteristic carbon peaks for (a) carbide and
(b) graphite
Auger
A n o t h e r m a j o r p r o b l e m with inert-ion s p u t t e r i n g is
the very difficult task of q u a n t i f y i n g the d e p t h s p u t
tered. S t a n d a r d s p u t t e r i n g rates for h o m o g e n e o u s
materials c a n be m e a s u r e d b u t m a y n o t be directly
related t o s p u t t e r i n g of sequential thin layer s t r u c
tures. A great deal of a d d i t i o n a l effort is r e q u i r e d in
this a r e a of m e a s u r a b l e inert-ion s p u t t e r i n g rates. T o
o v e r c o m e edge effects associated with the i o n - b e a m
shape, the ion b e a m is rastered a n d A E S is p e r f o r m e d
only in the m i d d l e , uniformly s p u t t e r e d area.
10.
Vacuum Requirements
for
of
Spectroscopy
^ S on AISI 5140
S on Fe-0.6 Sb
on AISI 5140
0 Sb on AISI 3 3 4 0
* S b on Fe-2.2 Sb
Sb on Fe - 0.6 Sb
PonFe-Ni-Cr-C-P
Sn on F e - N i - C r - C -
AES
T h e e x t r e m e surface sensitivity of A E S m a k e s it a
m a n d a t o r y r e q u i r e m e n t t h a t in o r d e r t o get g o o d
i n f o r m a t i o n t h e surface m u s t be k e p t clean. T h i s is
particularly t r u e for the case of very thin layers of
m a t e r i a l . F o r this r e a s o n A E S m u s t be d o n e in a
v a c u u m system with a very low p a r t i a l p r e s s u r e of
active gases, in p a r t i c u l a r H 2 0 . T o h a v e m i n i m a l
interference with t h e electron optics, a v a c u u m of
2
better t h a n 10 P a is r e q u i r e d . If the p r i m a r y consti
t u e n t s of the v a c u u m a r e inert gases a n d the p a r t i a l
pressure of the active gases in t h e c h a m b e r is below
7
10~ P a , t h e n clean surfaces c a n be m a i n t a i n e d d u r i n g
the m e a s u r e m e n t time. It s h o u l d be n o t e d t h a t a n
active gas with a sticking coefficient of u n i t y will cover
the surface with a m o n o l a y e r for ~ 1 s e x p o s u r e at
4
10 Pa.
Therefore, there is a need for high v a c u u m with
m i n i m a l active gases. T o o b t a i n this, all-metal systems
are preferred. In certain cases, limited a m o u n t s of
l o w - v a p o r - p r e s s u r e n o n m e t a l l i c O-ring seals c a n be
used. G o o d v a c u u m p r a c t i c e m u s t be followed t o
avoid virtual leaks in t h e system.
T o o b t a i n the v a c u u m , m o s t systems avoid oil
p u m p i n g systems b u t use a c o m b i n a t i o n of zeolites o r p t i o n p u m p s t o r o u g h p u m p t h e system a n d ion
p u m p s c o m b i n e d with t i t a n i u m s u b l i m a t i o n p u m p s t o
o b t a i n the best u l t i m a t e pressure. W h e r e quick t u r n
a r o u n d time is r e q u i r e d , heavily t r a p p e d t u r b o m o l ecular p u m p s a r e c o m i n g i n t o usage.
It s h o u l d be n o t e d t h a t the n a t u r e of t h e surface will
have a significant influence o n h o w g o o d a v a c u u m is
required. F o r s e m i c o n d u c t o r a n d oxide m a t e r i a l s t h e
r e q u i r e m e n t s a r e m u c h less stringent t h a n for clean
surface active m e t a l s , such as a l u m i n u m , t i t a n i u m a n d
iron. F o r t h e surface-active m a t e r i a l s , it is a d v i s a b l e
to p r e b a k e t h e system a t a b o u t 200 C t o d e s o r b t h e
w a t e r v a p o r from t h e walls of t h e c h a m b e r . T h e
b a k i n g greatly reduces t h e relative p a r t i a l p r e s s u r e of
w a t e r v a p o r p r e s e n t a n d lowers t h e a b s o l u t e p r e s s u r e
_ 8
of the system t o t h e low 1 0 P a r a n g e .
11. Applications
Electron
AES
z (nm)
Figure 9
Sputter profile from intergranular fracture surfaces of
steel: C(z) is the concentration of the element at a depth
below the surface; C(0) is the concentration at the surface,
C" is the concentration in the bulk material
m a j o r uses of m a t e r i a l s a r e c o n t r o l l e d by surface o r
interface p r o p e r t i e s as well as by thin layered struc
tures. In m e t a l l u r g y , the a r e a s of fracture a n d fatigue,
w h e r e new surfaces a r e created, bulk a n d grainb o u n d a r y diffusion, c o a t i n g s , a d h e s i o n , surface p r e p
arations, hydrogen embrittlement,
solidification,
p o w d e r m e t a l l u r g y , c o m p o s i t e s , diffusion b o n d i n g
a n d o t h e r s all h a v e p r o b l e m s related to surfaces a n d
interfaces a n d h a v e gained insights from A E S studies.
A p r o m i n e n t e x a m p l e of this h a s been the extensive
studies o n g r a i n - b o u n d a r y a n d interface fracture in
steels; Fig. 9 is a n inert-ion s p u t t e r i n g profile s h o w i n g
t h e local n a t u r e of g r a i n - b o u n d a r y segregation associ
a t e d with e q u i l i b r i u m segregation.
Similar types of results a r e o b t a i n e d in s e m i c o n d u c
t o r studies. T h e thin layered s t r u c t u r e s of high-devicedensity M O S m a t e r i a l s lead t o t h e r e q u i r e m e n t of
A E S as a q u a l i t y - c o n t r o l system. Localized elements
t h a t influence the electrical p r o p e r t i e s of the materials
c a n be identified using t h e surface-sensitive A E S . A n
e x a m p l e of a s e m i c o n d u c t o r layered s t r u c t u r e is given
in Fig. 10.
A n o t h e r a r e a w h e r e A E S is a d y n a m i c p r o b e is the
s t u d y of catalytic b e h a v i o r of m a t e r i a l s . In this case
33
Auger
Electron
Spectroscopy
Bibliography
10
15
20
25
30
Sputtering t i m e ( m i n )
35
Figure 10
Sputter profile through a semiconductor layered structure
Figure 11
2+
Sputter
profile of segregation to free surface of C a and
3+
Sc in MgO
34
Auger
7. Auger
Emission
Angular
Distribution
Energy analyzer
Phenomenon
Core-level i o n i z a t i o n of a n a t o m by a fast m o v i n g
electron o r a n r a y c a n result in a r e l a x a t i o n p r o c e s s
in which a n o u t e r electron fills t h e c o r e v a c a n c y a n d a
third electron, a n " A u g e r e l e c t r o n , " is ejected from
the a t o m . A u g e r electrons were first identified by
Pierre A u g e r in c l o u d c h a m b e r e x p e r i m e n t s a n d were
found t o h a v e discrete energies characteristic of the
emitting elements. R e c e n t d a t a suggest t h a t t h e A u g e r
emission process is inherently isotropic a n d t h a t the
observed a n g u l a r v a r i a t i o n s of signal intensity a r e d u e
to scattering by a t o m s n e i g h b o r i n g the emitter. T h u s ,
the a n g u l a r d i s t r i b u t i o n s c a n be m o d e l l e d in t e r m s of
p o i n t emitters a n d spherical scatterers of A u g e r elec
t r o n s . T h e emission of e a c h A u g e r electron is c o n
sidered to be a n isolated event. A u g e r t r a n s i t i o n s
exhibit relatively large b a n d w i d t h s (typically g r e a t e r
t h a n 10 eV) d u e to u n c e r t a i n t y - b r o a d e n i n g effects a n d
are often further b r o a d e n e d d u e t o p a r t i c i p a t i o n by
multiple t r a n s i t i o n s of slightly differing energy. T h i s is
in c o n t r a s t t o t h e n a r r o w linewidths of p h o t o e l e c t r o n
emission processes. It is i m p o r t a n t t o n o t e t h a t A u g e r
electron a n g u l a r d i s t r i b u t i o n s h a v e been r e p o r t e d t o
be p r o f o u n d l y different from p h o t o e l e c t r o n distribu
tions at the s a m e kinetic energy. T h e origins of this
difference a r e u n d e r investigation.
2. Measurement
Microscopy,
of Auger
Distributions
A p p a r a t u s e m p l o y e d for the m e a s u r e m e n t of a n g u l a r
d i s t r i b u t i o n s is illustrated in Fig. 1. M e a s u r e m e n t s a r e
p e r f o r m e d in a n u l t r a h i g h v a c u u m ( U H V ) c h a m b e r to
preserve s a m p l e cleanliness a n d t o p e r m i t u n o b
structed travel of the electrons. T o s t i m u l a t e A u g e r
emission, a p o r t i o n of the s a m p l e is i r r a d i a t e d with a n
electron b e a m at a fixed angle of incidence. T h e use of
near-grazing angles of incidence e n h a n c e s surface
(b)
Figure 1
(a) ADAM angular distributions are measured vs the
angular coordinates (a and ) of the detector. Auger
electron emission is stimulated by an incident electron
beam impinging on the sample at a fixed angle (11 from
the surface plane in this instance). An Auger electron
travelling along the selected trajectory (, ) must pass
through the angle resolving collimator and an energy
resolving analyzer before being amplifed and counted.
(b) Data are displayed in spherical coordinates
35
Auger Microscopy,
Angular
Distribution
e l e c t r o m o d u l a t e d , amplified, c o u n t e d a n d s y n c h r o
nously amplified by m e a n s of a lock-in amplifier; the
resulting signal is digitized a n d s t o r e d by a c o m p u t e r .
F o r o p t i m a l excitation efficiency, t h e kinetic energy of
the incident electron b e a m s h o u l d be at least four
times larger t h a n t h e b i n d i n g energy of t h e c o r e level
being ionized. Because t h e energy d i s t r i b u t i o n of a n
A u g e r process is n a r r o w e r t h a n t h a t of t h e b a c k
g r o u n d signals, h a r m o n i c o r digital differentiation is
c o m m o n l y e m p l o y e d t o e m p h a s i z e t h e A u g e r signal.
Since the a m p l i t u d e of the derivative is p r o p o r t i o n a l
t o the A u g e r signal a m p l i t u d e , the a n g u l a r distribu
tion can be o b t a i n e d b y t u n i n g t o a p r o m i n e n t feature
of the derivative s p e c t r u m , typically the negative
inflection. A typical a n g u l a r d i s t r i b u t i o n c o n t a i n s
27 000 d a t a p o i n t s , o n e p o i n t p e r degree of solid
angle. T h e m e a s u r e m e n t time for a c o m p l e t e distribu
tion is typically 2 h, b u t d e p e n d s o n the incident b e a m
c u r r e n t , the strength of the A u g e r t r a n s i t i o n a n d
signal-to-noise c o n s i d e r a t i o n s .
While metallic a n d s e m i c o n d u c t i n g samples are
generally found to be a m p l y stable, d a m a g e d u e t o the
incident b e a m is possible for s o m e s a m p l e s a n d c a n be
detected by r e p e a t e d o b s e r v a t i o n a l o n g a few trajec
tories. S a m p l e s susceptible to b e a m d a m a g e c a n be
studied by averaging multiple fast scans o b t a i n e d for
individual, freshly p r e p a r e d samples.
M u l t i p l e A u g e r t r a n s i t i o n s are detectable for all b u t
the highest elements: h y d r o g e n a n d helium are n o t
detected; lithium t h r o u g h n e o n exhibit a single s t r o n g
A u g e r b a n d ; heavier elements h a v e b o t h low- a n d
high-energy A u g e r processes. N a t u r a l l y , the strongest
A u g e r t r a n s i t i o n s p r o d u c e the m o s t distinct distribu
tions. L o w - e n e r g y A u g e r electrons (below a b o u t
100 eV) necessarily originate in the o u t e r m o s t few
a t o m i c layers a n d t h u s offer a d v a n t a g e s in t e r m s of
surface sensitivity a n d simplicity for the investigation
of crystalline solid samples a n d thin films. H i g h e r
energies p e r m i t deeper p r o b i n g of b u l k s t r u c t u r e a n d
are also useful for the investigation of m o n o l a y e r s a n d
thin films.
Angle-and-energy-resolving analyzers are also use
ful for a variety of o t h e r m e a s u r e m e n t s . F o r instance,
quantitative
low-energy
electron
diffraction
( Q L E E D ) is a c c o m p l i s h e d rapidly a n d with high
accuracy. Reflection high-energy electron diffraction
( H E E D o r R H E E D ) e x p e r i m e n t s a r e readily per
formed. W i t h the a d d i t i o n of x-ray o r ion sources,
angle-resolved x-ray p h o t o e l e c t r o n spectra ( A R X P )
a n d ion a n g u l a r d i s t r i b u t i o n s ( I A D ) c a n also be
measured.
3. Specimen
Requirements
S t r u c t u r a l i n f o r m a t i o n revealed by A D A M
the average s t r u c t u r e over t h e surface a r e a
by the incident b e a m . A c c o r d i n g l y , use of
incident b e a m samples the s t r u c t u r e of a
36
d a t a is for
stimulated
a focused
region as
4. Information
Available
from
ADAM
Auger
Microscopy,
Angular
Distribution
Figure 2
(a) ADAM image from silver Auger electrons at 355 eV in a monolayer of silver atoms containing an overlayer of iodine
atoms, all resting on a Pt(l 11) surface. Bright regions denote large Auger signals, (b) Structure corresponding to the
ADAM image in (a)
A D A M r e s p o n d s t o the local e n v i r o n m e n t of e a c h
emitting a t o m a n d gives a real-space projection of
average a t o m i c s t r u c t u r e . T h u s , A D A M d o e s n o t
require for its effectiveness t h e s a m e degree of longr a n g e o r d e r necessary for efficient diffraction. L o n g r a n g e o r d e r is likewise n o t absolutely necessary for
S T M o b s e r v a t i o n s , which p r o v i d e t h e spatially
resolved t o p o g r a p h y of a surface. A D A M is n o t
restricted t o c h a r a c t e r i z a t i o n of the o u t e r m o s t layer,
however, a n d p r o v i d e s s t r u c t u r a l i n f o r m a t i o n r e g a r d
ing b u r i e d interfaces a n d layered s t r u c t u r e s n o t
readily accessible t o S T M .
5.
Applications
A l t h o u g h A D A M is a new t e c h n i q u e , a variety of
useful a p p l i c a t i o n s h a v e a l r e a d y been r e p o r t e d a n d
n u m e r o u s future a p p l i c a t i o n s a r e envisioned.
5.7 Thin Films
F i g u r e 2a is t h e A D A M i m a g e from silver A u g e r
electrons (355 eV) in a m o n o l a y e r of silver a t o m s
c o n t a i n i n g a n overlayer of iodine a t o m s , all resting
o n a P t ( l l l ) surface. Bright regions of the i m a g e
d e n o t e large A u g e r signals a n d d a r k r e g i o n s a r e low
signals as defined b y t h e g r a y - s c a l e b a r . C l e a r l y
evident is a h e x a g o n a l a r r a y of s i l h o u e t t e s in t h e
silver signal i n t e n s i t y (^ = 50, 0 = 0, 60, 120,
180, 240 a n d 300) p r o d u c e d b y i o d i n e a t o m s
resting a t o p n e i g h b o r i n g silver a t o m s . T h e s t r u c t u r e
c o r r e s p o n d i n g t o this i m a g e is i l l u s t r a t e d in F i g . 2 b .
(,) =
-'
>(')
"
i=
(1)
w h e r e TV is t h e n u m b e r of e m i t t i n g a t o m s in the m o d e l ,
is t h e t r a n s p a r e n c y of the a t o m , ra,(0, ) is the
37
Auger Microscopy,
Angular
Distribution
|
[
Figure 3
Simulated angular distribution for silver Auger electrons
(355 eV) based on the structure shown in Fig. 2b
n u m b e r of a t o m s e n c o u n t e r e d by the A u g e r electron
a l o n g the p a t h (, ) a n d 7 a is a n o r m a l i z a t i o n function
which describes the s m o o t h a n d g r a d u a l increase of
the analyzer field of view with increasing p o l a r angle
of detection:
_ I expMsin(2g> + 2 7 0 ) ] - e x p ( - ^ ) \
38
^,) - (,)]2 \
[(,) ~ (,)]2
1 2/
( 3
5.2 Single
Crystals
Several single crystals h a v e been characterized by
A D A M a n d h a v e been f o u n d t o b e h a v e similarly.
Results for P t ( l l l ) a r e typical.
F i g u r e 4 gives the e x p e r i m e n t a l a n g u l a r distribu
tions of A u g e r electrons e m i t t e d from a P t ( l l l )
surface with kinetic energies of 65 eV a n d 1968 eV.
Clearly visible in the center of the 65 eV d i s t r i b u t i o n is
a Y - s h a p e d region of high intensity, c o r r e s p o n d i n g t o
the g a p s b e t w e e n a t o m s in the a t o m i c layer located
i m m e d i a t e l y a b o v e each e m i t t i n g p l a t i n u m a t o m . T h e
highest intensity is observed a l o n g the surface n o r m a l .
In c o n t r a s t , the 1968 eV d i s t r i b u t i o n displays highest
intensities a l o n g directions c o r r e s p o n d i n g t o the clear
est c h a n n e l s t h r o u g h the face-centered-cubic (fee)
crystal. T h a t is, the m o r e energetic A u g e r electrons
(1968 eV) p r o b e the near-surface b u l k s t r u c t u r e of the
crystal (10 n m ) , while the lower energy A u g e r elec
t r o n s (65 eV) p r o b e the o u t e r m o s t few a t o m i c layers.
A s i m u l a t i o n w h i c h relates the 65 eV d a t a t o a
m o d e l s t r u c t u r e is s h o w n in Fig. 5a. T h e best agree
m e n t b e t w e e n this g e o m e t r i c calculation a n d the d a t a
occurs w h e n p l a t i n u m a t o m s are t a k e n t o be
uniformly 4 0 % t r a n s p a r e n t with a r a d i u s e q u a l t o
9 0 % of t h e a t o m i c r a d i u s . A l t h o u g h t h e q u a n t i t a t i v e
a g r e e m e n t of intensities is g o o d , it is the locations of
the features which reveal t h e relative p o s i t i o n of
a t o m s . F o r instance, t h e Y - s h a p e d m a x i m u m in the
d a t a c o r r e s p o n d s precisely t o the g a p between a t o m s
in t h e layer i m m e d i a t e l y a b o v e e a c h e m i t t i n g a t o m .
T h e o t h e r features of the d a t a also correlate with t h e
features of the calculation: t h e d a r k e r regions n e a r t h e
p e r i m e t e r c o r r e s p o n d t o regions of t h e s t r u c t u r e a l o n g
which a n A u g e r electron e n c o u n t e r s m o r e t h a n o n e
a t o m in t h e overlying layer; features d u e to adjacent
emitters a n d scatterers a r e p r o m i n e n t because these
a r e t h e m o s t frequently o c c u r r i n g c o n t r i b u t i o n s .
D e e p e r layers also c o n t r i b u t e as is seen from a
detailed c o m p a r i s o n of the d a t a a n d the digital calcu
lation. A t o m i c v i b r a t i o n is expected to affect a n g u l a r
d i s t r i b u t i o n s b e c a u s e the a m p l i t u d e of t h e r m a l vibra
tion a t r o o m t e m p e r a t u r e is a b o u t 9 % of t h e a t o m i c
r a d i u s , a l t h o u g h the calculation depicted in Fig. 5a
d o e s n o t include a t o m i c v i b r a t i o n . T h e effect of
a t o m i c v i b r a t i o n h a s been i n t r o d u c e d i n t o calcula
tions described in t h e b i b l i o g r a p h y .
T h e near-surface a n d b u l k crystalline s t r u c t u r e s a r e
p r o b e d by the higher kinetic energy (1968 eV) A u g e r
electron d i s t r i b u t i o n . T o identify the s t r u c t u r e , a
c o m p a r i s o n is m a d e between the d i s t r i b u t i o n a n d
geometric projections as s h o w n in Fig. 5b. Projections
a r e g e n e r a t e d by calculating the trajectories b e t w e e n
all t h e a t o m s in a s s u m e d crystal m o d e l s . L a r g e r s p o t s
a r e e m p l o y e d t o represent trajectories a l o n g which the
closer i n t e r a t o m i c spacings a r e e n c o u n t e r e d . F i g u r e
Auger
Microscopy,
Angular
Distribution
Figure 4
Experimental angular distributions of Auger electrons emitted from a Pt(l 11) surface with kinetic energies of (a) 65 eV
and (b) 1968 eV. Highest intensities in (a) correspond to the gaps between atoms in the atomic layer immediately above
each emitting platinum atom. Highest intensities in (b) are observed along the trajectories corresponding to the clearest
channels through the face-centred-cubic platinum crystal
5b w a s calculated for t h e o u t e r m o s t eight
layers of the fee s t r u c t u r e of P t ( l 11).
atomic
5.3
Monolayers
Since a m o n o a t o m i c layer c o n t a i n s a t o m s l o c a t e d
between t h e e m i t t i n g a t o m s a n d the d e t e c t o r only
a l o n g trajectories n e a r g r a z i n g emission, the a n g u l a r
d i s t r i b u t i o n from a m o n o a t o m i c layer is essentially
Figure 5
(a) Simulated distribution of 65 eV Auger electrons from Pt(l 11). (b) Geometric projection of the interatomic directions in
the first eight atomic layers of an fee crystal. Larger spots correspond to closer interatomic spacings and the clearest
channels through the crystal
39
Auger
Microscopy,
Angular
Distribution
Figure 6
(a) Adsorption of iodine vapor at Pt(111) produces an adlattice Pt(l 11)(V? x y/l)Rl9.\-l,
consisting of a hexagonal
layer of iodine atoms containing three iodine atoms per unit cell. One iodine atom occupies an atop site (no. 1) while the
other two iodine atoms occupy threefold hollows (nos. 2, 3). (b) Two mirror image domains of the iodine (shaded circles)
adlattice are present. Each unit cell is rotated 19. relative to the P t ( l l l ) substrate and spans seven surface platinum
atoms (grid intersections), (c, d) Auger electrons emitted from adsorbed iodine atoms (circles) are blocked by neighboring
iodine atoms, producing silhouettes in the angular distribution: (c) one domain, (d) two domains, (e) The measured
angular distribution of 507-518 eV Auger electrons emitted from the iodine monolayer displays the silhouettes of
neighboring iodine atoms. Brighter colors represent stronger Auger signals (see scale at lower left). The center of the
image corresponds to emission normal to the surface ( = 0) and the edge of the main corresponds to grazing emission
( = 90). The gaps between neighboring iodine atoms give rise to intensity maxima ( = 70, = 30, 90, . . . , 330), while
minima occur along iodine-iodine internuclear direction ( = 70, = 0, 60, . . . , 300). The data have been averaged by
use of the observed threefold symmetry, (f) A digital simulation of the ADAM image for this known structure in which
iodine atoms are treated as isotropic point emitters and spherical scatterers of Auger electrons. The simulation includes 50
unit cells of each domain and predicts the data to a correlation coefficient of better than 0.98
40
Auger
m o n o a t o m i c layer is c o r r u g a t e d , such a s w h e n t h e
a t o m s o c c u p y n o n e q u i v a l e n t sites o n t h e s u b s t r a t e .
Several e x a m p l e s of flat a n d c o r r u g a t e d m o n o a t o m i c
layers h a v e been c h a r a c t e r i z e d t o d a t e b y A D A M ,
yielding structures w h i c h c o r r o b o r a t e t h o s e i n d i c a t e d
by S T M a n d L E E D .
T h e b e h a v i o r of a c o r r u g a t e d m o n o l a y e r is illus
t r a t e d by t h e following results. F i g u r e s 6a, b s h o w
m o d e l s o f t h e P t ( l 11)(V7 x V7)tfl9.1-I a d l a t t i c e
s t r u c t u r e b a s e d o n findings from L E E D a n d S T M .
Figures 6c, d aid in t h e visualization a n d c o m p a r i s o n
of the simulated (Fig. 6e) a n d e x p e r i m e n t a l ( F i g . 6f)
a n g u l a r d i s t r i b u t i o n s from t h e i o d i n e m o n o l a y e r
(518 eV). T h e features of t h e s i m u l a t i o n a c c u r a t e l y
predict t h o s e of t h e e x p e r i m e n t a l image: b r i g h t c h a n
nels a l o n g t h e 0 = 30, 90, . . . , 300 directions. T h e
best a g r e e m e n t with e x p e r i m e n t w a s f o u n d w h e n
iodine a t o m s in threefold h o l l o w s were t a k e n t o b e
closer t o t h e p l a t i n u m surface b y 0.06 n m a n d 0.08 n m
c o m p a r e d t o iodine a t o m s in onefold sites, reflecting
the influence of second-layer p l a t i n u m a t o m s . T h e s e
height differences a r e r e a s o n a b l e for onefold a n d
threefold sites a n d a r e in g o o d a g r e e m e n t with t h e
S T M results. I n a d d i t i o n t o t h e o b v i o u s q u a l i t a t i v e
similarity of t h e theoretical a n d e x p e r i m e n t a l d i s t r i b u
tions, a q u a n t i t a t i v e c o m p a r i s o n yields a c o r r e l a t i o n
coefficient R g r e a t e r t h a n 0.98. A faint c h a n n e l l i n g
Microscopy,
Angular
Distribution
41
c
Ceramic Materials:
Cathodoluminescence Analysis
C a t h o d o l u m i n e s c e n c e ( C L ) is the emission of light
in response t o electron r a d i a t i o n . Essentially, t h e
m e c h a n i s m is the r a d i a t i v e r e c o m b i n a t i o n of elec
t r o n - h o l e p a i r s c r e a t e d in a s a m p l e by incident
electrons a n d is t h u s m o s t c o m m o n l y o b s e r v e d in
materials with discrete b a n d g a p s in their electron
energy d i s t r i b u t i o n s : ceramics (including m i n e r a l s a n d
semiconducting materials), some organic polymers
a n d biological m a t e r i a l s a n d , u n d e r special c i r c u m
stances, s o m e m e t a l s . A s a p h e n o m e n o n , C L is widely
exploited in p h o s p h o r s for the fluorescent screens of
televisions, V D U s a n d such like.
T h e wavelength of the e m i t t e d r a d i a t i o n is related
to the energy of the electronic t r a n s i t i o n s via t h e d e
Broglie r e l a t i o n s h i p , such t h a t
s a m e time, C L is p r o v i n g t o be a powerful m e a n s of
c h a r a c t e r i z i n g t h e m i c r o s t r u c t u r e s of minerals a n d
m o d e r n ceramic materials.
1. Origins,
Sensitivity
and
Applicability
T h e m e c h a n i s m s of t h e p h o t o n emission observed in
C L a r e similar t o t h o s e o c c u r r i n g by o t h e r m e t h o d s of
electronic excitation a n d t h u s there a r e m a n y parallels
with p h e n o m e n a such as p h o t o l u m i n e s c e n c e (PL).
H o w e v e r , in P L the a c t i v a t i o n of luminescent centers
c a n be very sensitive t o the w a v e l e n g t h of the (light)
excitation r a d i a t i o n , w h e r e a s the electron b e a m exci
t a t i o n used for C L analysis usually allows all possible
luminescence m e c h a n i s m s t o o p e r a t e simultaneously.
P h o t o n emission by e l e c t r o n - h o l e r e c o m b i n a t i o n
c a n be assigned t o o n e of t w o basic categories d e p e n d
ing o n t h e n a t u r e of the energy states involved. If the
t r a n s i t i o n occurs a c r o s s a f u n d a m e n t a l b a n d g a p in
t h e m a t e r i a l , t h a t is, a b a n d g a p arising as a conse
q u e n c e of the native a t o m i c s t r u c t u r e a n d b o n d i n g ,
t h e n t h e emission is said t o b e intrinsic. If, however,
t h e electron t r a n s i t i o n involves energy states t h a t only
exist, for e x a m p l e , o n a c c o u n t of i m p u r i t y a t o m s o r
o t h e r defect s t r u c t u r e s , t h e n the emission is t e r m e d
extrinsic. T h e r e f o r e , v a r i a t i o n s in b a n d s t r u c t u r e d u e
to crystal s t r u c t u r e , i m p u r i t y species a n d defects cause
v a r i a t i o n s in the w a v e l e n g t h of the C L emission.
C h a n g e s in the local density of radiative r e c o m b i n a
tion centers m a y c a u s e v a r i a t i o n s in t h e C L intensity
a n d t h u s allow m a p p i n g of b a n d s t r u c t u r e c h a n g e s ,
defect densities a n d i m p u r i t y levels. In this w a y , C L
c a n p r o v i d e i n v a l u a b l e i n f o r m a t i o n for characterizing
m a t e r i a l s which is n o t easily accessible in o t h e r ways.
In a d d i t i o n , t h e t e c h n i q u e is n o n c o n t a c t i n g a n d
generally n o n d e s t r u c t i v e ( t h o u g h s o m e m a t e r i a l s m a y
suffer electron r a d i a t i o n d a m a g e ) . Sensitivity is such
t h a t d e t e c t i o n of individual dislocations is possible
a n d impurities c a n be detected a t typical s e m i c o n d u c
20
3
t o r d o p i n g levels (e.g., ^ 1 0 a t o m s m ~ ) which a r e
t o o dilute for detection b y x-ray m i c r o a n a l y s i s . H o w
ever, significant densities of defects m a y create such a
c o n t i n u u m of defect electron states t h a t radiative
r e c o m b i n a t i o n n o longer occurs a n d the C L emission
is " q u e n c h e d . "
S o m e t i m e s , the origin of C L is readily ascribable
(e.g., t o trace i m p u r i t y v a r i a t i o n s in otherwise defectfree, h i g h - p u r i t y s e m i c o n d u c t i n g materials). H o w
ever, in m o s t cases, t h e t w o categories of C L emission
a r e indistinguishable a n d t h u s it m a y be u n c e r t a i n
w h e t h e r a p a r t i c u l a r p h a s e exhibits C L intrinsically o r
by virtue of s o m e defect o r i m p u r i t y c o n t e n t . W h i l e
this m a y affect q u a n t i t a t i v e i n t e r p r e t a t i o n , it d o e s n o t
43
Ceramic
Materials:
Cathodoluminescence
Analysis
and
Techniques
44
Imaging
In the C L i m a g i n g m o d e , a direct i m a g e of t h e C L
emission from the surface region of the m a t e r i a l is
formed. F o r i n s t r u m e n t s o p e r a t i n g with a s c a n n i n g
electron b e a m , this is simply achieved by s y n c h r o n
ously s c a n n i n g a n d m o d u l a t i n g a c a t h o d e r a y t u b e
( C R T ) with the (amplified) o u t p u t from the detection
device. By use of the filter system, the images c a n be
wavelength selected.
2.2 Spectroscopic
Studies
In the C L s p e c t r o s c o p y m o d e t h e light emission c a n
be analyzed for its wavelength intensity s p e c t r u m a n d
a t t e m p t s m a d e t o c o r r e l a t e the o c c u r r e n c e of given
w a v e l e n g t h with the emission from k n o w n types of
defects.
Such studies benefit greatly from the use of low
s a m p l e t e m p e r a t u r e s (particularly t h a t of liquid he
lium) since this reduces t h e r m a l b r o a d e n i n g of the
p e a k s , c a n increase the intensity of C L emission b y
certain m e c h a n i s m s a n d c a n also help reduce m a t e r i a l
d a m a g e d u e t o h i g h - d o s e electron i r r a d i a t i o n . H o w
ever, such e x p e r i m e n t a l a r r a n g e m e n t s are b o t h costly
and complex.
3. Sample
Preparation
4. Spatial
Resolution
Ceramic
Materials:
Cathodoluminescence
Analysis
r e a s o n a b l e signal-to-noise r a t i o in t h e detected C L
emission, t h e electron b e a m - s a m p l e i n t e r a c t i o n
v o l u m e , the optical p r o p e r t i e s of t h e s a m p l e (e.g.,
a b s o r p t i o n a n d refractive index w h i c h d e t e r m i n e sig
nal escape d e p t h s ) a n d t h e e l e c t r o n - h o l e m i g r a t i o n
characteristics. H i g h - b r i g h t n e s s electron sources such
as L a B 6 a n d field e m i t t e r s h e l p t o i m p r o v e r e s o l u t i o n
by minimizing t h e incident p r o b e size necessary for a
given b e a m c u r r e n t . T h e size of t h e e l e c t r o n - s a m p l e
interaction v o l u m e c a n be e s t i m a t e d using M o n t e
C a r l o s i m u l a t i o n s a n d t h e v a r i a t i o n of electron p e n e
t r a t i o n with incident electron energy (typically oc E1)
allows c r u d e d e p t h profiling t o be u n d e r t a k e n as a
function of b e a m voltage E. H o w e v e r , a t higher b e a m
energies, the light g e n e r a t e d far below t h e surface
m i g h t be strongly a t t e n u a t e d o r m a y be scattered o r
diffused p r i o r t o escape. I n all cases, t h e d e p t h from
which C L i n f o r m a t i o n c a n be retrieved is typically
^ 20 a n d is d e p e n d e n t o n the s a m p l e m a t e r i a l a n d
the energy of t h e incident electron.
T h e use of thin specimens in S E M o r S T E M
p e r m i t s the size of t h e electron i n t e r a c t i o n v o l u m e
within the specimen t o be greatly r e d u c e d a n d c a n
offer potentially higher r e s o l u t i o n s a t t h e expense of
decreased e l e c t r o n - h o l e p a i r g e n e r a t i o n events.
After g e n e r a t i o n , the e l e c t r o n - h o l e p a i r s m i g r a t e
until they reach a r e c o m b i n a t i o n center. T h i s c a n be
quite d i s t a n t from t h e carrier g e n e r a t i o n site a n d , for
radiative t r a n s i t i o n s , serves t o d e g r a d e the r e s o l u t i o n .
In t h i n n e r specimens, n o n r a d i a t i v e surface r e c o m b i
n a t i o n b e c o m e s m o r e likely a n d while r e d u c i n g t h e
overall r a d i a t e d intensity also limits l o n g m i n o r i t y
carrier diffusion p a t h s a n d c a n e n h a n c e resolution.
Spatial r e s o l u t i o n c a n also be i m p r o v e d by the use of
time-resolved t e c h n i q u e s w h e r e t h e C L o b s e r v a t i o n s
are m a d e in s h o r t time intervals ( ~ 1 ns) t h a t limit t h e
d e g r a d a t i o n of r e s o l u t i o n d u e t o carrier diffusion.
H o w e v e r , t h e i n s t r u m e n t a t i o n for such studies is
sophisticated a n d usually limited t o t h e e v a l u a t i o n of
device m a t e r i a l s .
T h e r a d i a t i v e r e c o m b i n a t i o n time (i.e., t h e interval
between carrier excitation a n d r e c o m b i n a t i o n ) c a n be
r a t h e r l o n g (e.g., in long-persistence p h o s p h o r m a t e r
ials) a n d , for s c a n n i n g p r o b e t e c h n i q u e s , often re
quires the use of slow line speeds a n d frame times in
o r d e r t o avoid " s m e a r i n g " of t h e i m a g e .
5. Examples
of CL Characterization
of
Ceramics
5.1 Phase
Distributions
Figures l a , b s h o w t h e d i s t r i b u t i o n of p h a s e s in
c u r r e n t engineering c e r a m i c m a t e r i a l s as revealed by
C L in a S E M using a p a r a b o l i c m i r r o r d e t e c t i o n
a r r a n g e m e n t . In Fig. l a , the m i c r o s t r u c t u r e of a n
A l 2 0 3 - Z r 0 2 c e r a m i c c u t t i n g t o o l insert is revealed
to c o n t a i n a p p r o x i m a t e l y 1 Z r 0 2 particles (light
imaging), - 1 2 0 3 (mid-gray) a n d a p p r o x i m a t e l y
5-10 laths of a n u n e x p e c t e d , i m p u r e , a l u m i n a
p h a s e ( d a r k i m a g i n g ) . W i t h o u t C L , these laths c a n -
Figure 1
Examples of the use of panchromatic CL images (SEM) to
both distinguish and reveal the distribution of the phases
present in engineering ceramics: (a) three phases revealed
in an A l 2 0 3 - Z r 0 2 alloy; and (b) Grain-boundary films of
monoclinic Z r 0 2 delineated in a cubic/tetragonal (partially
stabilized) Zr0 2-4wt%CaO alloy
45
Ceramic Materials:
Cathodoluminescence
Analysis
Figure 2
The dislocation array around a 1 kg hardness indentation
in the (100) face of a large MgO single crystal revealed by
panchromatic CL imaging
6.
Conclusions
46
Figure 3
CL (SEM) images from new ceramic materials: (a) changing
levels of impurities/defects revealed in the growth rings of
a SiC fiber deposited on a (nonluminescent) metal wire
core (15 kV); and (b, c) 5 kV secondary electron and CL
images of individual diamond crystals early in the growth
of a diamond film for surface engineering
Ceramic
Bibliography
Brown L M, Younis Khan M, Chaudhri 1988 Quench
ing of cathodoluminescence at the centre of hardness
indentations on a (100) face of MgO. Philos. Mag. A 57:
187-96
Czernuszka J T, Page F 1985 Cathodoluminescence: a
microstructural technique for exploring phase distribu
tions and deformation structures in zirconia ceramics. J.
Am. Ceram. Soc. 68: C196-9
Marshall D J 1988 Cathodoluminescence of Geological
Materials. Unwin Hyman, London
Newbury D E, Joy D C, Echlin P, Fiori C E, Goldstein J I
1986 Advanced Scanning Electron Microscopy and X-Ray
Microanalysis. Plenum, New York
Pennycook S J, Brown L M, Craven A J 1980 Observation
of cathodoluminescence at single dislocation by STEM.
Philos. Mag. AAV. 589-600
Petroff , Lang D V, Strudel J L, Logan R A 1978
Scanning transmission electron microscopy techniques
for simultaneous electronic analysis and observation of
defects in semiconductors. In: Johari O, Becker R (eds.)
1978 Scanning Electron Microscopy, Pt. 1. Scanning
Electron Microscopy, Chicago, IL, pp. 325-32
Warwick C A 1989 Scanning cathodoluminescence of semi
conducting materials. Inst. Phys. Conf. Ser. 98: 447-70
Yacobi G, Holt D 1990 Cathodoluminescence Micros
copy of Inorganic Solids. Plenum, New York
T. F . P a g e
[University of N e w c a s t l e u p o n T y n e ,
Newcastle u p o n Tyne, U K ]
R. B a r r e t t
[CNRS, Grenoble, France]
7. Constituents
of a Particulate
Powders:
Packing
Characterization
2. Known
and Measurable
Quantities
System
3. Densities
and Specific
Volumes
47
Characterization
4. Volumetric Compositions
of Phases
iPlPi
T h e v o l u m e fraction % of t h e gas p h a s e is e q u a l to
1 - ,. T h e s u m of % a n d the values for all
c o n d e n s e d p h a s e s is e q u a l to unity.
T w o c o m m o n l y used p a r a m e t e r s a r e the p e r c e n t of
theoretical density a n d the percent p o r o s i t y . T h e
former is 100 times the v o l u m e fraction of solids
a n d the latter is 100 times the v o l u m e fraction of the
gas p h a s e (pr If the t e r m " v o i d s " is used to describe all
the space n o t occupied by solid, the v o l u m e fraction
of voids is 1 - (ps.
T h e b e h a v i o r of p a r t i c u l a t e systems d e p e n d s in
m a n y instances o n the space-filling characteristics of
the system. F o r different systems, c o n t a i n i n g different
c o n s t i t u t e n t s , c o m p a r i s o n s are meaningful only in
terms of v o l u m e fractions ( n o t weight fractions). F o r
e x a m p l e , consider a system of u n i f o r m spheres which
form a dense r a n d o m p a c k i n g at a v o l u m e fraction of
0.63. W h e n the voids a r e filled with water, the weight
fraction of solids in the system d e p e n d s o n the density
of the solid p h a s e . If t w o systems of u n i f o r m spheres
h a v i n g particles of different densities are c o m p a r e d ,
the weight fractions are different; h o w e v e r , the geo
metric a n d space-filling characteristics a r e the s a m e .
5, Specific Volumes of
Mixtures
48
Figure 1
Specific volume diagram
p o i n t O ) . F r o m the p o s i t i o n of t h e d a t a o n the g r a p h ,
several useful c o n c l u s i o n s c a n be d e d u c e d , as follows
in this section.
T h e straight line j o i n i n g p o i n t s A a n d describes
h o w the specific v o l u m e of t h e system varies with
c o m p o s i t i o n if n o gas p h a s e is present. T h e left-hand
side of this line is d a s h e d , since at lower w a t e r
c o n t e n t s t h e c o n d i t i o n of n o gas p h a s e is physically
unrealistic; since there is a limit t o h o w tightly the
particles c a n p a c k , t h e void v o l u m e c a n n o t c o n
t i n u o u s l y d i m i n i s h with the w a t e r v o l u m e .
T h e specific v o l u m e of a m i x t u r e c a n n o t fall b e l o w
line A B unless a chemical r e a c t i o n takes place, such as
the p a r t i a l dissolution of the solid in water. In the
absence of r e a c t i o n s , t h e d a t a m u s t fall o n o r a b o v e
line A B . W h e n a b o v e the line, t h e system c o n t a i n s a
gas p h a s e . T h e v o l u m e fractions of t h e three p h a s e s
c a n be d e t e r m i n e d by c o n s t r u c t i n g a vertical line
t h r o u g h the d a t a p o i n t O , a n d a n o t h e r line between
p o i n t s A a n d F . T h e v o l u m e fractions of solid, liquid
a n d gas a r e given b y the r a t i o of line lengths E D - E O ,
C D - E O a n d C O - E O , respectively.
In special cases, t h e p a c k i n g density of the particles
m a y r e m a i n c o n s t a n t as w a t e r is a d d e d to fill t h e
voids. F o r these cases, t h e v a r i a t i o n in specific v o l u m e
is represented by a straight line d r a w n from p o i n t G ,
the p a c k i n g specific v o l u m e of the d r y p o w d e r , t o
p o i n t H , w h e r e e x t r a p o l a t i o n of t h e line goes t o p o i n t
F . F r o m p o i n t G t o p o i n t H , t h e voids a r e being filled
with liquid, w i t h c o m p l e t e filling o c c u r r i n g a t p o i n t H .
T h e c o m p o s i t i o n at is t h e a m o u n t of w a t e r n e e d e d
to fill the void space completely for a given particle
packing.
A h y p o t h e t i c a l v a r i a t i o n in specific v o l u m e with
c o m p o s i t i o n for the a l u m i n a - w a t e r system is given as
the curve I J K L B . C o m p a r i n g the curve with the lines
Ceramic
Powders:
Packing
Characterization
A B a n d G F , it c a n be d e d u c e d h o w the space-filling
relations c h a n g e as w a t e r is a d d e d t o t h e d r y p o w d e r .
P o i n t I is t h e p a c k i n g specific v o l u m e of the d r y
p o w d e r . A s small q u a n t i t i e s of w a t e r a r e a d d e d , the
p a c k i n g density decreases (e.g., o w i n g t o capillary
effects) until p o i n t J is r e a c h e d . F r o m p o i n t J t o p o i n t
K, the p a c k i n g specific v o l u m e r e m a i n s c o n s t a n t
(equal t o t h e value at p o i n t G ) while w a t e r c o n t i n u e s
to fill the voids. B e y o n d p o i n t K , the p a c k i n g begins
to e x p a n d s o m e w h a t while t h e last a m o u n t s of gas in
the voids a r e being replaced by w a t e r . T h i s c o u l d
result, for e x a m p l e , b e c a u s e of n o n u n i f o r m d i s t r i b u
tion of w a t e r t h r o u g h o u t t h e voids. A t p o i n t L, all the
gas p h a s e is g o n e (since t h e d a t a fall o n line A B ) .
F r o m p o i n t L t o p o i n t B, a gas-free m i x t u r e of
a l u m i n a a n d w a t e r exists.
This m e t h o d o l o g y c a n be applied to a n y system in
which o n e i n d e p e n d e n t c o m p o s i t i o n a l v a r i a t i o n is
occurring. It c a n be a p p l i e d t o m u l t i c o m p o n e n t sys
tems if the r a t i o of certain p h a s e s r e m a i n s fixed. F o r
example, a system m a y b e c o m p r i s e d of solid 1, solid
2, liquid 1 a n d liquid 2 (the liquids a r e immiscible). If
b o t h the weight r a t i o s of solid 1 t o solid 2 a n d of
liquid 1 t o liquid 2 r e m a i n c o n s t a n t , a specific v o l u m e
d i a g r a m c a n be c o n s t r u c t e d in t e r m s of the weight
fractions of t o t a l solid a n d t h e weight fractions of
total liquid.
6. Packing
Inhomogeneities
T h e u n i f o r m i t y o f p a c k i n g t h r o u g h o u t a green b o d y is
i m p o r t a n t for u n i f o r m s h r i n k a g e a n d e l i m i n a t i o n of
p o r o s i t y d u r i n g firing. T w o scales of i n h o m o g e n e i t y
are the microscale a n d t h e m a c r o s c a l e . T h e microscale
involves d i m e n s i o n s of t h e o r d e r of m a g n i t u d e of
those of the particles. T h e m a c r o s c a l e involves d i m e n
sions c o m p a r a b l e t o t h e size of t h e b o d y (e.g., m m o r
cm). O n a microscale, voids t h a t a r e larger t h a n t h e
sizes of t h e particles a r e a p r o b l e m b e c a u s e they
c o m m o n l y r e m a i n after firing. A s a n e x a m p l e , Fig. 2
illustrates for a n a l u m i n a c o m p a c t h o w a local region
of higher p o r o s i t y results in t h e f o r m a t i o n of large
voids d u r i n g sintering.
T h e d i s t r i b u t i o n of void sizes c a n be e s t i m a t e d b y
m e r c u r y p o r o s i m e t r y . W h e n m e r c u r y is forced u n d e r
pressure t o fill t h e voids of a system, large p o r e s a r e
filled a t lower pressures t h a n small p o r e s . A c u r v e of
m e r c u r y v o l u m e i n t r u s i o n vs p r e s s u r e p r o v i d e s infor
m a t i o n o n void-size d i s t r i b u t i o n . D e n s i t y v a r i a t i o n s
o n a m a c r o s c a l e c a n be assessed by dividing the
sample i n t o small u n i t s (e.g., by cutting) a n d m e a s u r
ing the density of e a c h unit. I n s o m e cases, it is
possible t o i m p r e g n a t e t h e v o i d s with a resin o r sulfur
so t h a t m e t a l l o g r a p h i c cross sections c a n be o b t a i n e d
by c u t t i n g a n d polishing. U s i n g m i c r o s c o p y , v o l u m e
fractions of p h a s e s a n d d i s t r i b u t i o n characteristics
c a n be e s t i m a t e d . A n o t h e r m e t h o d is t o use a n x-ray
r a d i o g r a p h (Broese v a n G r o e n o u a n d K n a a p e n 1980)
Figure 2
Retention of low-density region in alumina during
sintering: (a) initial compact, (b) after 1 min at 1700C
(after Kingery et al. 1976 p. 482)
49
Ceramic
Powders:
Packing
Characterization
Bibliography
Detector
Incident
electron
beam
Bloch wave
X rays
G. Y. O n o d a
[University of F l o r i d a , Gainesville,
Florida, USA]
Channelling-Enhanced Microanalysis
T h e p r o d u c t s of i n t e r a c t i o n events b e t w e e n a n elec
t r o n b e a m a n d a m a t e r i a l , such as the characteristic
rays representative of t h e c o n s t i t u e n t elements of the
m a t e r i a l o r the electron energy loss c o r r e s p o n d i n g t o
x-ray p r o d u c t i o n , a r e c o m m o n l y used for chemical
analysis. In a m o d e r n t r a n s m i s s i o n electron m i c r o
scope e q u i p p e d with a n energy dispersive x-ray detec
t o r ( E D X S ) or a n electron energy loss s p e c t r o m e t e r
( E E L S ) , the ability t o p r o d u c e incident electron
p r o b e s with d i a m e t e r s of the o r d e r of 10 n m easily
(with a routinely available i m a g e r e s o l u t i o n of 2 5 n m ) results in a m i c r o a n a l y t i c a l t e c h n i q u e of high
spatial resolution, limited by t h e i n t e r a c t i o n v o l u m e
of the electron p r o b e a n d t h e electron t r a n s p a r e n t
s a m p l e ( a p p r o x i m a t e l y 5 0 - 2 0 0 n m thick). T h e tech
n i q u e of c h a n n e l l i n g - e n h a n c e d m i c r o a n a l y s i s further
refines the spatial resolution t o t h e level of specific
crystallographic site chemistry, with n o a t t e n d a n t
r e q u i r e m e n t of increased i n s t r u m e n t
capability
(Spence a n d T a f t o 1983, K r i s h n a n 1988).
1.
Principles
T h e principles of c h a n n e l l i n g - e n h a n c e d m i c r o a n a l y s i s
m a y be u n d e r s t o o d by e x a m i n i n g the s o l u t i o n s for the
e q u a t i o n s of d y n a m i c scattering describing the p r o p a
g a t i o n of a n electron b e a m t h r o u g h a m a t e r i a l . If a
thin crystal is o r i e n t e d in such a w a y t h a t only o n e
diffracted b e a m is excited, t h e s o l u t i o n h a s t w o r o o t s
leading t o the t w o Bloch w a v e functions (Hirsch et al.
1965). T h e physical implication of these s o l u t i o n s is
t h a t the electron c u r r e n t flow in t h e direction parallel
to the reflecting p l a n e s (i.e., parallel t o the incident
2
2
b e a m ) is m o d u l a t e d laterally as sin ng o r c o s ng t o
form s t a n d i n g waves with the periodicity of the set of
planes t h a t give rise t o t h e diffracted b e a m (see Fig. 1).
A t t h e exact B r a g g c o n d i t i o n b o t h w a v e s a r e excited
equally, while for positive o r negative d e v i a t i o n s from
the B r a g g o r i e n t a t i o n either of the t w o waves m a y be
preferentially excited. Since the w a v e function is t w o
d i m e n s i o n a l for the t w o - b e a m case, t h a t is, c o n s t a n t
in the direction n o r m a l to the p l a n e of Fig. 1, a
50
B l o c h wave 2
O9
Figure 1
The standing wave pattern of the primary electron beam
in relation to the atomic planes giving rise to a single
diffracted beam
2.
Applications
2.1 Planar
Channelling
Channelling-Enhanced
Microanalysis
Channelling
T h e site o c c u p a t i o n c a n be quantified if a n a s s u m p
tion is m a d e t h a t either A or a t o m s o c c u p y only o n e
of the sublattices a n d the p h a s e c o m p o s i t i o n is
k n o w n . In general the characteristic x-ray intensity /
for a n y element Xi (/ elements in the p h a s e ) for a given
o r i e n t a t i o n of the electron b e a m c a n be expressed as
a linear s u m of the c o n t r i b u t i o n s from each of the
parallel planes (, , A , ...)
= PXMX/XCXI\
+ PxMxfx{\
- Cx)l\
(1)
"=/
(2)
by Electron
Energy
Loss
51
Channelling-Enhanced
Microanalysis
XB
XB
Figure 2
(a) The channelling technique applied to the B2 structure shown in a [001] projection. The standing wave pattern with
g = 100 has intensity peaks on A planes or planes. The standing wave pattern with g = 110 has intensity peaks on
planes which are chemically identical, (b) Experimental spectra from a Ti-Al-Nb alloy with a B2 structure obtained with
a negative excitation error (S<0) and a positive excitation error ( S > 0 ) for g= 100. The spectra are normalized to the
titanium peak (not shown) and therefore indicate large changes in / T i/ / Nb but little change in / A, / / Nb for the two
orientations. Aluminum and niobium atoms therefore occupy the same sublattice. Note that g = 200 is also excited
illustrating the difficulty of attaining a strictly two-beam condition, and therefore the standing pattern in (a) will include
contributions from other Bloch waves. (For further details see Banerjee et al. 1988)
52
Chemical
3. Experimental
Requirements
Analysis
of Solid
Surfaces
Bibliography
Banerjee D, Gogia A K, Nandi , Joshi V A 1988 A new
ordered orthorhombic phase in a Ti 3Al-Nb alloy. Acta
Metall. 36: 871-82
Hirsch A, Howie A, Nicholson R B, Pashley D W,
Whelan J 1965 Electron Microscopy of Thin Crystals.
Butterworth, London
Krishnan 1987 When is parallel illumination best for
ALCHEMI? Ultramicroscopy 23: 199-204
Krishnan 1988 Atomic site and species determinations
using channelling and related effects in analytical electron
microscopy. Ultramicroscopy 24: 125-42
Krishnan , Thomas G 1984 A generalisation of atom
location by channelling enhanced microanalysis. J.
Microscopy 136: 97-101
Roussouw C J, Turner S, White J 1988 Axial electron
channelling analysis of perovskite. Philos. Mag. 57:
209^7
Spence J C H, Tafto J 1983 ALCHEMI: a new technique for
locating atoms in small crystals. J. Microscopy 130: 14754
Williams D 1984 Practical Analytical Electron Microscopy
in Materials Science. Philips Electron Optics Publishing,
Mahwah, NJ
D . Banerjee
[Defence Metallurgical R e s e a r c h
L a b o r a t o r y , H y d e r a b a d , India]
53
Chemical
Analysis
of Solid
Surfaces
7.
Vibrational
e~(E')
(a)
Spectroscopies
54
e(E)
Solid
vacuum
(b)
Figure 1
(a) A schematic view of the vibrational techniques,
infrared (ir) and low-energy-electron loss spectroscopies
(LEELS), probing a simple molecule adsorbed on a solid
surface, (b) A schematic representation of x-ray and
ultraviolet photoelectron spectroscopies (XPS and UPS,
respectively) and Auger electron spectroscopy (AES)
probing a solid surface. Energy is plotted on the vertical
axis with electrons bound to the solid being positioned
below the vacuum level and the kinetic energy of ejected
electrons is given by their position above the vacuum level
Chemical
1700
1800
240
780
1900
2000
2100
2200
1320
I860
2400
2940
Wavenumber
( c m ')
Figure 2
Carbon monoxide vibrational spectra: classical ir
absorption spectra for (a) the molecular complex Fe 2(CO) 9
(Cotton 1960) and (b) CO adsorbed on high-surface-area
nickel supported on S i 0 2 (Eischens et al. 1956); (c) the
electron-energy-loss spectrum for CO adsorbed on the
(100) crystal face of nickel (Andersson 1977)
A s a n e x a m p l e of t h e c h e m i s o r p t i o n a n a l o g u e , the
ir s p e c t r u m of C O c h e m i s o r b e d o n S i 0 2 - s u p p o r t e d
nickel is s h o w n in Fig. 2 b . H e r e a g a i n , there is a n
1
a b s o r p t i o n p e a k a b o v e 2000 c m " which is assigned t o
the linearly b o u n d C O molecule a n d a n a b s o r p t i o n
-1
p e a k below 2000 c m
ascribed t o the b r i d g e d form.
H o w e v e r , t h e b e h a v i o r of the spectra is c o m p l e x with
varying a m o u n t s of c h e m i s o r b e d C O , p e r h a p s as a
result of lateral i n t e r a c t i o n s b e t w e e n a d s o r b e d C O
molecules, C O being b o u n d t o a n a r r a y of surface
sites, o r d u e t o s u p p o r t i n t e r a c t i o n s .
T h e difficulty in o b t a i n i n g a detailed i n t e r p r e t a t i o n
of such e x p e r i m e n t s , as i n d i c a t e d earlier, stems largely
from t h e f o r m of the s a m p l e s r e q u i r e d , which are n o t
a m e n a b l e t o a d e q u a t e surface c h a r a c t e r i z a t i o n . H o w
ever, a n a l t e r n a t i v e t e c h n i q u e for s t u d y i n g the v i b r a
tional s t r u c t u r e of surfaces a n d a d s o r b e d species h a s
b e c o m e available which largely c i r c u m v e n t s this diffi
culty. T h e t e c h n i q u e t a k e s a d v a n t a g e of t h e energy
losses suffered b y very-low-energy electrons in scatter
ing from surfaces a n d a d s o r b e d species, a n d c a n be
Analysis
of Solid
Surfaces
2. Photoelectron
Spectroscopy
T h e v i b r a t i o n a l spectroscopies p r o v i d e i n f o r m a t i o n
c o n c e r n i n g local b o n d i n g , which ultimately h a s its
source in the electronic s t r u c t u r e of the system. T h e
p h o t o e l e c t r o n t e c h n i q u e s , o n the o t h e r h a n d , p r o b e
b o n d i n g in t e r m s of the electronic characteristics of
the system. T h i s is a c c o m p l i s h e d by exciting electrons
from their b o u n d states with nearly m o n o c h r o m a t i c
light (in the uv a n d x-ray p o r t i o n s of the e l e c t r o m a g
netic s p e c t r u m ) a n d energy a n a l y z i n g the resulting
p h o t o e l e c t r o n s . Historically, the energy r a n g e of the
r a d i a t i o n h a s been b r o k e n i n t o regions a c c o r d i n g to
the m o d e of p r o d u c t i o n a n d these h a v e been referred
to as ultraviolet ( U P S ) a n d x-ray ( X P S ) p h o t o e l e c t r o n
spectroscopies (for the m o s t p a r t , U P S h a s involved
valence-level a n d X P S core-level studies).
T h e core-level w o r k p r o b e s the local chemical en
v i r o n m e n t by l o o k i n g for c h a n g e s in core-level bind
ing energies as the chemical e n v i r o n m e n t is altered.
T h e s e chemical shifts result from valence-level c h a r g e
transfer a n d e n v i r o n m e n t a l electron-screening effects
( S i e g b a h n 1974). T h e a d v a n t a g e of the core-level
p h o t o e l e c t r o n t e c h i q u e is t h a t , since core-level bind
ing energies are characteristic of the p a r t i c u l a r a t o m
being excited, the results a r e a t o m specific (the overall
energy p o s i t i o n s p r o v i d i n g an elemental analysis
55
Surfaces
56
4
8
12
Relative electron energy (eV)
Figure 3
Ultraviolet photoelectron spectra for (a) CO adsorbed on
the (111) crystal face of palladium, (b) the molecular
complex Rh 6(CO) 16 and (c) the gas phase CO molecule
(Conrad et al. 1976). The energy scale is referred to the
Fermi energy
specific. R a t h e r , it t e n d s t o a v e r a g e c o n t r i b u t i o n s
from the system as a w h o l e . T h u s , m e a s u r e m e n t s o n
small coverages of C O o n p a l l a d i u m a r e m a d e with
difficulty b e c a u s e of t h e lack of c o n t r a s t with respect
t o the m e t a l d-level c o n t r i b u t i o n . T h i s lack of c o n t r a s t
is certainly evident from the fact t h a t n o indication is
given in Figs. 3a a n d 3b t h a t the bridged o r linear
b o n d i n g sites p r o d u c e spectral differences ( R h 6 ( C O ) 1 6
h a s four b r i d g e d a n d 12 linear b o n d i n g sites for C O ) .
F u r t h e r m o r e , there is n o i n d i c a t i o n of b a c k d o n a t i o n
of m e t a l d electrons i n t o t h e n o r m a l l y e m p t y 2n
a n t i b o n d i n g level of t h e C O as a result of the b o n d i n g .
T h e b a c k - b o n d i n g m o d e l , s h o w n in Fig. 4, h a s
b e c o m e very i m p o r t a n t in c o n c e p t u a l i z i n g the C O m e t a l i n t e r a c t i o n . Back d o n a t i o n i n t o the C O In
a n t i b o n d i n g state from the m e t a l d electrons helps t o
explain w h y the b o n d b e t w e e n c a r b o n a n d oxygen is
w e a k e n e d (as evidenced by the v i b r a t i o n a l results
discussed in Sect. 1) as a result of the m e t a l i n t e r a c t i o n
a n d is i m p o r t a n t in u n d e r s t a n d i n g the a d s o r p t i o n as
being the first step t o w a r d surface dissociation. T h i s
c o n c e p t h a s n o t been verified b e y o n d the v i b r a t i o n a l
Chemical
Figure 4
The back-bonding model for CO interactions. Relevant
metal d orbitals are shown to the left, CO orbitals to the
right and complex orbitals in the center. The primary
interaction results from the overlap of the filled 5
molecular orbital of CO with the empty metal d orbital.
The resulting charge transfer is partially compensated by
back donation from the filled metal d orbitals into the
normally empty antibonding CO In molecular orbital
3. Auger
Electron
Spectroscopy
A u g e r electron s p e c t r o s c o p y ( A E S ) , w h i c h h a s
received r e n e w e d a t t e n t i o n as a p r o b e of valence
electronic s t r u c t u r e ( R y e et al. 1979), s h o w s p r o m i s e
for yielding i n f o r m a t i o n w h i c h c o m p l e m e n t s a n d
extends t h a t o b t a i n e d from t h e p h o t o e l e c t r o n tech
niques. P h o t o e l e c t r o n s o r i g i n a t e from valence states
of the c o m p l e t e system a n d for c h e m i s o r p t i o n this c a n
involve electrons from the s u b s t r a t e as well as from
c h e m i s o r b e d species. In c o n t r a s t , A E S yields i n f o r m a
tion a b o u t the valence electronic s t r u c t u r e in t h e
i m m e d i a t e n e i g h b o r h o o d of a n a t o m i c p o s i t i o n . T h i s
localization results from t h e fact t h a t t h e initial step in
A E S is the ejection of a c o r e electron by either p h o t o n
or electron i m p a c t . T h u s , t h e initial state in A E S is t h e
final state in X P S . T h e system c a n t h e n relax by
h a v i n g this c o r e h o l e filled by a higher lying electron
with t h e excess energy being given to t h e ejection of a
second electron, t h e A u g e r electron. T h e chemical
Analysis
of Solid
Surfaces
57
Chemical
Analysis
of Solid
Surfaces
A ckno
wledgement
T h e w o r k of t h e a u t h o r s is s p o n s o r e d by t h e U S
D e p a r t m e n t of E n e r g y u n d e r C o n t r a c t N o . D E AC04-76-DP00789.
See also: Auger Electron Spectroscopy; Depth Profiling;
Electron Spectroscopy for Chemical Analysis; Infrared
Spectroscopy
Bibliography
-100
-80
-60
( F k- I c)
-40
-20
(eV)
Figure 5
Auger electron spectra for (a) C(KVV) of CO,
(b) N(KVV) of NO, (c) C(KVV) of Co(CO) 3NO and
(d) Mo(CO) 6. The notation C(KVV) refers to an initial
carbon K(ls) core hole and both final-state holes in the
valence levels
4.
Summary
T h e further d e v e l o p m e n t a n d e x p l o i t a t i o n of these
techniques, which are sensitive to chemical e n v i r o n
m e n t , offer great p o t e n t i a l for o b t a i n i n g a n u n d e r
s t a n d i n g of the n a t u r e of surface chemical reactivity.
U n f o r t u n a t e l y , n o n e of the t e c h n i q u e s presently avail
able are c a p a b l e of i n d e p e n d e n t l y p r o v i d i n g sufficient
i n f o r m a t i o n to achieve this u n d e r s t a n d i n g a n d a
concerted a p p r o a c h involving several of the m e t h o d s
is n o r m a l l y required. In a d d i t i o n , w o r k with wellcharacterized s u r f a c e - a d s o r b a t e systems a n d stan
d a r d m o l e c u l a r species is a n a b s o l u t e necessity. T h e
all pervasive influence of surface chemical effects in
m a t e r i a l s p r o p e r t i e s a n d processing, h o w e v e r , m a k e s
the c o m p l i c a t i o n s of m o d e r n surface research well
w o r t h the extra effort.
58
Composite
fiber c o m p o s i t e ( C F C ) p a n e l s o n satellite s t r u c t u r e s ,
which m i g h t be only 0.25 m m thick, to t h e 30 m long,
25 m m thick, G R P hull of a n a v a l m i n e h u n t e r . T h e
r e q u i r e m e n t s for n o n d e s t r u c t i v e e v a l u a t i o n ( N D E )
will therefore also vary widely a n d it is only possible
to give here a s h o r t guide t o t h e principles involved
a n d an i n t r o d u c t i o n to t h e t e c h n i q u e s available. F o r
simplicity the discussion will largely be limited t o
materials h a v i n g o r g a n i c m a t r i c e s . M e t a l - m a t r i x c o m
posites are of g r o w i n g i m p o r t a n c e a n d a significant
a m o u n t of N D E h a s been e m p l o y e d o n t h e m , b u t the
N D E r e q u i r e m e n t s a r e as yet far from clear ( R e y n o l d s
1986).
7. Nondestructive
Evaluation
Policy
T h e principal objective of n o n d e s t r u c t i v e e v a l u a t i o n
is to p r o v i d e a s s u r a n c e o n the q u a l i t y a n d s t r u c t u r a l
integrity of a p a r t i c u l a r c o m p o n e n t . T h i s m a y be
achieved either directly by using n o n d e s t r u c t i v e in
spection t e c h n i q u e s t o detect specific defects, o r in
directly by m o n i t o r i n g o r c o n t r o l l i n g the fabrication
process. T h e latter a p p r o a c h is, h o w e v e r , really only
an extension of t h e u s u a l process c o n t r o l p r o c e d u r e s
which a r e necessary in o r d e r t o achieve a consistent
p r o d u c t . A d d i t i o n a l N D E m i g h t be p r o v i d e d t o assist
in optimizing the fabrication p r o c e d u r e by, for ex
a m p l e , the a d d i t i o n of a device t o m o n i t o r t h e local
state of c u r e . T h e m a j o r i t y of N D E is, h o w e v e r ,
c o n c e r n e d with the d e t e c t i o n a n d c h a r a c t e r i z a t i o n of
defects o r a n o m a l i e s .
In o r d e r t o illustrate the types of defects t h a t
m i g h t be s o u g h t , consider, for e x a m p l e , a c a r b o n fiber c o m p o s i t e a e r o s p a c e c o m p o n e n t fabricated in a n
autoclave. T h e following defects are likely t o be of
importance: delaminations (separations
between
plies), d i s b o n d s , p o r o s i t y in the l a m i n a t e s o r b o n d
line, fiber m i s o r i e n t a t i o n , missing plies, v a r i a t i o n s in
fiber v o l u m e fraction (resin-rich o r resin-starved
areas), foreign inclusions a n d h o n e y c o m b c o r e misfit
(gaps a n d splices).
Clearly, in o r d e r t o decide which defects m u s t be
detected, a n d t o set defect-acceptance s t a n d a r d s , it is
necessary t o u n d e r s t a n d t h e effect t h a t a specific
defect h a s o n t h e p e r f o r m a n c e of a given c o m p o n e n t .
Inspection p r o c e d u r e s c a n be b o t h expensive a n d time
consuming and many composite components have
p r o v e d t o be surprisingly t o l e r a n t t o defects, so care
should be t a k e n t o e n s u r e t h a t t h e r e q u i r e m e n t s for
inspection a r e n o t unnecessarily r i g o r o u s ( S t o n e a n d
C l a r k e 1987).
A s a general guide it m a y be said t h a t there a r e t w o
m a i n a p p r o a c h e s t o t h e use of N D E t o assess quality.
T h e first a p p r o a c h a i m s t o p r o v i d e a q u a l i t a t i v e
assessment a n d is typified by t h e w a y t h a t r a d i o g r a
p h y is used t o assess w h e t h e r the level of p o r o s i t y is
acceptable. R a d i o g r a p h s of p r o d u c t i o n c o m p o n e n t s
are c o m p a r e d with t h o s e of d e v e l o p m e n t c o m p o n e n t s .
Materials:
Nondestructive
Evaluation
2.
Visual
Inspection
3. Ultrasonic
Inspection
59
Composite
Materials:
Nondestructive
Evaluation
Figure 1
-scan showing front and back surface reflections from a
ten-ply composite
Testing
3.4 Ultrasonic
C-Scan
In this type of p r e s e n t a t i o n a m o r e c o m p l e x s c a n n i n g
system is used such t h a t the t r a n s d u c e r is s c a n n e d in a
p l a n e parallel t o the surface of the specimen in a
rectilinear raster p a t t e r n . A r e c o r d e r p e n is c o u p l e d to
t h e t r a n s d u c e r m a n i p u l a t o r so t h a t t h e p e n m o v e m e n t
accurately r e p r o d u c e s the s c a n n i n g p a t t e r n . In this
w a y a p l a n view of the a t t e n u a t i o n d i s t r i b u t i o n is
o b t a i n e d , allowing, for e x a m p l e , a n assessment of the
lateral extent of d a m a g e . It is usual t o use a n i m m e r
sion system in which the t r a n s d u c e r is s c a n n e d in the
A-Scan
T h e simplest p r e s e n t a t i o n , t h e - s c a n , displays t h e
ultrasonic i n f o r m a t i o n a c q u i r e d at a single p o i n t in a
specimen. It is usually displayed o n a n oscilloscope, as
in Fig. 1, a n d consists of a series of echoes w h o s e
position a l o n g the h o r i z o n t a l axis c a n be calibrated in
t e r m s of d e p t h in t h e s a m p l e u n d e r test so t h a t t h e
position of a reflector c a n be m e a s u r e d . T h e a m p l i
t u d e of each e c h o will give s o m e i n d i c a t i o n of t h e size
a n d n a t u r e of the reflector.
It is i m p o r t a n t to n o t e t h a t , if a defect is present a n d
is of a type t h a t reflects a large fraction of the incident
s o u n d w a v e , then only a very small p r o p o r t i o n will
p r o p a g a t e b e y o n d the defect. A n y a d d i t i o n a l reflec
60
B-Scan
Figure 2
B-scan showing depth of impact damage in a CFC test
specimen where thickness tapers from 4 mm to 3 mm
Composite
Materials:
Nondestructive
Evaluation
Figure 3
C-scan showing area of impact damage of specimen in
Fig. 2
w a t e r t a n k a b o v e t h e specimen. If a single t r a n s d u c e r
is e m p l o y e d in a " p u l s e - e c h o " configuration, a glass
reflector plate placed b e h i n d t h e specimen is often
used. T h e received signal e c h o from t h e glass p l a t e is
m o n i t o r e d using a time-gate m o d u l e , which c o n v e r t s
the a m p l i t u d e of t h e largest reflection within a preset
time interval to a voltage. In simple systems this is
used t o p r o d u c e a gray-scale p r e s e n t a t i o n o n c u r r e n t sensitive p a p e r s h o w i n g t h e v a r i a t i o n in a t t e n u a t i o n .
F i g u r e 3 s h o w s a C-scan of t h e specimen used as a n
e x a m p l e of B-scanning in Fig. 2.
Alternatively this d a t a m a y be stored in a c o m
p u t e r , allowing t h e use of v a r i o u s c o l o r p r e s e n t a t i o n s .
Simple displays require t h e a r b i t r a r y selection of a
limited r a n g e of colors a n d a r e n o t always easy t o
interpret, b u t m o r e sophisticated systems c a n offer a
significant increase in the d y n a m i c r a n g e displayed.
T h e big a d v a n t a g e of c o m p u t e r s t o r a g e , h o w e v e r , lies
in its ability t o p r o d u c e , from a single scan, p r e s e n t a
tions c o r r e s p o n d i n g to different a t t e n u a t i o n t h r e s h
olds. W h e t h e r o r n o t c o m p u t e r s t o r a g e is used it is
i m p o r t a n t t o n o t e t h a t the t h r e s h o l d settings a r e
a r b i t r a r y a n d c o m p a r a t i v e l y small c h a n g e s c a n result
in quite different C-scans being p r o d u c e d . T h e C-scan
will only be meaningful if t h e r e l a t i o n s h i p b e t w e e n
the settings a n d t h e p a r a m e t e r p l o t t e d is k n o w n b y
calibration.
T h e r e a r e s o m e d i s a d v a n t a g e s in using i m m e r s i o n
testing e q u i p m e n t ( S t o n e a n d C l a r k e 1987); a l t e r n a
tive techniques are therefore s o m e t i m e s used.
3.5 Ultrasonic Jet Probes
A c o m m o n l y used t e c h n i q u e , which still uses w a t e r as
a c o u p l a n t , is the jet (or squirter) p r o b e t e c h n i q u e .
H e r e the c o m p o n e n t is n o t i m m e r s e d ; instead, the
coupling w a t e r impinges o n t o t h e surface of the
c o m p o n e n t in a jet a l o n g which the u l t r a s o u n d t r a
vels. T h e w a t e r jet acts as a w a v e g u i d e to t h e s o u n d .
T h e m a i n difficulty is t o m a k e sure, by correct design
Probes
In a p p l i c a t i o n s w h e r e t h e c o m p o s i t e m u s t n o t c o m e
i n t o c o n t a c t w i t h w a t e r , roller p r o b e s c a n be used.
T h e u l t r a s o n i c t r a n s d u c e r element is held inside a
wheel a n d the s o u n d p r o p a g a t e d i n t o the specimen
t h r o u g h a soft r u b b e r tire. T h i s t e c h n i q u e is generally
used a t low frequencies a n d c a n b e used for t h e r a p i d
d e t e c t i o n of in-service d a m a g e b u t is n o t really suit
able for its detailed c h a r a c t e r i z a t i o n .
3.7 Imaging
Systems
A c o n s i d e r a b l e a m o u n t of w o r k is being carried o u t in
t h e field of u l t r a s o n i c i m a g i n g systems, s o m e of which
is a i m e d a t i m a g i n g d a m a g e in c o m p o s i t e s . D e l a m i n a t i o n s a r e of p r i m e i m p o r t a n c e w h e n c o n s i d e r i n g
d a m a g e m e c h a n i s m s in C F C a e r o s p a c e structures,
a n d a n u l t r a s o n i c i m a g i n g system h a s recently been
d e v e l o p e d (Lloyd a n d W r i g h t 1986) specifically a i m e d
a t p r o v i d i n g a pictorial p r e s e n t a t i o n of t h e distribu
tion of d e l a m i n a t i o n s . Essentially such a system uses a
c o m b i n a t i o n of the B- a n d C-scan m e t h o d s to gener
ate isometrically projected images of defects as
p s e u d o - t h r e e - d i m e n s i o n a l displays. T h e software
p a c k a g e within this system e n a b l e s the viewer to select
viewing angle a n d r o t a t i o n a l p o s i t i o n of the object as
well as a n o p t i o n t o magnify. B o t h the a r e a a n d
t h r o u g h - t h i c k n e s s p o s i t i o n of t h e d a m a g e c a n there
fore be viewed with a clarity n o t possible by c o n v e n
tional u l t r a s o n i c t e c h n i q u e s (see Fig. 4.)
4. Radiographic
Methods
4.1 X- Radiography
R a d i o g r a p h y is b a s e d o n t h e differential a b s o r p t i o n
of p e n e t r a t i n g r a d i a t i o n . Because of v a r i a t i o n s in
thickness o r differences in a b s o r p t i o n characteristics
c a u s e d by v a r i a t i o n s in c o m p o s i t i o n , different p a r t s of
a c o m p o n e n t a b s o r b different a m o u n t s of r a d i a t i o n .
U n a b s o r b e d radiation passing through the compon
e n t m a y be r e c o r d e d o n film, viewed o n a fluorescent
screen o r m o n i t o r e d by a r a d i a t i o n d e t e c t o r . Access t o
t h e r e a r surface is therefore necessary, a n d this m a y
limit t h e a p p l i c a t i o n s for which r a d i o g r a p h y is suit
able. It is generally used t o reveal h i d d e n c h a n g e s in
thickness o r a r e a s h a v i n g a different density from the
s u r r o u n d i n g m a t e r i a l . It is therefore widely used t o
61
Composite
Materials:
Nondestructive
Evaluation
Figure 4
Ultrasonic image of impact damage of specimen in Fig. 2
62
4.2 Computer-Aided
Tomography
A c o n v e n t i o n a l r a d i o g r a p h is a t w o - d i m e n s i o n a l pres
e n t a t i o n of a t h r e e - d i m e n s i o n a l object, the density of
the i m a g e at each p o i n t in the r a d i o g r a p h being
g o v e r n e d by the t o t a l a t t e n u a t i o n experienced by t h a t
p a r t of t h e x-ray b e a m . T h e r e is n o i n f o r m a t i o n o n the
c o n t r i b u t i o n t h a t each element of the object m a k e s t o
the t o t a l a t t e n u a t i o n . C o m p u t e r - a i d e d t o m o g r a p h y
( C A T ) , o n the o t h e r h a n d , m e a s u r e s the intensity of xray t r a n s m i s s i o n a l o n g m a n y p a t h s in a single p l a n e ,
a n d uses a c o m p u t e r t o calculate the a t t e n u a t i o n
c o n t r i b u t e d by each element in the p l a n e ( G i l b o y a n d
F o s t e r 1982). Because industrial versions of such
systems a r e expensive, a p p l i c a t i o n s to c o m p o s i t e s
h a v e been s o m e w h a t limited b u t they are n o w being
used extensively for the inspection of rocket m o t o r s
a n d cases. E v e n units designed for medical use are
p r o v i n g v a l u a b l e for c o m p o n e n t s such as helicopter
r o t o r blades, an e x a m p l e of which is s h o w n in Fig. 6.
4.3 Neutron
Radiography
N e u t r o n r a d i o g r a p h y is often r e g a r d e d as a c o m p l e
m e n t a r y t e c h n i q u e to r a d i o g r a p h y ; in p a r t i c u l a r this
is because n e u t r o n s are strongly a b s o r b e d by the
lightest elements (including h y d r o g e n ) , w h e r e a s heavy
elements such as lead a r e relatively t r a n s p a r e n t t o
n e u t r o n s . N o n r e a c t o r sources of n e u t r o n s a r e avail
able b u t they a r e at present b o t h expensive a n d
s o m e w h a t c u m b e r s o m e ; f u r t h e r m o r e , the source size
is m u c h g r e a t e r t h a n t h a t available in r a d i o g r a p h y ,
t h u s r e d u c i n g the resolution a t t a i n a b l e . F o r these a n d
o t h e r r e a s o n s there h a v e been relatively few applica
tions of n e u t r o n r a d i o g r a p h y to c o m p o s i t e s . O n l y for
Figure 5
Penetrant enhanced ray of impact damage
Composite
Materials:
Nondestructive
Evaluation
5. Thermographic
Methods
T h e s e m a y be conveniently divided i n t o t w o m a i n
types: p a s s i v e w h e r e there is a n externally applied
h e a t i n g or c o o l i n g s o u r c e a n d a c t i v e w h e r e there
are internally g e n e r a t e d h e a t i n g o r c o o l i n g effects. I n
b o t h cases t h e surface t e m p e r a t u r e d i s t r i b u t i o n is
m o n i t o r e d a n d e x a m i n e d for a n o m a l i e s t h a t indicate
the presence of defects. T h e active m e t h o d , h o w e v e r ,
h a s only really f o u n d a p p l i c a t i o n in t h e m o n i t o r i n g of
fatigue tests w h e r e h e a t is g e n e r a t e d by fretting effects
at sites of internal d a m a g e .
In the passive m e t h o d , which h a s been m u c h m o r e
widely e m p l o y e d , t h e surface of a c o m p o n e n t is
subjected to a r a p i d t e m p e r a t u r e c h a n g e a n d t h e
s u b s e q u e n t h e a t flow m o n i t o r e d . A variety of h e a t
sources h a v e been investigated, v a r y i n g from simple
h o t - a i r g u n s t o b a n k s of flash t u b e s . T h e w a y in w h i c h
the h e a t is dissipated d e p e n d s o n t h e t h e r m a l c o n d u c
tivity of the c o m p o s i t e a n d o n the n a t u r e a n d l o c a t i o n
of a n y defects. If there is a d e l a m i n a t i o n in a l a m i n a t e ,
for e x a m p l e , t h e n less h e a t will be t r a n s m i t t e d
t h r o u g h t h e defective a r e a resulting in a h o t s p o t o n
the h e a t e d surface a n d a cold s p o t o n t h e b a c k
surface. It is possible t o m o n i t o r either t h e front o r the
b a c k surface ( p r o v i d e d t h a t this is accessible). By
a n a l o g y with u l t r a s o n i c s t e r m i n o l o g y t h e f o r m e r is
often called a p u l s e - e c h o t e c h n i q u e a n d t h e latter,
t h r o u g h t r a n s m i s s i o n . It is u s u a l for s o m e k i n d of
infrared-sensitive c a m e r a to be used a n d for the
o u t p u t t o be stored o n video t a p e . N o t only d o e s this
6.
Vibration
and Mechanical
Impedance
Methods
A l t h o u g h v i b r a t i o n t e c h n i q u e s f o r m e d t h e basis of
s o m e of t h e m o s t a n c i e n t m e t h o d s of N D T it is only
c o m p a r a t i v e l y recently t h a t they h a v e gained a scien
tific basis ( A d a m s a n d C a w l e y 1985). F o r convenience
these t e c h n i q u e s m a y be divided i n t o global a n d local
m e t h o d s . I n t h e former a w h o l e c o m p o n e n t is excited
by a pulse o r by c o n t i n u o u s excitation, a n d n a t u r a l
frequencies
and
damping
characteristics
are
m e a s u r e d . T h i s a p p r o a c h h a s been used t o p r o v i d e a
r a p i d m e t h o d of p r o d u c t i o n inspection for c o m
p o n e n t s of simple g e o m e t r y such as small missilel a u n c h e r t u b e s . W i t h local m e t h o d s only a small a r e a
is excited a n d its m e c h a n i c a l r e s p o n s e m e a s u r e d . Such
m e t h o d s h a v e t h e a d v a n t a g e of only r e q u i r i n g access
t o o n e surface a n d d o n o t need a c o u p l a n t . T h e y are
p a r t i c u l a r l y suited t o t h e d e t e c t i o n of d i s b o n d s
b e t w e e n thin c o m p o s i t e skins a n d a f o a m o r h o n e y
comb substructure.
7. Optical
Methods
63
Composite
Materials:
Nondestructive
Evaluation
stressed in s o m e w a y in o r d e r t o g e n e r a t e t h e b a c k
g r o u n d d i s p l a c e m e n t p a t t e r n s against which t h e
a n o m a l i e s a r e revealed. T h e w a y in which these dis
placements are generated m a y govern whether or not
a p a r t i c u l a r defect is revealed. Very simple m e t h o d s
are, however, often sufficient. F o r e x a m p l e , gentle
heating with a h o t - a i r g u n h a s p r o v e d a very effective
w a y of revealing d i s b o n d s between a c o m p o s i t e skin
a n d a h o n e y c o m b core.
8. Eddy
Current
Inspection
9. Acoustic
Emission
64
10. Adhesive-Bonded
Joints
C o m p o s i t e c o m p o n e n t s a r e frequently fabricated b y
adhesively b o n d i n g t o g e t h e r pre-cured elements. P o o r
b o n d i n g c a n easily result in p l a n e s of w e a k n e s s so t h e
inspection of b o n d lines is often necessary. H o w e v e r ,
a l t h o u g h t h e d e t e c t i o n of b o n d - l i n e defects is perfectly
feasible, n o n d e s t r u c t i v e m e a s u r e m e n t
of b o n d
strength is extremely difficult. A l s o , a clear distinction
m u s t b e d r a w n b e t w e e n t h e adhesive s t r e n g t h of t h e
interface b e t w e e n t h e a d h e r e n d a n d t h e adhesive
layer, a n d t h e cohesive strength of t h e adhesive itself.
Discrete defects, such as d i s b o n d s o r a r e a s of p o r o s
ity, a r e detectable in m u c h t h e s a m e w a y as they a r e
in t h e c o m p o s i t e itself. T h e presence of release film
c a n , however, cause a p r o b l e m . Small isolated a r e a s
of film a r e usually f o u n d w i t h o u t difficulty, b u t a
c o m p l e t e sheet of thin (0.07 m m ) polyester film is
m u c h h a r d e r t o find. T h i s is, in fact, very similar t o t h e
s i t u a t i o n e n c o u n t e r e d with a " s t u c k b o n d , " w h e r e t h e
t w o surfaces a r e in i n t i m a t e c o n t a c t b u t t h e b o n d h a s
n o s t r e n g t h . C o n t a m i n a t i o n of t h e a d h e r e n d surfaces
p r i o r t o b o n d i n g c a n b e highly d e t r i m e n t a l a n d diffi
cult t o detect ( S t o n e 1986).
11.
Conclusion
Compton
120
Scattering
60
90
8
6
150
30
_4
10 k e y
Bibliography
Adams R D, Cawley 1985 Vibration techniques in nondes
tructive testing. In: Sharpe R S (ed.) 1985 Research
Techniques in Nondestructive Testing, Vol. 7. Elsevier,
London.
Arrington 1987 Acoustic emission. In: Summerscales J
(ed.) 1987 Non-destructive Testing of Fibre Reinforced
Plastics Composites, Vol. 1. Elsevier, London
Gilboy W B, Foster J 1982 Industrial applications of
computerised tomography with and gamma radiation.
In: Sharpe R S (ed.) 1982 Research Techniques in Nondes
tructive Testing, Vol. 6. Elsevier, London
Lloyd A, Wright A 1986 An introductory investigation
into the performance of an ultrasonic imaging system.
Royal Aircraft Establishment Report TR 86063. RAE,
Farnborough, UK
McLaughlin V, Mirchand G, Ciekurs V 1987
Infrared thermographic flaw detection in composite lami
nates. J. Eng. Mater. Technol. 109: 146-50
Reynolds W 1986 Nondestructive testing techniques for
metal matrix composites. Harwell Report AERE R
13040. Harwell Laboratory, Didcot, UK
Sproat W H, Lewis W 1986 Barely visible impact damage
(BVID) detection in aircraft composites. Proc. AIAA/
SOLE 2nd Aerospace Maintenance Conf. American Insti
tute of Aeronautics, New York
Stone D E W 1986 Non-destructive methods of characteris
ing the strength of adhesive-bonded jointsa review.
Royal Aircraft Establishment Report TR 86058. RAE,
Farnborough, UK
Stone D E W , Clarke 1987 Non-destructive evaluation of
compositesan overview. Proc. 6th Int. Conf. Composite
Materials, 2nd European Conf. Composite Materials. Else
vier, London
Walker C A, McKelvie J 1987 Optical methods. In: Sum
merscales J (ed.) 1987 Non-destructive Testing of Fibre
Reinforced Plastics Composites, Vol. 1. Elsevier, London
D . E. W . S t o n e a n d B. C l a r k e
[Royal Aerospace Establishment,
Farnborough, UK]
180
i f
8
I
6
1
4
1 /
2
1
0
1
4
_ 3 02
e" sr" )
Figure 1
The Klein-Nishina cross section for Compton scattering
(as given by Eqn. (3)) plotted as a polar diagram for
incident photon energies Ex of 10 keV, 60 keV and
600 keV. The energy of the scattered photon E2 varies with
the angle of scattering according to Eqn. (2)
from t h e p r o p o r t i o n a l i t y b e t w e e n t h e intensity of t h e
scattered signal a n d t h e density of electrons from
w h i c h they a r e scattered. It results in d e n s i t o m e t r y
a n d i m a g i n g from t h e b a c k s c a t t e r e d signal in situa
tions w h e r e t r a n s m i s s i o n t e c h n i q u e s a r e ineffective for
nondestructive examinations.
1. Basic
Theory
T h e s c a t t e r i n g i n t e r a c t i o n is s h o w n schematically in
the inset t o F i g . 1. C o m p t o n ' s shift f o r m u l a
= (1 - c o s )
(1)
mirelates t h e w a v e l e n g t h shift t o t h e scattering angle
w h e r e h is P l a n c k ' s c o n s t a n t , m is t h e electron m a s s
a n d c is t h e velocity of light. It c a n also be written
m o r e usefully, if less economically, in t e r m s of the
p h o t o n energies a s
= EX
Compton Scattering
^ 6 0 0 k e V
\
1 + 4 ( 1 - cos )
(2)
mc
<3
65
Compton
Scattering
p r o b a b i l i t y of observing t h a t c o m p o n e n t of m o m e n
t u m . T h i s is k n o w n as the C o m p t o n profile J(p:)
which c a n be expressed by t h e e q u a t i o n
APZ)=
Figure 2
The energy of Compton scattered radiation as a function
of the angle of scattering for different incident photon
energies. Large energy losses occur for high-energy
photons at high angles of scattering
66
n(p) dpx
dpy
(4)
Compton
1000
500
E n e r g y (keV)
Figure 3
The mass attenuation coefficients for photoelectric
absorption, elastic scattering and Compton scattering in
concrete as a function of the photon energy (source: J
Hubbell (1969) National Bureau of Standards,
NSRDS-NBS 29)
2. Line Profile
Analysis
This is a i m e d a t p r o v i d i n g i n f o r m a t i o n a b o u t elec
tronic b e h a v i o r in t h e b u l k m a t e r i a l . Defects, inclus
ions, grain b o u n d a r i e s , i m p u r i t i e s a n d so o n h a v e n o
m e a s u r a b l e effect a t their n o r m a l c o n c e n t r a t i o n s . Al
t h o u g h the C o m p t o n line s h a p e is a projection of the
total electron d i s t r i b u t i o n (as s h o w n by E q n . (4)) it
retains a surprising sensitivity t o t h e b e h a v i o r of t h e
outer, s l o w - m o v i n g electrons involved in solid-state
b o n d i n g . T h i s research t o p i c h a s been c o v e r e d by
Williams (1977) a n d h a s been u p d a t e d in review
articles (see, for e x a m p l e , C o o p e r 1985).
G o o d resolution of the C o m p t o n line s h a p e m i g h t
be t h o u g h t of as, for e x a m p l e , 1 0 % of t h e F e r m i
m o m e n t u m in a m e t a l . Such resolution h a s only
recently b e c o m e available from the use of focusing xray optics. W h i l e the characteristic emission from a n
x-ray t u b e a n o d e r e m a i n e d as the source, the flux w a s
t o o low to m a k e such m e a s u r e m e n t s viable. I n s t e a d ,
the bulk of the w o r k of t h e 1980s t r a d e d r e s o l u t i o n
for statistical precision by replacing t h e crystal spec
t r o m e t e r with a s e m i c o n d u c t o r d e t e c t o r a n d t h e x-ray
source with a y-ray i s o t o p e e m i t t e r of generally higher
energy (i.e., greater t h a n 50 keV). In practice this h a s
Scattering
3. Densitometry
and
Imaging
67
Compton
Scattering
Figure 4
A comparison of scattering (detector at S) and
transmission (detector at T) geometries for the detection
of a void or inclusion of linear dimension / and
attenuation coefficient 0 embedded to a distance L in a
matrix characterized by an attenuation coefficient
Bibliography
Cooper J 1985 Compton scattering and electron momen
tum. Rep. Prog. Phys. 48: 415-81
68
M . J. C o o p e r
[University of W a r w i c k ,
Coventry, U K ]
Confocal
Detector
()
(b)
Figure 1
Schematic diagram of the confocal imaging mode: (a) the
basic principle of confocal illumination and imaging for
the in-focus plane; and (b) the rejection of out-of-focus
light in the imaging portion of the system for light
originating above and below the in-focus plane
b e h i n d the p l a n e of t h e d e t e c t o r p i n h o l e . T h u s , t h e
light is c o n v e r g i n g a t t h e p l a n e of t h e p i n h o l e a n d only
a small a m o u n t goes t h r o u g h the p i n h o l e t o be
detected b y t h e p h o t o m u l t i p l i e r . Light o r i g i n a t i n g
from p l a n e s d e e p e r in t h e specimen is indicated in
Fig. l b b y the d a s h e d line a n d is focused in front of
the p l a n e of t h e p i n h o l e . T h i s light is diverging at t h e
p i n h o l e a n d , a g a i n , very little passes t h r o u g h t o t h e
p h o t o m u l t i p l i e r . A t w o - d i m e n s i o n a l i m a g e is col
lected by s c a n n i n g either t h e b e a m o r t h e specimen.
Since light from object p l a n e s a b o v e a n d below t h e
p l a n e of focus is rejected from t h e i m a g e , this t w o d i m e n s i o n a l i m a g e is a n " o p t i c a l s e c t i o n " t h r o u g h the
specimen. A s such it c a n be a w a y of n o n d e s t r u c t i v e l y
imaging three-dimensional or internal structure.
Beam scanning instruments are the most c o m m o n
a n d are of t w o types. T h e first uses a laser as its light
source a n d g a l v a n o m i c m i r r o r s o r a c o u s t o o p t i c a l
devices t o scan t h e b e a m ( W h i t e et al. 1987, Pawley
1990). T h e a c o u s t o o p t i c a l device is used for t h e line
scan (i.e., t h e fast scan d i r e c t i o n ) a n d a g a l v a n o m i c
m i r r o r is used t o scan t h e lines t o form a frame (i.e.,
the slower direction). T h e a d v a n t a g e s of these instru
m e n t s is t h a t they scan a t video rates with laser light
sources. H o w e v e r , m o s t of t h e b e a m s c a n n e d instru
m e n t s use t w o g a l v a n o m i c m i r r o r s a n d a r e limited t o
frame rates of 0.25 s o r longer. T h e second b e a m
scanned type uses a r a p i d l y s p i n n i n g disk with a large
n u m b e r of p i n h o l e s a n d b r o a d b a n d light sources such
as m e r c u r y o r x e n o n l a m p s ( B o y d e et al. 1990, Pawley
1990). I n these i n s t r u m e n t s , t h e holes in t h e disk act as
b o t h illuminating a n d detecting p i n h o l e s ( B o y d e et al.
1990, Pawley 1990). A n a d v a n t a g e of this a p p r o a c h is
t h a t a large n u m b e r of object p o i n t s a r e i m a g e d a t t h e
s a m e time a n d t h e disk c a n be r o t a t e d very rapidly.
A n a r e a detector, such as a c h a r g e d c o u p l e d device
Optical
Microscopy
Confocal
Optical
Microscopy
1. Three-Dimensional
Surfaces
Visualization
of
Complex
70
Figure 2
A set of optical sections and a stereo pair of the fracture
surface of a plastic drinking cup. The eight optical
sections in (a) are separated by 100 in the direction.
The same field is shown in stereo in (b), but comprises 20
superimposed optical sections, each separated by 50 .
The width of the field in both (a) and (b) is 1500 . A
x 4 objective lens with a numerical aperture (NA) of 0.13
was used
Confocal
Optical
Microscopy
2. Three-Dimensional
Inside Transparent
Figure 3
A fracture surface of a plastic material that failed under
tension. The stereo image in (a) shows the perspective
looking down on the surface from above, and is composed
of 37 superimposed optical sections each spaced 10
apart along the direction. A similar field is imaged from
the side in (b), and this stereo pair is composed of 24
superimposed optical sections each separated by 10 .
The field width is 600 in both (a) and (b). A x 10 0.3
NA lens was used for both images
Visualization
Materials
of
Surfaces
S t r u c t u r e s inside t r a n s p a r e n t m a t e r i a l s c a n be visual
ized in three d i m e n s i o n s b y merely focusing i n t o the
m a t e r i a l . T h r e e factors influence t h e d e p t h t o which
i m a g e s c a n b e f o r m e d . T h e first is t h e w o r k i n g dis
t a n c e of t h e lens. T h e s e c o n d is t h e l i g h t - a b s o r b i n g
p r o p e r t i e s of t h e m a t e r i a l . T h e light m u s t traverse t h e
m a t e r i a l twice, o n c e w h e n i l l u m i n a t i n g t h e object a n d
a g a i n after it is reflected from t h e i n t e r n a l s t r u c t u r e .
H i g h l y a b s o r b i n g m a t e r i a l s will r a p i d l y decrease the
i m a g e signal-to-noise r a t i o as a function of d e p t h . T h e
t h i r d is t h e o p a c i t y of the i n t e r n a l s t r u c t u r e s . If a large
p e r c e n t a g e of t h e incident light is reflected from the
i n t e r n a l surface being i m a g e d , it m a y m a s k s t r u c t u r e s
d e e p e r in t h e m a t e r i a l .
A b l o c k of plexiglass t h a t h a s b e e n subjected t o a
m i c r o w a v e field is s h o w n in Fig. 4. T h e t o p surface of
t h e stereo i m a g e is 2500 b e l o w t h e surface of t h e
m a t e r i a l a n d e x t e n d s a n a d d i t i o n a l 1250 i n t o t h e
b l o c k . C a v i t a t i o n spheres a r e clearly s h o w n in a wide
r a n g e of sizes a n d a p p e a r t o b u d from e a c h o t h e r . T h e
larger spheres a r e c o m p o s e d of m a n y small b u b b l e s ,
w h i c h h a v e a large v a r i a t i o n in density within t h e
material. The dense areas appear to mask structures
t h a t m a y b e p r e s e n t d e e p e r in t h e m a t e r i a l . C a b l e
m a t e r i a l s for p o w e r lines a n d t h e interfaces b e t w e e n
s e m i c o n d u c t i v e a n d i n s u l a t i n g layers h a v e been
studied using these m e t h o d s ( H a r i d o s s et al. 1990).
3. Three-Dimensional
Visualization
of
Fibers
F i b e r s a r e increasingly i m p o r t a n t in a wide r a n g e of
m a t e r i a l s b o t h as t h e sole c o m p o n e n t a n d in c o m p o
sites. T w o p o l y e t h y l e n e fibers a r e s h o w n in stereo in
Fig. 5. T h e y were d r a w n in different w a y s , a n d s h o w
m a r k e d l y different s t r u c t u r e . T h e fiber in Fig. 5a is 40
times t h e size of t h o s e in Fig. 5b. B o t h fiber types
s h o w lines c o r r e s p o n d i n g t o surface s t r u c t u r e t h a t r u n
71
Confocal
Optical
Microscopy
Figure 4
Internal cavitation caused by a microwave field in a piece
of plexiglass. This stereo pair is composed of 25
superimposed optical sections each separated by 50
and represents a volume from 2500 to 3750 into
the material. The field width is 1500 . A x 4 0.13 N A
objective lens was used
4. Three-Dimensional
Circuits
Visualization
of
Integrated
72
Figure 5
Stereo images of polyethylene fibers. The fiber in (a) was
supplied by Dr Roger Porter, Polymer Sciences,
University of Massachusetts at Amherst. The field width is
600 and was recorded with a 10 0.3 objective
lens. The fiber in (b) was drawn from a gel and was
provided by Dr Richard Stein, Department of Chemistry,
University of Massachusetts at Amherst. The field width is
150 and was recorded with a 20 0.7 objective
lens and an electronic zoom of 2
Confocal
Optical
Microscopy
Figure 7
Volume rendered images of the fields in Figs. 6a,b. Voxel
View software from Vital Images (Deerfield, IA) was used
on an IBM RISC 6000 320 Power Graphics Workstation
to volume render the images of the IBM chips: (a) is a
reconstruction of the microprocessor chip shown in stereo
in Fig. 6a; and (b) is a reconstruction of the memory chip
shown in stereo in Fig. 6b that has been optimized to
demonstrate surface texture, particularly that of the base
area to the left
cknowledgements
T h i s w o r k w a s partially s u p p o r t e d b y U S Public
H e a l t h Service g r a n t s R R 02984 a n d R R 01219
a w a r d e d b y t h e N a t i o n a l C e n t e r for R e s e a r c h R e
s o u r c e s a n d N S F g r a n t D I R 9108492 s u p p o r t i n g t h e
c o n f o c a l facility a n d t h e Biological M i c r o s c o p y a n d
Image Reconstruction Resource.
See also: Acoustic Microscopy; Optical Microscopy; Scan
ning Electron Microscopy
73
Confocal
Optical
Microscopy
Bibliography
Boyde A 1985 Stereoscopic images in confocal (tandem
scanning) microscopy. Science 230: 1270-2
Boyde A, Xiao T, Corle F, Watson F, Kino G S 1990
An evaluation of unilateral TSM for biological applica
tions. Scanning 12: 273-9
Brakenhoff G J, Blom P, Barends 1979 Confocal scanning
light microscope with high aperture immersion lenses.
/. Microsc. 117: 219-32
Feiling-Wang, Ching-Bo-Juang, Bustamante C, Wu A Y
1990 Electrooptic properties of (Pb, La) (Zr, Ti)0/sub 3/,
BaTio/sub 3/(Sb, Ba)Nb/sub 2/O/sub 6/ and Ba/sub 2/
NaNb/sub 5/O/sub 15/ thin films by a confocal scanning
differential polarization microscope. Proc. 4th Int. SAMPE
Electronics Conf. SAMPE, Covina, CA, pp. 712-21
Haridoss S, Shinozaki D M, Cheng C 1990 Laser scanning
confocal light microscopy of cable materials. IEEE Int.
Symp. Electrical Insulation. Institute of Electrical and
Electronics Engineers, Toronto, Canada
Hell S, Wijnaendts-van-Resandt R W 1989 The application
of polarized confocal microscopy for the size measure
ment of resist structures. Proc. SPIE 1139: 92-8
Minsky 1961 Microscopy apparatus. US Patent No.
3,013,467
Minsky 1988 Memoir on inventing the confocal scanning
microscope. Scanning 10: 128-38
Monahan V, Benschop J 1990 Object contrast in the
confocal microscope and applications to lithographic
metrology. Proc. SPIE 1261: 72-8
Pawley J (ed.) 1990 Handbook of Biological Confocal
Microscopy. Plenum, New York
Petford N, Miller J A 1990 SLM confocal microscopy: an
improved way of viewing fission tracks. J. Geol. Soc,
London 147: 217-18
Szarowski D H, Smith L, Herchenroder A, Matuszek G,
Swann J W, Turner J 1992 Optimized reflection
imaging in laser scanning confocal microscopy: applica
tions to neurobiology. Scanning 14: 104-11
Thomason J L, Knoester A 1990 Application of confocal
scanning optical microscopy to the study of fibrereinforced polymer composites. J. Mater. Sci. Lett. 9:
258-62
Toy D A 1990 Confocal microscopy: the ups and downs of
3-D profiling. Semicond. Int. 13: 120-3
Turner J N, Szarowski D H, Smith L, Marko M, Leith A,
Swann J W 1991 Confocal microscopy and threedimensional reconstruction of electrophysiologically
identified neurons in thick brain slices. J. Electron
Microsc. Tech. 18: 11-23
van der Voort H T M , Brakenhoff G J, Baarslag W 1989
Three-dimensional visualization methods for confocal
microscopy. / . Microsc. 153: 123-32
White J G, Amos W B, Fordham 1987 An evaluation of
confocal versus conventional imaging of biological struc
tures by fluorescent light microscopy. / . Cell Biol. 105:
41-8
Wilson T, Sheppard C J R 1984 Theory and Practice of
Scanning Optical Microscopy. Academic Press, London
Wright S J, Schatten G 1991 Confocal fluorescence micros
copy and three-dimensional reconstruction. J. Electron
Microsc. Tech. 18: 2-10
J. N . T u r n e r a n d D . H . S z a r o w s k i
[New Y o r k S t a t e D e p a r t m e n t of H e a l t h ,
Albany, New York, USA]
74
7. Gaseous
1.1
Corrosion
Kinetics
In t h e l a b o r a t o r y , t h e r a t e of c o r r o s i o n o r o x i d a t i o n
of a m e t a l o r alloy is m o s t simply m e a s u r e d in t e r m s
Corrosion
and Oxidation
Study
Techniques
Table 1
3
Classification of corrosion and oxidation study techniques
Type
Kinetics
Thickness
(m)
10"
10"
10-
Scratching electrode
Weight loss
AC impedance
Rotating disk
Artificial pits and crevices
Constant strain
Local
Chemistry
Differential reflectance
Ellipsometry
EXAFS
Mossbauer
Raman
Infrared
Coulometric reduction
Microelectrode
"
10~
"
Local
Morphology
10
10"
Aqueous
Ellipsometry
Light microscopy
Flexure
SEM
"
Local
Gaseous
Quartz piezobalance
XPS/AES
Microbalance
Volumetric measurement
AES depth profile
Thermobalance
Metallographic examination
SIMS
Electron diffraction
AES/XPS
XRD
STEM
Laser optical and Raman spectroscopy
Taper sections XRF
Spark source mass spectrometry
AES
Analytical TEM
Holography
TEM
Markers
RBS/RNR
SEM
Flexure and vibration
SEM
a AES, Auger electron spectroscopy; , electron probe microanalysis; EXAFS, extended x-ray absorption fine structure spectroscopy; RBS,
Rutherford backscattering; RNR, resonant nuclear reactions; SEM, scanning electron microscopy; SIMS, secondary-ion mass spectroscopy; STEM,
scanning transmission electron microscopy; TEM, transmission electron microscopy; XPS, x-ray photoelectron spectroscopy; XRD, x-ray diffraction;
XRF, x-ray fluorescence
e n c l o s u r e c a n t h e n b e e v a c u a t e d as a s t a n d a r d state a t
t h e c o m m e n c e m e n t a n d e n d of t h e test e x p o s u r e . Such
a b a l a n c e is usually t e r m e d a m i c r o b a l a n c e a n d is
useful also in w o r k i n g with toxic a n d high- o r lowp r e s s u r e e n v i r o n m e n t s o r w i t h a t m o s p h e r e s which
w o u l d c o n d e n s e at r o o m t e m p e r a t u r e . A t a s u b n a n o m e t e r level of thickness, a q u a r t z p i e z o b a l a n c e m a y
be used. A t such trivial levels of r e a c t i o n t h e investi
g a t o r is likely t o be interested less in c o r r o s i o n t h a n in
adsorption phenomena. One problem with complex
gas a t m o s p h e r e s c o n t a i n i n g several p o t e n t i a l react a n t s (e.g., 0 2 , C , C l 2 o r S 4) is t h a t of d e t e r m i n i n g their
reacting p r o p o r t i o n s . A n a l y s i s of t h e p r o d u c t after
e x p o s u r e yields t h e gross u p t a k e s , b u t o n a c o n t i n u
o u s o r s e m i c o n t i n u o u s basis, analysis of t h e a t m o s
p h e r e m u s t b e used. T h i s m e a s u r e m e n t gives rise t o a
series of v o l u m e t r i c m e t h o d s in w h i c h t h e c h a n g e in
p a r t i a l p r e s s u r e of a c o m p o n e n t in a k n o w n isother
m a l v o l u m e of gas is m o n i t o r e d .
Position-sensitive m e a s u r e m e n t s of t h e extent of
75
Corrosion
and Oxidation
Study
Techniques
o x i d a t i o n can be m a d e by d e t e r m i n a t i o n of the c o r r o
sion p r o d u c t thickness. T h i s m e a s u r e m e n t is often
m a d e intermittently by t a k i n g m e t a l l o g r a p h i c s a m
ples, b u t in the case of s u b m i c r o m e t e r films c a n be
m o n i t o r e d c o n t i n u o u s l y by c h a n g e s in interference
colors. In t h e l a b o r a t o r y , m e a s u r e m e n t of shifts in
p h a s e angle a n d intensity b e t w e e n incident a n d re
flected light p e r m i t s the i n f o r m a t i o n available t o be
e x p a n d e d b y the t e c h n i q u e s of ellipsometry.
T h e results of thickness m e a s u r e m e n t s m a y be
e x t r a p o l a t e d in time t by use of a n a p p r o p r i a t e r a t e
2
law. I m p o r t a n t e x a m p l e s are (a) p a r a b o l i c , x = k{t,
which applies w h e n diffusion across the c o r r o s i o n
p r o d u c t is r a t e controlling; (b) linear, = k2t, which
applies w h e n the c o r r o s i o n p r o d u c t offers n o
impedance
to
reaction;
and
(c)
logarithmic,
x = k3\n(\ + ct), w h e n a passive layer of limiting
thickness is reached. T h e coefficients kl9 k2, k3 a n d c
are all c o n s t a n t at a given t e m p e r a t u r e . T h e d a t a
can be i n t e r p o l a t e d a n d , with care, e x t r a p o l a t e d
in t e m p e r a t u r e by the A r r h e n i u s r e l a t i o n s h i p , k =
kx exp( Q/RT). T h e value of the a c t i v a t i o n energy Q
m a y indicate the n a t u r e of the c o n t r o l l i n g t r a n s p o r t
-1
step; for e x a m p l e , ~ 2 0 0 kJ m o l indicates solid-state
diffusion. T h e value is r e d u c e d by s h o r t circuit diffu
sion, a l o n g grain b o u n d a r i e s for e x a m p l e , or surface
diffusion.
1.2
Chemistry
excited p h o t o e l e c t r o n s p e c t r o s c o p y ( X P S o r E S C A ) ,
which yields a c o m p o s i t i o n within 5 % t o g e t h e r w i t h
firm a s s i g n a t i o n of the b o n d i n g state of m o s t species,
including oxygen a n d c a r b o n . Analysis for h y d r o g e n
is n o t possible a n d spatial resolution t o a r o u n d
200 is only j u s t b e c o m i n g available. T h i s is, h o w
ever, a n a r e a of c u r r e n t d e v e l o p m e n t a n d localized
analysis of thin films is best u n d e r t a k e n by A u g e r
electron analysis ( A E S ) , which is often c o m b i n e d with
s c a n n i n g electron m i c r o s c o p y ( S E M ) for g o o d visual
c o n t r o l of t h e a r e a analyzed. Identification of crystal
s t r u c t u r e in this thin-film region m u s t be b y electron
diffraction. O n very flat single-crystal surfaces, lowenergy electron diffraction ( L E E D ) is useful, b u t
generally reflection high-energy electron diffraction
( R H E E D ) w o u l d be used. C o n v e n t i o n a l t r a n s m i s s i o n
p a t t e r n s from films r e m o v e d from the surface, b y
m e t h a n o l i c iodine solution for e x a m p l e , m a y still be
the best m e t h o d .
F o r films of several m i c r o m e t e r s in thickness, t h e xr a y electron p r o b e m i c r o a n a l y z e r ( ) is of excep
t i o n a l value a n d widely available in the form of a n
energy-dispersive x-ray d e t e c t o r ( E D X A ) m o u n t e d o n
a n S E M . Special facilities a r e n e e d e d for elements
below s o d i u m in t h e periodic table, a n d c a r b o n is the
practical limit. Valence states a r e n o t available by
E D X A a n d X P S c a n be used o n fractured o r spalled
interfaces within thick scales, often t o great effect.
S t r u c t u r a l i n f o r m a t i o n within this r a n g e c a n be
o b t a i n e d by x-ray diffraction ( X R D ) in a d d i t i o n t o
E D methods.
Very thick films c a n be e x a m i n e d in scans across
m e t a l l o g r a p h i c sections by , o r in t o t a l by t h e
m e t h o d s of b u l k analysis, x-ray fluorescence ( X R F )
or s p a r k s o u r c e m a s s spectroscopy.
Investigation of local c o m p o s i t i o n a l v a r i a t i o n s in
thin films a n d p a r t i c u l a r l y for light elements (below
s o d i u m ) is best achieved by A E S a n d c o m p o s i t i o n a l
v a r i a t i o n s in thick films c a n be followed by a m e t h o d
in which A E S is o p e r a t e d in sequence with oxide
r e m o v a l by a n energetic ion b e a m t o yield a d e p t h
profile. A c o m p l e m e n t a r y m e t h o d for this f o r m of
analysis is t h e e x a m i n a t i o n of thin sections of oxide
scale in the analytical t r a n s m i s s i o n electron m i c r o
scope ( A T E M ) . Special p r o v i s i o n c a n be m a d e with
s o m e of these v a c u u m m e t h o d s for c o r r o s i o n p r o
cesses t o be studied in situ using h e a t e d gas cells.
Alternatively laser-excited optical s p e c t r o s c o p y o r
R a m a n s p e c t r o s c o p y , which d o n o t require a v a c u u m ,
c a n be used.
1.3
Morphology
M o r p h o l o g i c a l c h a n g e s d u r i n g g r o w t h of a n oxide
scale a r e i m p o r t a n t t o b o t h t h e c o r r o s i o n scientist a n d
the engineer. T h e s e a r e s h a p e a n d profile c h a n g e s
i n d u c e d by preferred crystallinity, directional g r o w t h
o r locally accelerated a t t a c k . S u c h p h e n o m e n a fre
q u e n t l y give rise t o stress. T h u s , i m p o r t a n t experi
m e n t s in which inert m a r k e r s are placed o n the
Corrosion
2. Aqueous
Corrosion
2.1 Kinetics
W h i l e electrochemical m e a s u r e m e n t s f o r m t h e basis
for t h e s t u d y of a q u e o u s c o r r o s i o n , t h e e m p h a s i s
d e p e n d s o n t h e kinetic region of i m p o r t a n c e . T h e
initial p e r i o d of r e a c t i o n is i m p o r t a n t for t h e light it
t h r o w s o n the r a t e of p a s s i v a t i o n of n e w surface a s it
w o u l d be e x p o s e d d u r i n g t h e fracture of m e t a l s . T h i s
rate, in t u r n , d e t e r m i n e s w h e t h e r a c r a c k c o n t i n u e s t o
p r o p a g a t e o r w h e t h e r , instead, t h e c r a c k b e c o m e s
b l u n t u n d e r t h e a c t i o n of electrochemical dissolution.
T h e p r o b l e m of i n s t r u m e n t a t i o n for w o r k in this
region is t h a t of r e s p o n s e r a t e , since r e c o r d s of events
o c c u r r i n g over millisecond p e r i o d s a r e r e q u i r e d . T h e
m a j o r design feature is t h e m e a n s p r o v i d e d t o e x p o s e
new surface w i t h i n t h e electrolyte a t a c o n t r o l l e d
m o m e n t . I n p o l a r o g r a p h y this is d o n e b y d r o p p i n g a
liquid m e t a l , m e r c u r y , from a n orifice; in t h e case of
n o r m a l m e t a l s it c a n only b e d o n e m e c h a n i c a l l y , for
e x a m p l e b y s t r a i n i n g o r s c r a t c h i n g t h e electrode. T h e
p o t e n t i a l of t h e surface relative t o a s t a n d a r d cell t h e n
indicates t h e p e r i o d d u r i n g w h i c h m e t a l is e x p o s e d ,
the c u r r e n t flow t h r o u g h t h e electrode gives t h e in
s t a n t a n e o u s r a t e of r e a c t i o n , w h i c h diminishes a s t h e
film heals, a n d t h e c h a r g e transferred indicates t h e
thickness of t h e film f o r m e d . I n a useful v a r i a n t of t h e
t e c h n i q u e a circular scratch is described b y a stylus o n
a r o t a t i n g disk.
T h e vast b o d y of studies o n a q u e o u s c o r r o s i o n is
c o n c e r n e d n o t with t h e p a s s i v a t i o n stage b u t w i t h
either t h e steady loss of m e t a l from unfilmed o r p a r t l y
filmed surfaces o r t h e loss of passivity of a surface
u n d e r chemical o r electrochemical a c t i o n . I n t h e s t a n
d a r d three-electrode test cell, t h e p o t e n t i a l of t h e
testpiece o r w o r k i n g electrode relative t o t h e s t a n d a r d
electrode is m e a s u r e d b y a very h i g h - i m p e d a n c e
electrometer as a function of t h e c u r r e n t flow b e t w e e n
and Oxidation
Study
Techniques
t h e w o r k i n g electrode a n d a c o u n t e r electrode. W h e n
a p o t e n t i o s t a t i c circuit is used, t h e c u r r e n t flow is
varied a u t o m a t i c a l l y until a preset p o t e n t i a l is reached
a n d held, w h e r e a s in a g a l v a n o s t a t i c circuit it is the
p o t e n t i a l w h i c h is varied. C o m m e r c i a l electronic de
vices a r e available t o p e r f o r m these functions a n d
m a k e it possible t o scan t h e p o t e n t i a l of the s a m p l e in
a stepwise, c o n t i n u o u s o r repetitive p a t t e r n .
W h e n t h e external c u r r e n t is p a s s e d t h r o u g h the
electrode, its p o t e n t i a l c h a n g e s as a n e w b a l a n c e
b e t w e e n the a n o d i c a n d c a t h o d i c r e a c t i o n s is e s t a b
lished. A t high c u r r e n t s (100 o r 1000 times t h e c o r r o
sion c u r r e n t ) , t h e r e a c t i o n a p p r o p r i a t e t o t h e direction
of t h e c u r r e n t is sufficiently d o m i n a n t for the testpiece
t o b e h a v e as a single electrode. Its p o t e n t i a l t h e n
varies logarithmically with t h e m e a s u r e d c u r r e n t I
a c c o r d i n g t o t h e Tafel e q u a t i o n
V = log
I/I0
I0)
Corrosion
and Oxidation
Study
Techniques
d e p e n d s o n h y d r o d y n a m i c p a r a m e t e r s because of the
i m p o r t a n c e of m a s s transfer t h r o u g h the b o u n d a r y
layer. Such s i t u a t i o n s c a n be m o d e l l e d a n d c o n t r o l l e d
in the l a b o r a t o r y b y m e a n s of electrodes in the f o r m
of r o t a t i n g disks o r cylinders, using e q u a t i o n s for
b o u n d a r y layer thickness d e v e l o p e d originally by
Levich.
Locally high c o r r o s i o n rates, as in crevices o r in
pits, a r e of p a r t i c u l a r c o n c e r n in a q u e o u s c o r r o s i o n
a n d in this situation t h e overall c u r r e n t flow t h r o u g h
the electrode c a n b e irrelevant o r even misleading.
S t a n d a r d forms of crevice a r e p r o d u c e d b y tightening
testpieces t o g e t h e r a t a c o n t r o l l e d t o r q u e while pits
c a n be simulated using t h e relevant m e t a l as t h e lead
in a pencil-type electrode. In t h e latter instance, p r i o r
dissolution of t h e m e t a l c o r e p r o d u c e s t h e artificial
pits a n d charges t h e m with t h e a p p r o p r i a t e s o l u t i o n .
Special m e t h o d s a r e used t o p r e v e n t salt precipitates
in the pits, b u t thereafter pitting c o r r o s i o n rates c a n
be studied in isolation from general c o r r o s i o n . T h e
m o s t serious form of local c o r r o s i o n is t h a t which
occurs conjointly with applied stress which m a y be
static (stress-corrosion cracking) o r cyclic ( c o r r o s i o n
fatigue). Early m e t h o d s for t h e s t u d y of stressc o r r o s i o n c r a c k i n g utilized a static strain, i m p o s e d b y
c o n s t r a i n i n g the test pieces in a " C " jig for e x a m p l e ,
b u t m o r e m o d e r n m e t h o d s use a c o n s t a n t strain r a t e
applied by m e a n s of a t e n s o m e t e r , which is f o u n d t o
predict a c t u a l failure m o r e closely.
2.2
Chemistry
Surfaces a r e c a p a b l e of being e x a m i n e d in a m u l t i t u d e
of w a y s o n c e they a r e r e m o v e d from t h e test m e d i u m
b u t the validity of this a p p r o a c h m u s t be checked
against conclusions d r a w n from in situ e x a m i n a t i o n
by specialist m e t h o d s . F o r the earliest p h a s e of
g r o w t h , ellipsometry a n d differential reflectometry
h a v e been e m p l o y e d . T h i n (5 n m ) passive films c a n be
e x a m i n e d by E X A F S (extended x-ray a b s o r p t i o n fine
structure), by M o s s b a u e r s p e c t r o s c o p y , o r by laser
R a m a n s p e c t r o s c o p y in t h e presence of a t least thin
films of w a t e r . T h i c k e r films c a n be e x a m i n e d in situ
by infrared s p e c t r o s c o p y o r electrochemically by ex
a m i n a t i o n of the c o u l o m e t r i c r e d u c t i o n s p e c t r u m .
T h e s t u d y of t h e chemistry of local c o r r o s i o n b y in situ
m e t h o d s is very difficult, b u t m i c r o e l e c t r o d e s c a n be
inserted i n t o crevices a n d pits using the techniques
traditionally e m p l o y e d b y microbiologists.
2.3
Morphology
T h e thickness a n d texture of deposits f o r m e d in a n
a q u e o u s e n v i r o n m e n t c a n be very i m p o r t a n t in o p e r
ating p l a n t , because of their effect o n h e a t transfer
a n d , t h r o u g h friction factors, o n pressure d r o p . Such
overall effects m a y be easier t o m o n i t o r in situ t h a n
they are to e x a m i n e in detail. E a r l y stages of r o u g h e n
ing c a n be studied by ellipsometry o r h o l o g r a p h y , a n d
light m i c r o s c o p y c a n be e m p l o y e d for the s t u d y of
surface t e x t u r e o n t h e m i c r o m e t e r scale. T h e flexure
78
m e t h o d s e m p l o y e d in d r y o x i d a t i o n to m e a s u r e stress
a r e valid, b u t h y d r o d y n a m i c d i s t u r b a n c e associated
with t h e cyclic m e t h o d s m a y m a k e these u n a c c e p
table.
3.
Conclusion
T h e r e a d e r will h a v e discovered t h a t c o r r o s i o n m e t h
o d s cover t h e w h o l e b r e a d t h of techniques for c h e m
ical a n d physical analysis. It is h o p e d t h a t this review
will h a v e placed t h e g r o u p s of techniques i n t o their
c o n v e n t i o n a l c o n t e x t a n d will t h u s h a v e helped the
r e a d e r t o m a k e a n efficient literature search. N o
scientist s h o u l d , h o w e v e r , be d i s s u a d e d by this review
from c o m b i n i n g techniques with i m a g i n a t i o n in o r d e r
t o best suit their o w n needs.
See also: Corrosion: Test Methods; X-Ray Absorption
Spectroscopy: EXAFS and XANES Techniques
Bibliography
Azzam R M, Bashara 1977 Ellipsometry and Polarised
Light. North-Holland, Amsterdam
Birks N, Meier G 1983 Introduction to High Temperature
Oxidation of Metals. Edward Arnold, London
Frankenthal R P, Kruger J (eds.) 1978 Passivity of Metals.
Electrochemical Society, Princeton, NJ
Hearle J W S, Sparrow J T, Cross (eds.) 1972 The Use of
the Scanning Electron Microscope. Pergamon, Oxford
Mansfeld F 1976 The polarization resistance technique for
measuring corrosion currents. In: Fontana G, Staehle
R W (eds.) 1976 Advances in Corrosion Science and
Technology, Vol. 6. Plenum, New York, pp. 163-262
Mulvey T, Webster R 1974 Modern Physical Techniques
in Materials Technology. Oxford University Press, Oxford
Parkins R 1979 Development of strain-rate testing and its
implications. In: Ugianski G M, Payer J (eds.) 1979
SCCThe Slow Strain Rate Technique, STP 665. Amer
ican Society for Testing and Materials, Philadelphia, PA,
pp. 5-25
Rapp R A (ed.) 1970 Techniques of Metals Research, Vol. 4,
Pt. 2. Interscience, New York
Seah , Briggs D (eds.) 1983 Practical Surface Analysis by
Auger and X-Ray Photoelectron Spectroscopy. Wiley,
Chichester, UK
Shreir L L (ed.) 1976 Corrosion, 2nd edn. NewnesButterworths, London
J. E. Castle
[University of Surrey,
Guildford, U K ]
Corrosion:
1. Corrosion
Test
Methods
Table 1
Recommended guidelines for field tests
Type of test
Standard
Atmosopheric exposure
Process industries test in plants
Surface sea water
Oil production test
ASTM
ASTM
ASTM
NACE
G50
G4
G52
RP-07-75
Objectives
2. Service
Test
Tests
3. Laboratory
Tests
L a b o r a t o r y c o r r o s i o n tests m a y b e divided i n t o a
n u m b e r of categories, including i m m e r s i o n tests,
79
Corrosion:
Test
Methods
Table 2
Recommended guidelines for laboratory immersion tests
Type of test
Atmospheric pressure test
Vibratory cavitation erosion test
Process industries immersion test
Autoclave testing in high-temperature
water
Dynamic testing in high-temperature
water
Zirconium alloys in high-temperature
water
Method
specification
ASTM G31
ASTM G32
NACE TM-01-69
NACE TM-01-71
NACE TM-02-74
ASTM G2
80
goal, b o t h in t e r m s of p r o d u c i n g c o r r o s i o n similar t o
t h a t which o c c u r s in t h e a t m o s p h e r e a n d in p r o d u c i n g
results in a timely m a n n e r . H o w e v e r , they h a v e been
useful in d e v e l o p i n g m o r e resistant c o a t i n g s , such as
p a i n t s a n d e l e c t r o d e p o s i t e d c o a t i n g s for o u t d o o r use.
T h e so-called accelerated tests h a v e been devised t o
speed u p the c o r r o s i o n process even further. T h e y a r e
used p r i m a r i l y as q u a l i t y a s s u r a n c e tests carried o u t
o n lots of m a t e r i a l for a c c e p t a n c e in specific a p p l i c a
tions. In these tests, significant c h a n g e s a r e m a d e in
the corrosive e n v i r o n m e n t in o r d e r t o accelerate t h e
c o r r o s i o n process. T h i s a p p r o a c h h a s b e e n widely
used t o d e v e l o p e l e c t r o d e p o s i t i o n systems for a u t o
m o t i v e a n d o t h e r d e c o r a t i v e a p p l i c a t i o n s . I n this case,
acceleration of t h e c o r r o s i o n process is achieved b y
a d d i n g , for e x a m p l e , acetic acid a n d c u p r i c ions. T h i s
is t h e basis of t h e C o p p e r Accelerated Acetic A c i d Salt
S p r a y ( C A S S ) test ( A S T M B368). T h e C o r r o d k o t e
test ( A S T M B380) e m p l o y s b o t h cupric a n d ferric ion
a d d i t i o n s . T h i s a p p r o a c h h a s also been used in evalu
a t i n g t h e stress-corrosion c r a c k i n g of v a r i o u s alloys
a n d a n u m b e r of specific test e n v i r o n m e n t s h a v e
evolved for this p u r p o s e . Accelerated tests a r e usually
specific for a m a t e r i a l system a n d c a n n o t be used
generally with a n y a s s u r a n c e t h a t t h e results will be
meaningful except for t h e specific m a t e r i a l for which
the test w a s developed.
T h e r e c o g n i t i o n t h a t t h e c o r r o s i o n process in
a q u e o u s systems is electrochemical in n a t u r e h a s led
m a n y investigators t o e x a m i n e the possibility of using
electrochemical t e c h n i q u e s in c o r r o s i o n testing. Elec
t r o c h e m i c a l testing t e c h n i q u e s h a v e t h e a d v a n t a g e of
o p e r a t i n g directly o n t h e c o r r o s i o n m e c h a n i s m a n d as
a result c a n yield a variety of i n f o r m a t i o n n o t readily
available from o t h e r types of testing. Electrochemical
tests c a n be used t o m e a s u r e t h e c o r r o s i o n r a t e
i n s t a n t a n e o u s l y t h r o u g h t h e p o l a r i z a t i o n resistance
a p p r o a c h (see Corrosion and Oxidation Study Tech
niques). T h u s , results c a n be o b t a i n e d in situ a n d very
quickly. Electrochemical t e c h n i q u e s c a n be used t o
vary t h e oxidizing p o w e r of the e n v i r o n m e n t a n d a t
t h e s a m e time t o m e a s u r e the r e s p o n s e of m a t e r i a l s t o
this v a r i a t i o n . S u c h tests h a v e given us a m u c h b e t t e r
u n d e r s t a n d i n g of t h e p e r f o r m a n c e of passive m a t e r
ials such as stainless steels. S o m e s t a n d a r d electro
chemical test m e t h o d s a r e listed in T a b l e 3.
4. Standardized
Test
Methods
T h e use of s t a n d a r d m e t h o d s in c o r r o s i o n testing h a s
b e c o m e m o r e i m p o r t a n t in recent years b e c a u s e of the
recognition t h a t there a r e m a n y pitfalls for investi
g a t o r s w h o use c o r r o s i o n tests. A n u m b e r of s t a n
d a r d s h a v e been referred t o in the p r e c e d i n g section
a n d a d d i t i o n a l s t a n d a r d s a r e being d e v e l o p e d b y a
n u m b e r of o r g a n i z a t i o n s , i n c l u d i n g t h e A m e r i c a n
Society for T e s t i n g a n d M a t e r i a l s , t h e British
Corrosion:
Table 3
Electrochemical test standards
Title
Reference method for potentiostatic and
potentiodynamic polarization
measurements
Potentiodynamic polarization resistance
measurements
Conventions applicable to
electrochemical measurements on
corrosion testing
Measurement of impedance of anodic
coatings on aluminum
FACT (Ford Anodized Aluminum
Corrosion Test)
Test
Methods
Bibliography
Designation
ASTM G5
ASTM G59
ASTM G3
ASTM B457
ASTM B538
S t a n d a r d s I n s t i t u t i o n , t h e N a t i o n a l A s s o c i a t i o n of
Corrosion Engineers and the International Standards
Organization.
See also: Corrosion and Oxidation Study Techniques
81
D
Depth Profiling
A d v a n c e d m a t e r i a l s science a n d t e c h n o l o g y c a n b e
characterized b y a n increasing i m p o r t a n c e of surfaces,
interfaces a n d thin films. F o r e x a m p l e , thin-film s t r u c
tures for microelectronic devices, optical, w e a r - a n d
corrosion-resistant c o a t i n g s , surfaces modified by ion
i m p l a n t a t i o n , electron o r laser b e a m r a d i a t i o n , a n d so
o n a r e b a s e d o n t h e u n d e r s t a n d i n g a n d c o n t r o l of
processes a n d p h e n o m e n a a t t h e a t o m i c scale. T h e
resulting p r o p e r t i e s as well as r e a c t i o n s a t surfaces
a n d interfaces, such as o x i d a t i o n a n d c o r r o s i o n , segre
gation a n d interdiffusion c a n only be u n d e r s t o o d if
the relevant c h a n g e s of t h e chemical c o m p o s i t i o n at
a n d n e a r interfaces a r e k n o w n . T h i s requires a q u a n t i
tative spatially resolved chemical a n d s t r u c t u r a l
analysis. In view of t h e p l a n a r s t r u c t u r e of thin films,
analysis of the i n - d e p t h d i s t r i b u t i o n of chemical c o m
position with high r e s o l u t i o n is of p r i m a r y i m p o r t
ance. T h e r e f o r e it is n o t surprising t h a t n u m e r o u s
m e t h o d s h a v e been d e v e l o p e d for this p u r p o s e , for
e x a m p l e , t h e n o n d e s t r u c t i v e m e t h o d s of R u t h e r f o r d
backscattering spectrometry (RBS), nuclear reaction
analysis ( N R A ) a n d p r o t o n - i n d u c e d x-ray emission
( P I X E ) , a n d t h e destructive m e t h o d s of m i c r o s e c t i o n ing the s a m p l e followed b y chemical analysis (for a
survey, see W e r n e r a n d G a r t e n 1984). A m o n g these,
the c o m b i n a t i o n of m i c r o s e c t i o n i n g b y i o n s p u t t e r i n g
with surface analysis t e c h n i q u e s is m o s t frequently
applied, because these depth-profiling m e t h o d s a r e
applicable t o practically a n y k i n d of m a t e r i a l a n d
allow the a t t a i n m e n t of o p t i m u m d e p t h r e s o l u t i o n
over a wide d e p t h r a n g e from a t o m i c m o n o l a y e r s u p
to several m i c r o m e t e r s .
T h e a i m of this article is t o s u m m a r i z e t h e funda
m e n t a l aspects a n d t h e p r e s e n t state of u n d e r s t a n d i n g
a n d o p t i m i z a t i o n of d e p t h profiling by s p u t t e r i n g in
materials research. F o r t h e physical principles of the
analysis m e t h o d s a n d for further details, see t h e
a p p r o p r i a t e review articles by O e c h s n e r (1984),
W e r n e r a n d G a r t e n (1984) a n d H o f m a n n (1990).
7. Principles
of Depth
Profiling
by
Sputtering
T h e m o s t frequently a p p l i e d m e t h o d s of surface
analysis a r e s e c o n d a r y ion m a s s s p e c t r o m e t r y ( S I M S ) ,
s e c o n d a r y n e u t r a l s m a s s s p e c t r o m e t r y ( S N M S ) , ion
scattering s p e c t r o m e t r y (ISS), A u g e r electron s p e c t r o
m e t r y ( A E S ) a n d x-ray p h o t o e l e c t r o n s p e c t r o m e t r y
( X P S o r E S C A , electron s p e c t r o m e t r y for chemical
analysis) (see, for e x a m p l e , W e r n e r a n d G a r t e n 1984).
W h e r e a s S I M S a n d S N M S a n a l y z e t h e sputtered
m a t t e r , A E S , X P S a n d ISS analyze the r e m a i n i n g
surface. T h e d e p t h of i n f o r m a t i o n of these techniques
is of t h e o r d e r of 1 n m o r below, which is a p r e r e q u i
site for o b t a i n i n g high i n - d e p t h resolution. H o w e v e r ,
they differ m a r k e d l y with respect t o e l e m e n t a l specifity a n d sensitivity, chemical i n f o r m a t i o n , b a c k
g r o u n d , d y n a m i c r a n g e , lateral r e s o l u t i o n a n d d e p t h
of i n f o r m a t i o n . T h e s p u t t e r i n g p r o c e s s is i n d e p e n d e n t
of t h e analysis m e t h o d a n d c a n therefore be c o n
sidered separately.
H i g h spatial r e s o l u t i o n m e t h o d s like s c a n n i n g
A u g e r m i c r o s c o p y ( S A M ) c a n be used in a n a l t e r n a t
ive w a y t o reveal t h e i n - d e p t h d i s t r i b u t i o n by lateral
s c a n n i n g over a bevelled section of a s a m p l e . H i g h
r e s o l u t i o n is o b t a i n e d with t h e t e c h n i q u e of c r a t e r
edge profiling ( H o f m a n n 1990, 1991a) a t t h e rim of a
s p u t t e r c r a t e r with slope angle a, because the magnifi
3
c a t i o n factor 1 / t a n a typically is a b o u t 10 , t h a t is,
1 laterally c o r r e s p o n d s t o 1 n m in d e p t h . T h e m a i n
a d v a n t a g e of this t e c h n i q u e is t h a t a d e p t h profile c a n
be o b t a i n e d after s p u t t e r i n g , i n f o r m a t i o n lost d u r i n g
s p u t t e r i n g c a n be retrieved a n d t h e signal-to-noise
figure c a n be i m p r o v e d .
C o m m e r c i a l i n s t r u m e n t s for d e p t h profiling consist
of a n ion g u n , a s a m p l e stage a n d a m a s s analyzer
( S I M S ) , ion energy analyzer (ISS) o r electron energy
a n a l y z e r ( A E S , X P S ) . A E S a n d X P S need a n electron
g u n o r a n x-ray s o u r c e , respectively. All these facilities
a r e a s s e m b l e d in a stainless steel c h a m b e r with a n ion,
t u r b o m o l e c u l a r o r c r y o p u m p t o m a i n t a i n a base
p r e s s u r e of reactive gases in the u l t r a h i g h v a c u u m
8
( U H V , ^ 1 0 " P a ) r a n g e . T h i s is necessary t o avoid
d i s t o r t i o n s c a u s e d by surface r e a c t i o n s of reactive
species such as C O , H 2 0 a n d h y d r o c a r b o n s . O f
c o u r s e , inert a r g o n which is m o s t often used as
b o m b a r d m e n t gas supply for t h e ion g u n m a y be
p r e s e n t with a higher p a r t i a l p r e s s u r e u p to a b o u t
2
10- Pa.
S p u t t e r e r o s i o n p r o c e e d s o n a n a t o m i c scale ( C a r t e r
et al. 1982). T h e r e f o r e , a d e p t h resolution in the
m o n o l a y e r regime s h o u l d be achievable. H o w e v e r ,
s p u t t e r i n g is n o t a n ideal layer-by-layer erosion b u t is
the result of a c o m p l e x ion b e a m - s a m p l e i n t e r a c t i o n
process. T h i s process i n d u c e s a variety of d i s t o r t i o n a l
effects o n b o t h surface m o r p h o l o g y a n d c o m p o s i t i o n ,
83
Depth
Profiling
I-fit)
Quantitative
s u r f a c e analysis
Sputtering
removal rate
X ' f i z )
Sputtering-induced
alterations of surface
composition and morphology
Figure 1
Principles of sputtering profile evaluation; conversion of a
measured profile, I=f(t)
to a true concentration profile
c a u s e a n o n l i n e a r i t y in t h e d e p t h - t i m e relation w h i c h
w o u l d r e q u i r e auxiliary t e c h n i q u e s of in situ m e a s u r e
m e n t of t h e i n s t a n t a n e o u s s p u t t e r i n g r a t e ( O e c h s n e r
1984), which a r e generally t o o c o m p l i c a t e d for p r a c t i
cal profiling.
1.2 Calibration of
Composition
T h e general p r o b l e m of quantification of surface
analysis m e t h o d s is b e y o n d t h e scope of this article
a n d is t h e subject of special p u b l i c a t i o n s ( W e r n e r a n d
G a r t e n 1984, B e n n i n g h o v e n et al. 1987). W h e r e a s in
A E S a n d X P S quantification is i n d e p e n d e n t of s p u t t e r
e r o s i o n , b o t h a r e directly c o u p l e d in S I M S a n d
S N M S . T h e m a i n a d v a n t a g e of the latter m e t h o d s is
their low b a c k g r o u n d a n d large c o n c e n t r a t i o n r a n g e
(see Sect. 3), w h i c h allows trace analysis, a n d their
capability of h y d r o g e n detection. W h e r e a s A E S a n d
X P S s h o w only a w e a k m a t r i x d e p e n d e n c e of their
sensitivity, S I M S is difficult t o quantify b e c a u s e t h e
i o n i z a t i o n p r o b a b i l i t y strongly varies with c o m p o s i
tion. S p u t t e r i n g with O J i o n s in S I M S is a m e t h o d t o
r e d u c e t h e m a t r i x effect, while p o s t i o n i z a t i o n of s p u t
tered n e u t r a l s as in S N M S allows a practically m a t r i x i n d e p e n d e n t c a l i b r a t i o n . A first-order quantification
in A E S a n d X P S c a n be achieved by the use of
elemental sensitivity factors.
Q u a n t i t a t i v e analysis d e p e n d s o n t h e chemical
b o n d i n g state of t h e elements w h i c h is directly
observed in X P S . In A E S , p e a k s h a p e a l t e r a t i o n s d u e
to chemical b o n d i n g m a y c h a n g e t h e p e a k - t o - p e a k
height values of t h e spectra in t h e u s u a l derivative
m o d e . Recently, least-squares fitting of s t a n d a r d spec
t r a as well a s factor analysis h a s been i n t r o d u c e d t o
e x t r a c t q u a n t i t a t i v e l y t h e chemical i n f o r m a t i o n in
d e p t h profiling ( N e l s o n 1984, H o f m a n n a n d Steffen
1989) (see Sect. 3).
2. Distortional
Effects
Profiling
Conditions
and Optimized
Sputter
Depth
Table 1
Survey of the main distortional effects in sputter profiling
Effect
Category
Instrumental
factors
Ion-beaminduced effects
Sample
characteristics
gives a c o n t r i b u t i o n t o Az p r o p o r t i o n a l t o t h e s p u t
tered d e p t h ; this m e a n s it is p r e p o n d e r a n t for large
d e p t h s (Sean a n d H u n t 1983). T h e d e p t h of i n f o r m a
tion d e p e n d s o n t h e analysis m e t h o d a n d o n t h e
sample c o m p o s i t i o n . It is o p t i m u m in I S S , w h e r e only
the first m o n o l a y e r is detected, a n d in S I M S o r S N M S
with low i o n energy w h e r e it is of t h e o r d e r of 1-2
m o n o l a y e r s given by t h e origin of t h e s p u t t e r e d
particles. I n electron spectroscopies ( A E S a n d X P S ) ,
the electron escape d e p t h p e r p e n d i c u l a r t o t h e
surface d e t e r m i n e s t h e d e p t h of i n f o r m a t i o n . It is of
the o r d e r of 0 . 3 - 3 n m , d e p e n d i n g o n t h e kinetic
energy of t h e respective A u g e r o r p h o t o e l e c t r o n line
a n d o n t h e angle o f emission t o t h e surface n o r m a l
(Seah a n d D e n c h 1979). F o r very thin layers
of < 5 n m thickness, t h e latter p r o p e r t y p r o v i d e s a
A
true
profile
\
\
measured profile~\X
\
^
y'
y'\
/
/
/
1
\
\
- resolution function
\
\
\
-\
2 = - ^
Sputtered
depth
(z)
Figure 2
Definition of the depth resolution (84%-16%) = 2 for
a Gaussian resolution function at a sharp interface A-B
Profiling
n o n d e s t r u c t i v e profiling t e c h n i q u e using v a r i a t i o n s of
the angle of emission, for e x a m p l e , by tilting the
s a m p l e . Angle-resolved X P S h a s b e c o m e particularly
p o p u l a r for t h e d e t e r m i n a t i o n of overlayer thick
nesses a n d of elemental d i s t r i b u t i o n in t h e altered
layer in s p u t t e r i n g (Bussing a n d H o l l o w a y 1985).
Most fundamental are ion-bombardment-induced
effects resulting from a l t e r a t i o n s of s a m p l e c o m p o s i
tion a n d m o r p h o l o g y o n a n a t o m i c scale. Surface
m i c r o r o u g h e n i n g d u e t o t h e statistical n a t u r e of the
s p u t t e r i n g p r o c e s s (Seah et al. 1981) a n d a t o m i c
mixing in t h e collisional c a s c a d e ( A n d e r s e n 1979) are
inevitable ( C a r t e r et al. 1982). B o t h effects result in a n
initial increase of Az with the s q u a r e r o o t of d e p t h (Az
1/2
oc z ) a n d t e n d t o s a t u r a t e a t a d e p t h of the o r d e r of
the projected ion r a n g e . W h e r e a s the surface m i c r o r o u g h e n i n g c o n t r i b u t i o n Azs results in a b o u t 2 - 5
m o n o l a y e r s d e p e n d i n g o n surface t r a n s p o r t a n d sur
face b i n d i n g energy, t h e a t o m i c mixing c o n t r i b u t i o n
Azk d e p e n d s m a i n l y o n projectile a n d b u l k m a t e r i a l s
p a r a m e t e r s . Similar t o t h e ion r a n g e , Azk increases
with t h e ion energy a n d decreases with the angle of
incidence ( A n d e r s e n 1979). T h i s is seen in Fig. 3,
w h e r e t h e results of Az for t a n t a l u m - s i l i c o n m u l t i
+
layers at different A r ion energies a n d incidence
angles a r e depicted ( H o f m a n n 1991a). O b v i o u s l y , low
ion energy a n d / o r high incidence angle a r e required
for o p t i m i z e d d e p t h resolution. A s a n e x a m p l e , Fig. 4
+
s h o w s the i m p r o v e m e n t o b t a i n e d b y using 1 keV A r
+
at a n incidence angle of = 80 instead of 3 keV A r
a t = 50, in o r d e r t o disclose a 7 n m thick TiSi
interlayer o n a silicon s u b s t r a t e a t a t o t a l s p u t t e r e d
d e p t h of 200 n m ( P a m l e r et al. 1990a).
I o n b o m b a r d m e n t frequently causes preferential
s p u t t e r i n g of o n e c o m p o n e n t a n d results in a further
profile d i s t o r t i o n , as recognized, for instance, in the
d r o p of the oxygen signal in A E S profiling of a T a 2 O s
layer ( H u n t a n d Seah 1983). A n a c c o m p a n y i n g
c h a n g e in t h e t o t a l s p u t t e r i n g yield m a y lead t o a
c h a n g e in the t i m e - d e p t h relation, a n d a n increased
a s y m m e t r y is o b s e r v e d w h e n s p u t t e r i n g t h r o u g h a n
interface of m a t e r i a l s with different s p u t t e r i n g yields
( H o f m a n n 1991a). In s o m e m a t e r i a l s , segregationa n d r a d i a t i o n - e n h a n c e d diffusion lead t o further p r o
file d i s t o r t i o n s . C h a r g i n g of i n s u l a t o r s m a y cause
e l e c t r o t r a n s p o r t of m o b i l e ions. In A E S , electron
s t i m u l a t e d d e s o r p t i o n m a y act like a n a d d i t i o n a l
selective s p u t t e r i n g , while s a m p l e h e a t i n g by a n in
tense, focused electron b e a m leads t o e n h a n c e d interdiffusion d u r i n g profiling. C o n e a n d ripple f o r m a t i o n
a r e p r o b a b l y d u e t o r a d i a t i o n - i n d u c e d diffusion a n d
r e d e p o s i t i o n a n d a r e frequently o b s e r v e d in unidirec
t i o n a l s p u t t e r i n g a t larger s p u t t e r e d d e p t h , leading to
a d e g r a d a t i o n of d e p t h r e s o l u t i o n (Cirlin et al. 1991).
S a m p l e characteristics a r e of c o n s i d e r a b l e influence
in d e p t h profiling. T h e original surface r o u g h n e s s
causes a n a d d i t i o n a l profile b r o a d e n i n g d e p e n d i n g
m a i n l y o n t h e ion b e a m angle of incidence a n d o n the
s p u t t e r e d d e p t h ( Z a l a r a n d H o f m a n n 1987). Because
85
Depth
Profiling
Figure 3
AES depth profiling results
of a tantalum-silicon multilayer structure of 20 nm alternating silicon (d = 7 nm) and tantalum
+
(d= 3 nm) layers: (a) Ar ion energy Epl = 1 keV, incidence angle = 68; (b) Epl = 3 keV, = 56; (c,d) depth resolution
A determined from the amplitude as a function of Epl (c) and of (d) (after Hofmann 1991a)
A z = [Z(^,)J
1 / 2
0)
Depth
Q_
10
f(bf~
20
30
40
N + Ti
/
y
/"
10
50
20
Ti
1
1
30 40
1
50 60
Si
/ \
70 80 \.l
90 1
100
.-/.
Figure 4
Depth profiles of a TiN layer on top of silicon with a
titanium interlayer, sputter
profiled with different
+
+
conditions: (a) 3 keV A r , = 50 and (b) 1 keV A r ,
= 80 (after Pamler et al. 1990a, Wiley, Chichester,
UK, reproduced with permission)
3. Quantitative
10
20
60
70
30
40
50
()
Figure 5
Depth resolution as a function of the ion incidence
angle for smooth ( ) (i? a = 0.012 ) and rough ( O )
(Ra = 0.06 ) Ni-Cr+ multilayers at = 25 nm depth
(1 keV and 3 keV A r bombardment, respectively) and for
anodic
Ta 2O s-Ta layers ( , ) at = 30 nm depth (1 keV
+
Ar bombardment) (after Hofmann 1990)
Profiling
Evaluation
of Sputtering
Profiles
87
Depth
Profiling
/(z)=
100
200
300
400
Sputter time (min)
(\
Ni
Cr
100
200
300
Sputter time (min)
400
X(z)g(z-z')dz'
(2)
500
Figure 6
XPS depth profiling of multilayer structure of Ni-Cr with
16 alternating layers of 30 nm thickness
on a silicon
+
substrate, sputtering with 3 keV A r ions, = 45:
(a) with stationary sample and (b) with rotating sample
(1 rpm)
Table 2
Survey of optimized sputter depth profiling conditions
Category
Sample ambient
Ion beam
Analyzing
conditions
Sample
characteristics
88
Condition
low residual
reactive gas pressure
8
(<10~ Pa)
"free" sample mount to prevent
redeposition
constant uniform intensity (scanning)
low beam energy (^ 1 keV)
high-mass ion species (or reactive species)
large incidence angle for smooth sample
(>60)
low incidence angle for rough sample
(<60)
two differently inclined beams
small analysis area relative to crater size
at the center of the crater (AES, XPS)
gating of analysis signal from the center
of the crater (SIMS, ISS)
sample rotation
smooth, polished surface
noncrystalline, no second phases
oxides, semiconductors
components with similar sputtering yields,
negligible diffusion and segregation and
good electrical and thermal
conductivities
Figure 7
Measured SIMS profile of +a silicon delta marker in GaAs
at z = 50 nm for 1.2 keV 0 ion bombardment at = 2
incidence angle, adapted from Badheka et al. (1990). The
full drawn curve shows a fit of the measured data using
superposition of an atomic mixing term (w = 1.5 nm) and
a Gaussian roughness broadening (cr = 1.5 nm). The
leading and trailing edges are approximated by
exponential functions with A L = 1.3 nm and = 3.4 nm
over one decade (after Hofmann 1991c)
Depth
to
exp. data
0(5IOeV)
calc. profile
true profile
10
Depth
15
20
25
(monolayers)
Figure 8
Example of the true, normalized in-depth distribution
evaluation with Eqn. (3). Measured data ( ) are from
the
+
oxygen (510eV) AES sputtering profile (1 keV A r ) of a
passive layer on a Fe-18%Cr-8%Ni stainless steel. The
full drawn line is the optimum fit calculated from the true
in-depth distribution (
) with (0) = 5.5 monolayers.
The missing oxygen in the first layer is due to
carbohydride contamination; the nonvanishing oxygen
content at larger depth can be explained by ion beam
shadowing due to surface roughness (after Sanz and
Hofmann 1986)
Profiling
= 970
2 monolayers min"
=III9K
Monolayers
Monolayers
Figure 9
AES depth profiles of the segregation layer on indium at a grain boundary of bicrystals of a Ni-1.2 at.% In alloy,
quenched from 970 K, 1119 and 1311 K. The in-depth distributions (b-d) result from the analysis of the sputtering
profiles in (a) using Eqn. (3) (after Muschik et al. 1989)
89
Depth
Profiling
/() =
( -
/
0
1)
-fv
+
"
Remarks
90
Sputtering time ( s )
10
12
14
16
18
20
Depth (monolayers)
Figure 10
(a) Depth profile of the chemical composition of a passive
layer on Fe-18%Cr (24 h in 0.5n H 2 S 0 4 at 1 V (NHE)).
Normalized fractions of the metallic (Cr(met),Fe(met))
and oxidic (Cr(ox),Fe(ox)) standard components in the
Auger spectra between 20 eV and 70 eV are plotted as a
function of the sputtering time, (b) Concentrations of the
alloy elements in metallic and oxidic states after fitting all
fractions of the respective components from (a) with Eqn.
(3) (after Steffen and Hofmann 1989)
Depth
Extensive studies of t h e d e p e n d e n c e of t h e d e p t h
resolution o n v a r i o u s e x p e r i m e n t a l p a r a m e t e r s h a v e
s h o w n t h a t o p t i m u m profiling c o n d i t i o n s a r e m e t b y
using h i g h - m a s s , low-energy i o n s for b o m b a r d m e n t a t
high incidence angles. S a m p l e r o t a t i o n d u r i n g profil
ing is increasingly e m p l o y e d t o a v o i d extensive s a m p l e
r o u g h e n i n g d u r i n g s p u t t e r i n g . T h e f u n d a m e n t a l limits
of d e p t h r e s o l u t i o n u n d e r o p t i m i z e d profiling c o n
ditions a r e surface m i c r o r o u g h e n i n g a n d a t o m i c mix
ing w h i c h ultimately limit t h e o b t a i n a b l e r e s o l u t i o n t o
a few n a n o m e t e r s .
A k n o w l e d g e of t h e d e p t h r e s o l u t i o n function
allows d e c o n v o l u t i o n of n o r m a l i z e d m e a s u r e d p r o
files t o o b t a i n t h e original i n - d e p t h d i s t r i b u t i o n o f
c o m p o s i t i o n . F o r t h i n films of several n a n o m e t e r s
thickness, a precision in t h e a t o m i c m o n o l a y e r r a n g e
can be o b t a i n e d .
See also: Auger Electron Spectroscopy; Chemical Analysis
of Solid Surfaces; Electron Spectroscopy for Chemical
Analysis; Ion Backscattering Analysis; Particle-Induced XRay Emission
Bibliography
Andersen 1979 The depth resolution of sputter profil
ing. Appl. Phys. 18: 131-6
Badheka R, Wadsworth M, Armour D G, van den Berg J,
Clegg J 1990 Theoretical and experimental study of the
broadening of dilute delta-doped Si spikes in GaAs
during SIMS depth profiling. Surf. Interface Anal. 15:
550-8
Benninghoven A, Rudenauer F G, Werner W 1987
Secondary Ion Mass Spectrometry. Wiley, New York
Bussing T, Holloway 1985 Deconvolution of concentra
tion depth profiles from angle resolved XPS data. / . Vac.
Sci. Technol. 13: 1973-81
Carter G, Gras-Marti A, Nobes J 1982 Theoretical
assessments of major physical processes involved in the
depth resolution in sputter profiling. Radiat. Eff. 62: 11952
Cirlin , Cheng T, Ireland P, Clemens 1990 Influence
of ion mixing, ion beam-induced roughness and temperat
ure on the depth resolution of sputter depth profiling of
metallic bilayer interfaces. Surf. Interface Anal. 15: 33743
Cirlin , Vajo J J, Doty R E, Hasenberg C 1991 Ioninduced topography, depth resolution and ion yield dur
ing SIMS depth profiling of a GaAs/AlGaAs superlattice:
effects of sample rotation. / . Vac. Sci. Technol. A 8: 1395401
Hofmann S 1986 Determination of depth resolution from
measured sputtering profiles of multilayer structures:
equations and approximations. Surf. Interface Anal. 8:
87-9
Hofmann S 1990 Depth profiling in AES and XPS. In:
Briggs D, Seah (eds.) 1990 Practical Surface Analy
sis, 2nd edn., Vol. 1. Wiley, Chichester, UK, pp. 143-99
Hofmann S 1991a Compositional depth profiling by sputter
ing. Prog. Surf. Sci. 36: 35-87
Hofmann S 1991b High resolution compositional depth
profiling. J. Vac. Sci. Technol. A 9: 1466-76
Profiling
Diffusion:
Novel
Measurement
Methods
1. Quasielastic
Neutron
= 2hDK
(2)
^,)
= .(
f ( K )T
)22
nh \ ( / ( ) / ) + /
(3)
NC
= 2hf{K)h
(4)
All t h e i n f o r m a t i o n a b o u t t h e j u m p diffusion is c o n
tained in the a v e r a g e residence time a n d the w i d t h
function f(K) which is d e t e r m i n e d solely by the geo
m e t r y of the lattice sites.
Scattering
92
(a)
(b)
Figure 1
Neutron scattering geometry: (a) in real space, (b) in
momentum space. k0, E0, k' and E' are the wave vectors
and energy of the neutrons before and after the scattering
process; is the scattering vector (after Zabel 1984)
Diffusion:
(KJ,\
= 2 /\2
(6)
T i nc = 2hDK
(7)
(8)
where D0 is t h e p r e e x p o n e n t i a l , is t h e a c t i v a t i o n
energy, k is t h e B o l t z m a n n c o n s t a n t a n d is t h e
temperature.
In the preceding discussion, v i b r a t i o n o f the a t o m s
w a s neglected. P r o v i d e d it c a n b e a s s u m e d t h a t this
m o t i o n is u n c o u p l e d from the j u m p m o t i o n , it c a n b e
included in the analysis by m u l t i p l y i n g SiDC(K, ) by a
2
2
2
D e b y e - W a l l e r factor e x p ( - A T < w w h e r e <w > is
the m e a n s q u a r e a m p l i t u d e o f t h e v i b r a t i o n .
1.2 Coherent Scattering Function and Diffusion
C o h e r e n t quasielastic n e u t r o n scattering is m u c h
m o r e c o m p l e x t h a n t h e i n c o h e r e n t case b e c a u s e o f
pari c o r r e l a t i o n s in a t o m i c m o t i o n . A p p r o x i m a t e
expressions h a v e been d e v e l o p e d b e t w e e n .S'coh(A', )
a n d D\ see especially d e G e n n e s (1959).
2. Nuclear
Magnetic
Resonance
Novel
Measurement
Methods
(9)
constant
(10)
+ constant,
In , = Ea/kT+
7 > Tmin
(10a)
Diffusion:
Novel
Measurement
Methods
(11)
2000
3000
4000
5000
/-')
where M0 is the e q u i l i b r i u m value in H0 a n d TXp
is the s p i n - l a t t i c e r e l a x a t i o n time in the r o t a t i n g
reference frame. T h i s r e l a x a t i o n c a n be observed by
spin-locking the m a g n e t i z a t i o n for s o m e time At, t h e n
suddenly t u r n i n g off this field a n d o b s e r v i n g the F I D .
T h e a m p l i t u d e of the F I D is p r o p o r t i o n a l t o M. By
repeating this shift of pulse sequence for v a r i o u s
values of At, it is possible to extract TXp from E q n . (11)
a n d a from e q u a t i o n s similar t o E q n s . (10a, b).
2.4 Concluding
Remarks
T h e c o m b i n a t i o n of T2, Tx a n d TXp d a t a c a n extend the
d e t e r m i n a t i o n of Ea over a wide r a n g e of t e m p e r a t u r e s
a n d diffusion coefficients. F o r e x a m p l e , in the case of
lithium m e t a l , N M R d a t a h a v e p e r m i t t e d d e t e r m i
n a t i o n of the self-diffusion coefficient over eight o r d
ers of m a g n i t u d e ; see Fig. 2. F o r a n e x a m p l e of a m o r e
detailed analysis of , a n d Tx d a t a , refer to Messer
a n d N o a c k (1975).
3. Mossbauer
Effect
94
Figure 2
Temperature dependence of T]p and T2 in solid lithium;
all variables are described fully in text (after Stokes 1984)
3.1 Mossbauer
and
Diffusion
Diffusion:
Novel
Measurement
Methods
(b)
Figure 3
Schematic representation of (a) a translational jump in the
direction of emission causing a loss of coherence and a
resulting broadening of the Mossbauer line, and (b) a
jump perpendicular to the direction of emission which
preserves phase coherence and results in no broadening
(after Mullen 1984)
In a w a y q u i t e reminiscent of Q E N S a n d i n c o h e r e n t
scattering, it is possible t o associate t h e b r o a d e n i n g of
the r e s o n a n c e line with diffusion. Singwi a n d Sjolander (1960) h a v e t r e a t e d t w o m o d e l s : c o n t i n u o u s
diffusion as in a liquid, a n d h o p p i n g m o t i o n w i t h a
long residence time a s in m o s t solid-state diffusion
situations. I n b o t h cases, t h e b r o a d e n i n g c a n be
expressed as
=
IhDK
W h e n t h e net b r o a d e n i n g d u e t o diffusion e q u a l s t h a t
d u e t o t h e n u c l e a r lifetime , this leads t o a lower
1 3
2
_1
limit in diffusion coefficient of 1 0 " m s (in solids)
5 7
for F e .
4. Secondary-Ion
Mass
Spectroscopy
T h e use of s e c o n d a r y - i o n m a s s s p e c t r o s c o p y ( S I M S )
c a m e a b o u t b e c a u s e of t h e lack of s u i t a b l e r a d i o i s o
t o p e s for oxygen, n i t r o g e n a n d o t h e r light elements.
T h e s e light elements were first a n a l y z e d directly u s i n g
nuclear r e a c t i o n s (see Sect. 5) a n d indirectly using t h e
i s o t o p e e x c h a n g e m e t h o d (e.g., A u s k e r n a n d Belle
1961). I n recent y e a r s , h o w e v e r , S I M S i n s t r u m e n t s
h a v e b e c o m e sufficiently w i d e s p r e a d t h a t t o a large
extent S I M S h a s p u s h e d aside t h e n u c l e a r r e a c t i o n s a s
t h e m e t h o d of choice. Several reviews of S I M S a s
applied t o diffusion h a v e been p u b l i s h e d (e.g., P e t u s key 1984, K i l n e r 1986).
4.1
to
Diffusion
Description
5. Nuclear
Reaction
Analysis
95
Diffusion:
Novel
Measurement
Methods
of Resonant
Nuclear Reactions
to
Reactions
to
6. Rutherford
Backscattering
Analysis
R u t h e r f o r d b a c k s c a t t e r i n g ( R B S ) analysis a g a i n
m a k e s use of nuclear i n t e r a c t i o n s b u t the incident
b e a m particles reemerge u n c h a n g e d except for a
r e d u c t i o n in energy (see Ion Backscattering
Analysis).
T h e loss in energy is d u e in p a r t t o elastic recoil of the
nuclei in the target (sample). T h e m a g n i t u d e of the
96
Bibliography
Auskern A B, Belle J 1961 Oxygen ion self-diffusion in
uranium dioxide. / . Nucl. Mater. 3: 267-76
Chudley C T, Elliott R J 1960 Neutron scattering from a
liquid on a jump diffusion model. Proc. Physc. Soc. 77:
353-61
de Gennes G 1959 Liquid dynamics and inelastic scatter
ing of neutrons. Physica 25: 825-39
Kilner J A 1986 New techniques for studying mass transport
in oxides. Mater. Sci. Forum 7: 205-22
Landford W A, Benenson R, Burman C, Wielunski L 1984
Nuclear-reaction analysis for diffusion studies. In: Murch
et al. 1984, pp. 155-77
Messer R, Noack F 1975 Nuclear magnetic relaxation by
self diffusion in solid lithium: ,-frequency dependence.
Appl. Phys. 6: 79-88
Mullen J C 1984 Mossbauer diffusion studies. In: Murch et
al. 1984, pp. 59-81
Murch G E, Birnbaum Cost J R (eds.) 1984 Nontraditional Methods in Diffusion. Metallurgical Society of
AIME, Warrendale, PA
Diffusion:
Novel
Measurement
Methods
97
Elastomers: Spectroscopic
Characterization
I s o p r e n e a n d 1,3-butadiene c a n be linearly p o l y m e r
ized t o p o l y m e r s h a v i n g cis-1,4, /raws-1,4, vinyl-1,2
a n d , in the case of p o l y i s o p r e n e , vinyl-3,4 isomeric
structures. T h e m i c r o s t r u c t u r e s of p o l y b u t a d i e n e a n d
p o l y i s o p r e n e a r e k n o w n t o h a v e a p r o f o u n d effect o n
their e n d - u s e p r o p e r t i e s . T h e r e f o r e , t h e m i c r o s t r u c t u r e m u s t be d e t e r m i n e d in o r d e r t o e v a l u a t e these
relationships. In t h e early years low m o l e c u l a r weight
model c o m p o u n d s a n d model elastomeric samples
with varying a m o u n t s of t h e m i c r o s t r u c t u r e s were
used as s t a n d a r d s , since t h e p u r e c o m p o n e n t m a t e r i a l s
were n o t available; h o w e v e r , these m o d e l c o m p o u n d s
are n o t a d e q u a t e in this respect. W i t h the discovery of
stereospecific catalysts, it is n o w possible t o synthesize
p o l y b u t a d i e n e s a n d p o l y i s o p r e n e s with m i c r o s t r u c
tures a p p r o a c h i n g 1 0 0 % regularity, w h i c h serve as
ideal s t a n d a r d s . T h e s p e c t r o s c o p i c t e c h n i q u e s m o s t
often used t o c h a r a c t e r i z e this u n s a t u r a t i o n m i c r o s t r u c t u r e of e l a s t o m e r s a r e infrared s p e c t r o s c o p y ,
high-field ( > 270 M H z ) p r o t o n n u c l e a r m a g n e t i c
resonance spectroscopy ( - N M R ) and carbon-13
1 3
nuclear m a g n e t i c r e s o n a n c e s p e c t r o s c o p y ( C - N M R ) .
1. Infrared
Analysis
of
Polybutadiene
U
1150
IOOO
800
Wavelength
(cm
- 1
600
Figure 1
Out-of-plane C-H bending bands of CH and CH 2 for
(a) commercial polybutadiene, (b) vinyl-1,2-polybutadiene,
(c) cis-1,4-polybutadiene and (d) iras-l,4-polybutadiene
99
Elastomers:
Spectroscopic
D
D
= CxE\
Characterization
+ C2E\
2
= Cl E + C2E 2 +
3
= Cl E\ + C2E 2
CiE\
2
C3E 3
C3E]
w h e r e D is t h e a b s o r b a n c e a t t h e frequency i p e r u n i t
s a m p l e length, is t h e a b s o r p t i v i t y , a n d C is t h e
c o n c e n t r a t i o n of t h e c o m p o n e n t s . T h e subscripts refer
to t h e c o m p o n e n t s . values c a n b e o b t a i n e d b y
p l o t t i n g t h e a b s o r b a n c e a t each w a v e l e n g t h versus
c o n c e n t r a t i o n . T h e a b o v e e q u a t i o n s c a n b e inverted
by reciprocal m a t r i x m e t h o d s a n d solved with t h e
aid of a c o m p u t e r by s u b s t i t u t i n g t h e a b s o r b a n c e
readings.
A least-squares curve-fit m e t h o d h a d been applied
to each p u r e p o l y m e r s t a n d a r d over t h e entire r a n g e
- 1
of 1150-645 c m . T h e c o m m e r c i a l s a m p l e s were fit
ted in t h e s a m e spectral region. T h e m e t h o d s d e
veloped b y H a m p t o n , Silas, Binder a n d M o r e r o gave
results in which t h e vinyl c o n c e n t r a t i o n s were within
2. High-Resolution
NMR
of
Polybutadiene
H i g h - r e s o l u t i o n - N M R h a s n o t p r o v e d suitable for
t h e d e t e r m i n a t i o n of cis-trans
ratios in p o l y b u t a
diene, since t h e r e s o n a n c e s a r e n o t resolvable a t 60
a n d 100 M H z . T h e d e v e l o p m e n t of high-field N M R
s p e c t r o m e t e r s o p e r a t i n g a t 270 M H z o r g r e a t e r h a s
m a d e it possible t o d e t e r m i n e t h e a s - 1 , 4 , trans-1,4 a n d
vinyl-1,2 c o n t e n t of p o l y b u t a d i e n e (Santee et al.
1973). T h e r e s o n a n c e s in t h e s p e c t r u m o c c u r a s fol
lows: 1.3, 2.0, 4 . 8 , 5.4 a n d 5.6 p p m a n d h a v e been
( C H 2 - C = CH - C H 2 )
Ail
JUU
"T~
"
120
IOO
80
Chemical shift
60
40
20
( ppm ]
Figure 2
13
C-NMR spectra of solid rubbers (a) cw-polyisoprene and (b) ira/w-polyisoprene. Spectra were obtained on a solid-state
NMR operating at 37.7 MHz (carbon frequency). Conditions: single-pulse experiment with proton decoupling during
acquisition and magic angle spinning at 1.8 kHz
100
Elastomers:
3. Infrared
Analysis
of
Polyisoprene
4. High-Resolution
NMR
of
Polyisoprene
H i g h - r e s o l u t i o n - N M R c a n be used t o distinguish
1,4-polyisoprene from 3,4-polyisoprene b y t h e reso
n a n c e lines o b s e r v e d a t 5.02 a n d 4.73 p p m , respect
ively. T h e chemical shifts of t h e m e t h y l p r o t o n s in
trans- a n d cw-polyisoprene h a v e been f o u n d t o differ
by 0.07 p p m (1.67 p p m for t h e cis a d d u c t a n d
1.60 p p m for t h e trans a d d u c t ) . I n synthetic p o l y i s o
p r e n e w h i c h c o n t a i n s s o m e 3,4 u n i t s , t h e m e t h y l
p r o t o n r e s o n a n c e of t h e trans a d d u c t a n d t h e 3,4
a d d u c t a r e u n r e s o l v a b l e . T h e m e t h y l e n e p r o t o n reso
nances for cis a n d trans n a t u r a l r u b b e r a r e a l s o
1 3
u n r e s o l v a b l e (Stehling a n d B a r t z 1966). W i t h C N M R the individual c a r b o n r e s o n a n c e lines a r e dis
tinguishable (Fig. 2). T h e cw-polyisoprene c a r b o n
chemical shifts a r e as follows: - c a r b o n , 135.7 p p m ;
^-carbon, ~ 1 2 6 ppm; y-carbon, ~ 3 4 p p m ; d-carbon,
28 p p m ;
and
-carbon,
25 p p m .
For
trans-
Properties
Bibliography
Binder J L 1954 Analysis of polybutadienes and butadienestyrene copolymers by infrared spectroscopy. Anal.
Chem. 26: 1877-82
Binder J L, Ransaw C 1957 Analysis of polyisoprenes by
infrared spectroscopy. Anal. Chem. 29: 503-8
Duch W, Grant D M 1970 Carbon-13 chemical shift
studies of the 1,4-polybutadienes and the 1,4-polyisoprenes. Macromolecules 3: 165-74
Hampton R R 1949 Infrared analysis of low temperature
polymers. Anal. Chem. 21: 923-6
Hampton R R 1972 Applied infrared spectroscopy in the
rubber industry. Rubber Chem. Technol. 45: 546-626
Hatada K, Kitayama T, Terawaki Y, Tanaka Y, Sato
1980 Structural dependence of carbon-13 NMR spinlattice relaxation times of 1,4-polyisoprenes. Polym. Bull.
2: 791-7
Mochel V D 1972 Carbon-13 NMR of polymers. J. Macromol. Sci., Rev. Macromol. Chem. 8: 289-347
Morero D, Santambrogio A, Porri L, Ciampelli F 1959
Infrared analysis of polybutadienes obtained by stereospecific synthesis. Chim. Ind. (Milan) 41: 758-62
Santee R Jr, Chang R, Morton 1973 300 MHz proton
NMR of polybutadiene measurement of cis-trans iso
meric content. J. Polym. Sci., Polym. Lett. Ed.U: 449-52
Silas R S, Yates J, Thornton V 1959 Determination of
unsaturation distribution in polybutadienes by infrared
spectrometry. Anal. Chem. 31: 529-32
Stehling F C, Bartz W 1966 Determination of molecular
structure of hydrocarbon olefins by high resolution nu
clear magnetic resonance. Anal. Chem. 38: 1467-79
J. L. K o e n i g a n d D . J. P a t t e r s o n
[Case W e s t e r n Reserve University,
Cleveland, O h i o , U S A ]
101
Elastomers:
Properties
t h e r m a l p r o p e r t i e s ; effect of t e m p e r a t u r e ; e n v i r o n
m e n t a l resistance; permeability; a n d a d h e s i o n , c o r r o
sion a n d staining. T h i s article presents a r a t i o n a l e for
these varied tests r a t h e r t h a n a t t e m p t i n g t o s u m m a r
ize such a large field.
Property
Tests
on
Elastomers
Physical p r o p e r t i e s of e l a s t o m e r s are d e t e r m i n e d for
quality c o n t r o l , for c o m p l i a n c e with specifications o r
for research a n d d e v e l o p m e n t .
Tests used for o t h e r solid m a t e r i a l s a r e seldom
directly applicable t o e l a s t o m e r s because of their
m a n y u n i q u e p r o p e r t i e s . Stresses, for e x a m p l e , are
very d e p e n d e n t o n time a n d t e m p e r a t u r e a n d a r e
n o n l i n e a r with strain. Because of the u l t r a h i g h deformability a n d low m o d u l i of e l a s t o m e r s , their test
e q u i p m e n t m u s t be a c c u r a t e a t higher d i s p l a c e m e n t s
a n d lower forces t h a n a r e n e e d e d for m o s t engineering
m a t e r i a l s . G o o d reproducibility of results c a n be
o b t a i n e d only from t h o r o u g h l y d e v e l o p e d m e t h o d s ,
which is o n e of t h e r e a s o n s for t h e m a n y s t a n d a r d i z e d
tests t h a t exist. E l a s t o m e r s m a y also h a v e u n i q u e
values of P o i s s o n ' s r a t i o , frictional p r o p e r t i e s a n d t h e
G o u g h - J o u l e effect, a n d h a v e very high energy stor
age. Hysteresis is also high a n d there is n o metallictype yield p o i n t . M a n y of these differences from o t h e r
engineering m a t e r i a l s relate directly t o the n a t u r e of
the force of r e t r a c t i o n from a d e f o r m a t i o n , which is
m o s t l y d u e t o e n t r o p y in e l a s t o m e r s b u t t o internal
energy in m o r e rigid m a t e r i a l s ( B r o w n a n d R e a d
1984).
2. Nature
of
Tests
102
3. Quality
Control
Elastomers:
h a v i n g correct p r o p e r t i e s h a v e been a d d e d in t h e
correct p r o p o r t i o n s a n d t h a t t h e specified m i x i n g
p r o c e d u r e h a s been followed. M o r e tests o n elas
t o m e r s a r e p r o b a b l y m a d e for c o n t r o l t h a n for a n y
o t h e r r e a s o n . H o w e v e r , q u a l i t y c o n t r o l a t o n e stage,
say p o l y m e r m a n u f a c t u r e , b e c o m e s a c c e p t a n c e cri
teria a t a n o t h e r stage, say t h e m a n u f a c t u r e of r u b b e r
sheeting.
4.
Specifications
Specifications state t h e r e q u i r e m e n t s t h a t m u s t b e m e t
by a m a t e r i a l o r p r o d u c t . T h e y d i c t a t e t h e tests t o be
m a d e a n d a c c e p t a b l e test results. Specifications m a y
be m a d e b y a design engineer w h o requires c e r t a i n
performances, by a customer to ensure a uniform
product or adequate quality, by the manufacturer to
detect irregularities d u r i n g fabrication o r by a regula
tory agency t o m a i n t a i n safety s t a n d a r d s . D u p l i c a t e
tests a r e often m a d e by t h e final inspection d e p a r t
m e n t of a p r o d u c e r a n d b y t h e a c c e p t a n c e l a b o r a t o r y
of a c o n s u m e r o r m e r c h a n d i s e r . T h i s requires t h a t t h e
e q u i p m e n t a n d p r o c e d u r e s used b y e a c h g r o u p s h o u l d
give results t h a t differ b y n o m o r e t h a n a n agreed
a m o u n t . Systems for classifying r u b b e r s b y line call
o u t given in A S T M S t a n d a r d s D 2 0 0 0 a n d D 1 2 0 7 a r e
useful in writing specifications, especially for a u t o m o
tive a p p l i c a t i o n s .
Tests m a d e for c o n f o r m a n c e t o specifications, like
t h o s e for q u a l i t y c o n t r o l , h a v e results t h a t either
p e r m i t o r d o n o t p e r m i t a c c e p t a n c e . Tests discussed in
t h e following sections a r e m o r e c o m p r e h e n s i v e in t h a t
they c a n be used t o c h a r a c t e r i z e t h e subject m a t e r
ials a n d a r e useful for research a n d d e v e l o p m e n t
purposes.
5. Suitability
for Particular
Applications
C o m p r e h e n s i v e tests o n e l a s t o m e r s a r e r e q u i r e d for
c o m p o u n d d e v e l o p m e n t , for e n g i n e e r i n g a p p l i c a t i o n s
a n d for v a l i d a t i o n of theoretical studies. Often s t a n
d a r d i z e d , such tests m a y r a n g e in c o m p l e x i t y from
simple d e t e r m i n a t i o n of t r e n d s in t h e level of s o m e
p r o p e r t y t o t h o r o u g h , designed e x p e r i m e n t s for deter
m i n i n g p r a c t i c a l levels o f m a n u f a c t u r i n g variables for
o p t i m u m c o m b i n a t i o n s of p r o p e r t i e s .
A designed e x p e r i m e n t consists of a statistical p r o
c e d u r e t h a t requires systematic d e t e r m i n a t i o n of m u l
tiple p r o p e r t i e s (responses) o n a m u l t i v a r i e d system. It
usually requires c o m p u t e r - a i d e d analysis. E l a s t o m e r s
a r e p a r t i c u l a r l y suited t o this t y p e of o p t i m i z a t i o n of
t h e wide r a n g e of p r o p e r t i e s a n d c o m b i n a t i o n s t h e r e o f
t h a t c a n be achieved. A m o t o r m o u n t , for e x a m p l e ,
m a y require t h a t static m o d u l u s , d y n a m i c m o d u l u s
a n d energy a b s o r p t i o n r e m a i n w i t h i n s t a t e d limits
over a stated r a n g e of t e m p e r a t u r e , l o a d , frequency,
a m p l i t u d e a n d c o n c e n t r a t i o n of o z o n e a n d c e r t a i n
Properties
6. Special
Considerations
for
Testing
Elastomers
R e p r o d u c i b i l i t y of results, especially b e t w e e n l a b o r a
tories, is very p o o r for e l a s t o m e r s unless detailed
i n s t r u c t i o n s a r e given a n d followed. T h o s e for pretest
p r o c e d u r e s m u s t include s a m p l i n g , mixing, t y p e of
m o l d , m o l d g e o m e t r y , vulcanizing time a n d t e m p e r a
t u r e a n d rest time before testing; f o r m i n g test pieces
by c u t t i n g , buffing o r plying; t h e r m a l a n d m e c h a n i c a l
c o n d i t i o n i n g ; a n d a v o i d a n c e of specific interferences
such a s surface c o n t a m i n a t i o n , i r r a d i a t i o n , o z o n e o r
o t h e r c h e m i c a l a t t a c k , strains, high t e m p e r a t u r e , crys
tallization o r u n d u e aging time.
E q u a l l y detailed i n s t r u c t i o n s a r e necessary for the
i n t e r p r e t a t i o n of test results. T h e s e include scope,
significance a n d applicability of results, precision a n d
validity, a c c u r a c y c h e c k s , c a l c u l a t i o n a n d p r e s e n t a
tion of results. Tests o n e l a s t o m e r s a r e often macfe t o
r a n k a series of sainples; t h e results a r e relative with
n o necessity t o m e e t specified values. C o r r e c t i o n s for
d a y - t o - d a y variability a r e often m a d e b y inclusion of
a c o n t r o l c o m p o u n d with e a c h of a series of experi
mental compounds.
S o m e tests yield basic p r o p e r t i e s such a s t h e r m a l
c o n d u c t i v i t y , specific h e a t , t h e r m a l e x p a n s i o n , density
a n d refractive index. T h e s e a r e i n d e p e n d e n t of t h e
m e a s u r i n g i n s t r u m e n t a n d m e t h o d . Values of these
c o n s t a n t s for typical vulcanizates of s o m e c o m m o n
p o l y m e r s h a v e b e e n p u b l i s h e d by W o o d (1975).
U s u a l l y , h o w e v e r , results a r e highly d e p e n d e n t o n
b o t h t h e test m e t h o d a n d t h e c h o s e n c o n d i t i o n s within
that method. F o r example, the statement that a
2
v u l c a n i z a t e h a s a m o d u l u s of 5.0 M N m " is m e a n i n g
less unless t h e state a n d r a t e of d e f o r m a t i o n a r e given
103
Elastomers:
Properties
a l o n g with t h e t e m p e r a t u r e . F u r t h e r m o r e , t h e value
m u s t b e identified as Y o u n g ' s m o d u l u s o r rigidity
m o d u l u s , as e q u i l i b r i u m o r t r a n s i e n t , a s t a n g e n t o r
secant, w h e t h e r b a s e d o n original o r a t t a i n e d cross
section a n d w h e t h e r d e t e r m i n e d o n t h e first o r subse
q u e n t d e f o r m a t i o n s . T h e s e a r e s o m e of t h e m a n y
i m p o r t a n t details t h a t a r e included in s t a n d a r d i z e d
tests.
7.
T h e c o h e r e n t scattering of electrons b y m a t e r i a l s is
t e r m e d diffraction. F o r crystalline solids, c o n s t r u c t i v e
interference of diffracted electrons only o c c u r s in
specific directions with respect t o t h e incident w a v e .
T h e resulting diffraction p a t t e r n s c a n b e used t o
a n a l y z e t h e a t o m i c s t r u c t u r e of a specimen in several
w a y s , d e p e n d i n g o n t h e specific diffraction t e c h n i q u e s
used.
E l e c t r o n s c a n b e r e g a r d e d a s waves h a v i n g a w a v e
length g o v e r n e d b y their energy. T o a g o o d a p p r o x i
m a t i o n a t nonrelativistic energies,
F . S. C o n a n t
[Firestone Tire a n d R u b b e r C o m p a n y ,
Akron, Ohio, USA]
Electron Diffraction
Standards
Tests m a y be s t a n d a r d i z e d a t i n t e r n a t i o n a l , n a t i o n a l
o r industrial level. T h e y r e p r e s e n t a c o n s e n s u s of
interested p a r t i e s including p r o d u c e r , c o n s u m e r , sales
m a n a g e r , r e g u l a t o r a n d theoretician. T h e y a r e usually
o u t g r o w t h s of tests d e v e l o p e d for c o m p a n y u s e ,
agreement between producer a n d consumer, or m a d e t o - o r d e r tests for p a r t i c u l a r research o r d e v e l o p m e n t
w o r k . O n l y b y such b r o a d - b a s e d i n p u t c a n t h e inclu
sion of all necessary c o n s i d e r a t i o n s b e a s s u r e d .
S o m e 300 s t a n d a r d s o r r e c o m m e n d a t i o n s o n r u b
ber h a v e been d e v e l o p e d b y t h e I n t e r n a t i o n a l S t a n
dards Organization (ISO). Various national bodies
such as A N S I in t h e U S A , BSI in t h e U K , G O S T in
Russia, A F N O R in F r a n c e a n d D I N in G e r m a n y c a n
supply I S O s t a n d a r d s o n request. T h e s e g r o u p s also
h a v e c o m p r e h e n s i v e s t a n d a r d s of their o w n w h i c h
usually c o n f o r m essentially t o c o r r e s p o n d i n g I S O
s t a n d a r d s if they exist. M o s t of t h e A N S I s t a n d a r d s
a r e included in t h e A S T M Annual Book of Standards.
A widely accepted list of s t a n d a r d test t e m p e r a t u r e s
a n d o t h e r i n t r a s t a n d a r d a g r e e m e n t s such a s rest t i m e
between c u r i n g a n d testing a r e very helpful for o p e r a
tional efficiency a n d for c o r r e l a t i n g results from dif
ferent tests.
T h e v a r i o u s types of s t a n d a r d s include test m e t h
o d s , specifications, t e r m i n o l o g y , classification, p r a c
tice, guide a n d i n f o r m a t i o n . All o f these c o n t r i b u t e
to c o m m u n i c a t i o n a m o n g interested p a r t i e s , w h i c h
includes t h o s e t h a t m a k e o r d i n a n c e s a n d set tariff
rates.
= (\.5/
/2
(1)
w h e r e V is in electron volts a n d is in n a n o m e t e r s .
Since electrons i n t e r a c t very efficiently with b o t h t h e
nucleus a n d t h e electron c l o u d a s they p e n e t r a t e a
solid, they r a p i d l y lose energy, a n d c o h e r e n t scatter is
impossible. T h e r e f o r e electron diffraction is only use
ful for s t u d y i n g t h e surfaces o f b u l k m a t e r i a l s o r t h e
i n t e r n a l s t r u c t u r e of very thin (<^ 0.5 ) specimens.
T h e s t u d y of surfaces is p e r f o r m e d using low-energy
electron diffraction ( L E E D ) w h e r e V is 5 - 5 0 0 eV (see
Electron
Diffraction,
Low-Energy),
a n d reflection
high-energy electron diffraction ( R H E E D ) w h e r e is
5-500 k e V . T h e s t u d y o f t h i n foils is a l m o s t i n v a r i a b l y
p e r f o r m e d w i t h a t r a n s m i s s i o n electron m i c r o s c o p e
( T E M ) , in w h i c h electron i m a g e s c a n b e f o r m e d
c o n c u r r e n t l y from t h e a r e a t h a t is diffracting. T h i s
latter t e c h n i q u e r e p r e s e n t s a m a j o r a p p l i c a t i o n o f
electron diffraction t o t h e s t u d y of m a t e r i a l s , a n d is
e m p h a s i z e d in this article.
Bibliography
7. Theory
104
of Electron
Diffraction
(2)
kk = b(cosfix
(3)
-cosfi2)
Ik = c(cos yx - c o s y2)
(4)
w h e r e h, k a n d / a r e integers w h i c h c o r r e s p o n d t o t h e
Electron
Diffraction
factors a r e k n o w n as t h e a t o m i c scattering f a c t o r / ( )
a n d t h e s t r u c t u r e factor F(6), respectively. T h e value
off () is given b y
/()
Figure 1
(a) The coherent scattering of electron waves by a row of
atoms as described by the Laue equations, (b) The
reflection of electron waves by parallel atomic planes of
spacing d as described by the Bragg equation. Reflection
of electrons from the dotted plane spacing d/2 would
result in destructive interference and no diffracted
intensity (assuming all planes are identical)
(5)
) (-/)
(6)
w h e r e m0 is t h e rest m a s s o f t h e electron, e is t h e
electronic c h a r g e , h is P l a n c k ' s c o n s t a n t , is t h e
a t o m i c n u m b e r a n d fx is t h e a t o m i c scattering factor
for r a y s . E q u a t i o n (6) is a c o m b i n a t i o n of R u t h e r
ford scattering effects from t h e nucleus a n d scattering
f r o m t h e electron c l o u d . F r o m E q n . (6) it c a n b e seen
t h a t diffracted intensity is strongly p e a k e d in t h e
f o r w a r d d i r e c t i o n ( small), a n d h i g h e r - Z a t o m s scat
ter m o r e strongly.
T h e a m p l i t u d e scattered b y a u n i t cell F(0) c a n b e
c a l c u l a t e d b y s u m m i n g t h e values /()
for e a c h of
a t o m s in t h e u n i t cell, t a k i n g i n t o a c c o u n t t h e p h a s e
difference b e t w e e n e a c h scattering p o i n t . T h u s , t h e
scattering from a p a r t i c u l a r (hkl) p l a n e is given b y
n0)hkl
+ kyn + lzn)]
(7)
w h e r e xn9 yn, zn a r e t h e a t o m i c c o o r d i n a t e s of t h e t h
a t o m a n d the exponential term represents the phase
2
difference. T h e a c t u a l intensity is given b y F(0)hkl
.
Clearly for different crystal s t r u c t u r e s different
intensities will arise from t h e s a m e (hkl) p l a n e , a n d
u n d e r specific g e o m e t r i c a l c o n d i t i o n s F(6) a n d t h e
s c a t t e r e d intensity will b e z e r o . F o r e x a m p l e , in F i g .
l b , t h e d o t t e d line represents a p l a n e o f a t o m s spacing
d/2, from w h i c h scattered electrons w o u l d destructi
vely interfere with electrons diffracted from t h e p l a n e s
of s p a c i n g d, giving z e r o diffracted intensity. S u c h s o called systematic absences a r e characteristic of speci
fic s t r u c t u r e s (e.g., w h e n h + k + / is o d d , F(6) = 0 in
b o d y - c e n t e r e d - c u b i c s t r u c t u r e s ) . Similarly, if m o r e
t h a n o n e a t o m t y p e is p r e s e n t (e.g., in alloys), t h e n
differences in f(9) b e t w e e n different a t o m s c a n give
rise t o large c h a n g e s in diffracted intensity, such a s t h e
presence of intensity w h e r e systematic absences a r e
expected.
2. Indexing
Diffraction
Patterns
= (dhkly /(2/X)
(8)
a n d if a s p h e r e of d i a m e t e r 2/ ( t e r m e d t h e E w a l d
sphere) is inscribed within t h e reciprocal lattice a n d
g o i n g t h r o u g h t h e origin, t h e n a n y p o i n t s in t h e lattice
105
Electron
Diffraction
R a t h e r t h a n c a r r y o u t this exercise for every situa
tion, it is c o m m o n practice t o orient t h e specimen
such t h a t a low-index z o n e (e.g., a l o n g b e a m direction
[01 ] a s in F i g . 3) of p l a n e s is diffracting, a n d t h e n t o
compare the observed pattern with standard ones.
T h e fact t h a t it is possible t o o b t a i n diffraction from
several p l a n e s in a z o n e a t o n c e is also d u e t o t h e effect
of t h e specimen s h a p e o n t h e diffracted intensity
d i s t r i b u t i o n . T h e diffraction s p o t is only a m a t h e m a t i
cal p o i n t if t h e specimen is infinite in all directions.
F o r e x a m p l e , a T E M specimen is effectively infinite
( ~ 3 m m ) in t h e p l a n e of t h e specimen, a n d very thin
( < 0 . 5 ) parallel t o t h e electron b e a m . T h i s m e a n s
t h a t t h e diffracted intensity c a n b e represented in t h e
reciprocal lattice a s a r o d stretched parallel t o t h e
electron b e a m in reciprocal space, r a t h e r t h a n as a
p o i n t . T h e r e f o r e , over a r a n g e of angles, t h e E w a l d
s p h e r e will still intercept t h e r o d a n d diffracted inten
sity will still exist, a s s h o w n in F i g . 4. T h i s is equiva
lent t o saying t h a t t h e L a u e c o n d i t i o n is relaxed in o n e
d i m e n s i o n in t h e T E M o w i n g t o t h e specimen s h a p e ;
Reciprocal
spacing
lattice
\/dhkl
* 3
nm
-1
Figure 2
(a) The Ewald sphere-reciprocal lattice construction,
showing how Bragg's law is only satisfied by atomic
planes whose reciprocal lattice spots lie on the surface of
the sphere. If the specimen or beam orientation is
changed, as can be done routinely in the TEM, then
different planes will diffract and the diffraction pattern will
change, (b) Relative magnitudes of the Ewald sphere and
reciprocal lattice in the TEM showing that the surface of
the sphere is almost planar with respect to the reciprocal
lattice
106
Figure 3
Electron diffraction pattern of an Al-Li-Cu-Mg alloy.
The intense fundamental spots correspond to a section
through the reciprocal lattice of the face-centered-cubic
aluminum structure, normal to <0lT>. The area from
which the pattern was obtained is shown in the inset.
Small precipitates of Al 2CuMg are visible in the
background and platelike precipitates of ASl 2CuLi can be
clearly seen. These precipitates give rise to the faint
diffraction spots and the streaks normal to the plane of
the Al 2CuLi plates (courtesy of S. F. Baumann)
Electron
as a r o d o r s t r e a k n o r m a l t o t h e p l a n e of t h e plate. I n
this m a n n e r , i n f o r m a t i o n c o n c e r n i n g t h e s h a p e a n d
v o l u m e fraction of t h e diffracting species c a n b e
o b t a i n e d from t h e p a t t e r n .
Incident
4. Convergent-Beam
lattice
rods
Figure 4
Schematic diagram showing the effect of the shape of the
diffracting volume (in this case the thin foil specimen) on
the reciprocal lattice spot
Information
in Electron
Diffraction
Electron
Diffraction
Patterns
Diffraction
Patterns
A s well as the c r y s t a l l o g r a p h i c i n f o r m a t i o n p r e s e n t in
the d i s t r i b u t i o n of f u n d a m e n t a l s p o t s in t h e diffrac
tion p a t t e r n , such as in F i g . 3, o t h e r k i n d s of i n f o r m a
tion c a n often be o b t a i n e d from diffraction p a t t e r n s .
First, t h e c o m b i n a t i o n of electron i m a g i n g w i t h
diffraction i n f o r m a t i o n p e r m i t s identification o f
the c r y s t a l l o g r a p h i c characteristics of s e c o n d - p h a s e
particles, dislocations a n d p l a n a r defects. Secondly,
because all periodic s t r u c t u r e s c a n diffract, such p h e
n o m e n a as dislocation a r r a y s in interfaces, a r r a y s of
a n t i p h a s e b o u n d a r i e s in o r d e r e d m a t e r i a l a n d peri
odic a r r a y s of precipitates, as in s p i n o d a l m i c r o s t r u c tures, all give rise t o diffraction effects in t h e p a t t e r n
which c a n be discerned a n d often q u a n t i t a t i v e l y
interpreted.
E x a m p l e s of these effects c a n b e seen in F i g u r e 3.
T h e specimen is a c o m p l e x a l u m i n u m alloy with a
face-centered-cubic crystal s t r u c t u r e , a n d t h e intense
s p o t s represent diffraction m a x i m a from t h e crystal
planes of t h e {200} a n d {111} type, characteristic of
planes in the [OlT] z o n e axis, d o w n w h i c h t h e b e a m is
travelling. T h e r o w s of less intense s p o t s arise from
s e c o n d - p h a s e precipitates of A l 2 C u M g a n d A l 2 C u L i .
T h e A l 2 C u L i p h a s e is p r e s e n t as very thin plates in t h e
p l a n e parallel t o the b e a m , a n d a c c o r d i n g l y t h e L a u e
c o n d i t i o n is relaxed for diffraction b y these p l a t e s (see
inset, Fig. 3), such t h a t t h e diffracted intensity a p p e a r s
Figure 5
Convergent beam [001] electron diffraction pattern for
garnet; two HOLZ rings are clearly visible as well as
HOLZ lines within the diffracted intensity disks (courtesy
of M. Raghaven)
107
Electron
Diffraction
to t h e distance of a p p r o a c h t h a t w o u l d be expected if
t h e m a t e r i a l were t o crystallize.
See also: Electron Diffraction, Low-Energy; Transmission
Electron Microscopy: Convergent-Beam and Microdiffraction Techniques; X-Ray and Neutron Diffraction Studies of
Amorphous Solids
Bibliography
Figure 6
Central (000) disk in convergent beam pattern from < 111 >
oriented pure copper showing HOLZ lines crossing the
concentric extinction fringes. The HOLZ lines show the
true triad symmetry down < 111 > (courtesy of K. S.
Vecchio)
5. Diffraction
from
Amorphous
Materials
108
Electron
Diffraction,
Low-Energy
w h e r e m is t h e electron m a s s , V is t h e scattering
p o t e n t i a l a n d is t h e e l e c t r o n energy. F o r a m o n o
c h r o m a t i c c o l l i m a t e d b e a m in v a c u o (V=0),
the
+
s o l u t i o n is a p l a n e w a v e of w a v e v e c t o r k described
b y t h e w a v e function
= exp(i
.r)
I n m o s t t h e o r e t i c a l w o r k u n i t s a r e used in which
h = m = e = 1, t h e u n i t of l e n g t h is the B o h r r a d i u s
a n d t h e u n i t of energy is t h e H a r t r e e (27.2 eV).
T h e s y m m e t r y of t h e surface d i c t a t e s t h a t m o m e n
t u m parallel t o t h e surface c a n o n l y b e c h a n g e d by
discrete a m o u n t s :
g = IA + mB
w h e r e / a n d m a r e integers. T h e v e c t o r s g define t h e
reciprocal lattice a n d t h e v e c t o r s A a n d a r e given by
Figure 1
(a) The diffraction of an incident beam into a series of
discrete beams, and (b) a plan view of a typical pattern
made on the fluorescent screen
1. The Diffraction
Pattern
A = (Ax,Ay)
= 2n(byt
= (Bx,By)
= 2 ( - ay,ax)/(axby
- bx)/(axby
bxay)
bxay)
w h e r e t h e v e c t o r s a a n d b define t h e sides of t h e u n i t
m e s h of t h e surface in real s p a c e . T h e s e e q u a t i o n s c a n
readily be inverted t o find a a n d b:
a = (ax,ay)
= 2n(By9
b = (bx,by)
- Bx)/(AxBy
BxAy)
-
BxAy)
2. Calculation
of Diffracted
Intensities
+
G i v e n a n incident w a v e e x p ( i * . r ) , t h e a m p l i t u d e s of
t h e reflected w a v e s a r e r e q u i r e d . T h e reflected w a v e s
h a v e w a v e functions of t h e f o r m
Rg Qxp(ik~
where
.r)
is t h e a m p l i t u d e a n d
= [ * , + gX*ky
+ gy> ~
|*|| + f | )
1 / 2
It is c u s t o m a r y t o m o d e l t h e surface a s c o m p r i s i n g a
step d o w n in p o t e n t i a l ( k n o w n as t h e surface b a r r i e r ) ,
a series of spherically s y m m e t r i c a l p o t e n t i a l s r e p r e
senting t h e a t o m s a n d a c o n s t a n t p o t e n t i a l V0 b e t w e e n
atoms. Neglecting backscattering by the barrier, the
+
incident w a v e is t r a n s m i t t e d i n t o t h e crystal ^~
109
Electron
Diffraction,
Low-Energy
exp(iAo . r ) , w h e r e
is t h e a m p l i t u d e a n d w h e r e t h e
w a v e vector Kq h a s c o m p o n e n t s given by
kx,ky,
l 2
(2E-2V0) l
T h e t r a n s m i t t e d w a v e e n c o u n t e r s successive layers of
a t o m s , e a c h layer scattering t h e electrons. If multiple
+
scattering is neglected, a b e a m (1^ .r) is incident
o n a layer located a t Rj a n d w a v e s a r e scattered
f o r w a r d s a n d b a c k w a r d s with w a v e functions
w h e r e t h e a m p l i t u d e s a r e given by
2
1 1
-8
gg
lm
I'm'
exp[i(*0
^Iml'm'h'
, D =
(
r - o ^ ( ^ M l )
w h e r e K' is t h e c h a n g e in m o m e n t u m o n scatter
ing, is t h e t e m p e r a t u r e in K , m is t h e a t o m i c m a s s in
units of t h e electron m a s s , KB is B o l t z m a n ' s c o n s t a n t
1
6
in H a r t r e e s K (3.169 x 10~ ) a n d is t h e D e b y e
t e m p e r a t u r e in K . U n f o r t u n a t e l y , multiple scattering
interferes severely with t h e simple t h e o r y of in t e r m s
of t h e r m a l v i b r a t i o n s a n d e a c h p e a k h a s its o w n
effective d e t e r m i n e d b y t h e multiple scattering c o n
ditions. O n l y a p a r t i a l t h e o r y is available.
-K~).nc]
,i = 0
= -
er^ M-
/[l - e x p i ( t f 0
- -
).c]
).c = 2nm
w h e r e m is a n integer. F o r t u n a t e l y , V0 in t h e expres
+
sion for K 0 is c o m p l e x a n d therefore Rg0 h a s only
m a x i m a b u t even s o , t h e k i n e m a t i c a p p r o x i m a t i o n h a s
severe deficiencies in practice. Scattering, especially
f o r w a r d scattering, is n o t w e a k a n d multiple scatter
ing m a k e s a large c o n t r i b u t i o n t o R^. T h e s o l u t i o n of
the multiple scattering p r o b l e m for low-energy elec
t r o n s is o n e of t h e m i n o r t r i u m p h s of t h e electronic
110
3. The Scattering
Potential
Electron
(-
+ 0) =
T h e solution is a p l a n e w a v e with
kT^J(2E),
/l(atomic units) = -
Low-Energy
T o assist in t h e c o m p a r i s o n of t h e o r y a n d experi
m e n t v a r i o u s a u t o m a t e d criteria of a g r e e m e n t h a v e
b e e n devised (by Z a n a z z i a n d J o n a a n d b y P e n d r y t o
n a m e only t w o ) . T h e R factor m u s t stress t h e i m p o r t
a n c e of p e a k p o s i t i o n s , d e - e m p h a s i z e t h e difficult t o
r e p r o d u c e a b s o l u t e intensities a n d give s o m e n o r m a
lized i n d i c a t i o n of g o o d n e s s of fit. I n t h e latter scheme
referred t o , a function of 1(E) is defined:
l
y(E) =
k^-V0i/J(2E)
Diffraction,
L- /(L- +V 0i)
where
L(E) =
V ( 2 ) / ( 2 K 0 i)
r\dI/dE)
> 2 | 0 |
4. Surface
Structure
Determination
L o w - e n e r g y electrons p r o b e t o j u s t t h e right d e p t h in
a solid t o d e t e r m i n e t h e c r y s t a l l o g r a p h y a s s o c i a t e d
with t h e surface region o n a n a t o m i c scale. L o w energy electron diffraction ( L E E D ) h a s p r o v e d t o b e
by far t h e m o s t effective t o o l a n d of t h e several
h u n d r e d o r so s t r u c t u r e s k n o w n a l m o s t all were
d e t e r m i n e d b y L E E D . T h e first step in surface struc
t u r e d e t e r m i n a t i o n is t o find t h e t w o - d i m e n s i o n a l u n i t
m e s h of t h e surface. T h i s c a n b e d o n e b y m e a s u r e
m e n t of t h e diffraction p a t t e r n . L o c a t i o n of a t o m s
within t h e cell affects t h e intensities of diffracted
b e a m s ; t h e u s u a l p r o c e d u r e is t o guess a trial s t r u c t u r e
a n d refine it until t h e o b s e r v e d intensity/energy spec
t r a c o r r e s p o n d t o t h e calculated o n e s . D i r e c t inver
sion p r o c e d u r e s a r e n o t available for L E E D .
Needless t o say, a g r e e m e n t with e x p e r i m e n t is never
perfect. L o c a t i o n s of p e a k s a n d their relative inten
sities c a n b e r e p r o d u c e d q u i t e well, b u t a b s o l u t e
intensities a r e r a t h e r sensitive t o a n u m b e r o f
difficult-to-determine p a r a m e t e r s a n d fare less well.
F o r reliable structure d e t e r m i n a t i o n s a large d a t a b a s e
is needed. F o u r b e a m s m e a s u r e d at four different
angles of incidence in t h e r a n g e 2 0 - 1 5 0 eV a r e r e g a r d e d
as a g o o d d a t a set for a simple surface structure.
Naturally the m o r e i n f o r m a t i o n there is t o b e extracted
from the curves t h e larger t h e base m u s t be.
_my -y Y dE
ih
em
w h e r e SE is t h e t o t a l r a n g e of d a t a s u m m e d over t h e
s e p a r a t e r a n g e s for e a c h b e a m a n d e a c h angle. W h e n
R differs for u n i t y by m o r e t h a n RR t h e deviation is
significant. Typically RR m i g h t b e 0.2. T y p i c a l mini
m u m values of R a r e 0.2 for a very g o o d s t r u c t u r e , 0.3
for a g o o d o n e a n d 0.4 for a n only satisfactory
d e t e r m i n a t i o n . T h e p r o b l e m is t o scan t h r o u g h t h e
p a r a m e t e r s m i n i m i z i n g R b u t checking for false
m i n i m a a n d for c o r r e l a t e d variables w h i c h result in
r e d u c e d a c c u r a c y for t h o s e p a r a m e t e r s .
5. Other Applications
of LEED
Theory
T h e r e a r e m a n y e x p e r i m e n t s in w h i c h t h e basic L E E D
state o c c u r s c o u p l e d t o s o m e o t h e r process in t h e
surface. T h e m o s t c o m m o n e x a m p l e is in a p h o t o emission e x p e r i m e n t in w h i c h t h e e m i t t e d electron is
t r a n s m i t t e d o u t of t h e surface b y a time-reversed
L E E D s t a t e t h e so-called "final s t a t e " of p h o t o emission t h e o r y . Diffraction in t h e final state c a n lead
t o s u b s t a n t i a l r e d i s t r i b u t i o n of flux b e t w e e n different
angles of emission, a n d a n y q u a n t i t a t i v e t h e o r y of
p h o t o e m i s s i o n m u s t include a p r o p e r L E E D calcula
tion. O t h e r emission processes such a s A u g e r a n d
x-ray excited p h o t o e m i s s i o n also c o u p l e t o L E E D
states. E l e c t r o n energy loss s p e c t r o s c o p y , in which t h e
reflected b e a m is energy a n a l y z e d for its inelastic
s p e c t r u m , involves t w o L E E D states: t h e incident
b e a m a n d t h e e m i t t e d b e a m w h i c h is a time-reversed
L E E D state.
Ill
Electron
Diffraction,
Low-Energy
T h e e x t e n d e d x-ray a b s o r p t i o n fine s t r u c t u r e h a s
sometimes been called " i n t e r n a l L E E D " because the
electron kicked o u t of t h e shell of o n e a t o m is
s u b s e q u e n t l y reflected b a c k t o s o m e degree by the
s u r r o u n d i n g a t o m s . T h i s reflection coefficient m o d u
lates the a b s o r p t i o n coefficient as t h e e m i t t e d electron
energy varies with the incident x-ray energy, j u s t as
the electron c u r r e n t t o a crystal in a L E E D experi
m e n t is m o d u l a t e d by t h e reflection coefficient.
See also: Auger Electron Spectroscopy; Electron Diffrac
tion; X-Ray Absorption Spectroscopy: EXAFS and
XANES Techniques
Transmitted
electrons
Raised T E M
viewing screen
Ramping coil
Magnetic prism" \
spectrometer
//*<^J
To scintillator
" p h o t o m u l t i p l i e r system
No - loss electron'
paths (energy E)
Selecting slit in
back - focal plane
(dispersion plane)
Bibliography
Dobson J, Pendry J B, Humphreys C J (eds.) 1978
Electron Diffraction 1927-77. Institute of Physics, Bristol,
UK
Feuerbacher B, Fitton B, Willis R F 1978 Photoemission and
the Electronic Properties of Surfaces. Wiley, Chichester,
UK
Heinz K, Miiller 1982 Structural Studies of Surfaces,
Springer Tracts in Modern Physics, Vol. 91. Springer,
Berlin
McRae G 1979 Electronic surface resonances of crystals.
Rev. Mod. Phys. 51: 541-68
Pendry J 1974 Low Energy Electron Diffraction. Academic
Press, London
van Hove A, Tong S Y 1979 Surface Crystallography by
LEED. Springer, Berlin
Webb , Lagally G 1973 Elastic scattering of low
energy electrons from surfaces. Solid State Phys. 28: 301405
J. B. P e n d r y
[Imperial College of Science, T e c h n o l o g y
and Medicine, London, U K ]
112
Spectrometer
collection
semiangle -
Figure 1
Schematic diagram of a magnetic prism spectrometer
Instrumentation
E E L S is usually p e r f o r m e d using a m a g n e t i c - p r i s m
s p e c t r o m e t e r placed below t h e T E M viewing screen.
A s s h o w n in F i g . 1, t h e s p e c t r o m e t e r e n t r a n c e a p e r
t u r e selects electrons t r a n s m i t t e d t h r o u g h a specific
region of t h e specimen w i t h a collection semiangle
w h i c h is usually < 100 m r a d . D e s p i t e this small collec
tion angle, a l m o s t all t h e energy-loss electrons a r e
g a t h e r e d b y t h e s p e c t r o m e t e r , b e c a u s e they a r e
strongly f o r w a r d scattered. T h e electrons a r e separ
a t e d b y t h e m a g n e t i c field of t h e s p e c t r o m e t e r a n d
focused i n t o a dispersion p l a n e w h e r e their p o s i t i o n is
a function of their energy loss (). T h i s s p e c t r u m is
displayed b y r a m p i n g t h e electron dispersion a c r o s s
a n e n t r a n c e slit t o a s c i n t i l l a t o r - p h o t o m u l t i p l i e r sys
tem coupled to a computer-controlled multichannel
analyzer ( M C A ) .
2. The Energy-Loss
Spectrum
T h e s p e c t r u m in Fig. 2 is a p l o t of intensity I a g a i n s t
energy loss AE for 1 2 0 k e V electrons t r a n s m i t t e d
t h r o u g h a thin foil of p u r e lithium (which is a n
element t h a t is n o t d e t e c t a b l e b y x-ray s p e c t r o m e t r y in
the electron m i c r o s c o p e ) . T h e m a j o r p e a k 7 0 c o n t a i n s
t h o s e electrons t r a n s m i t t e d t h r o u g h t h e s a m p l e with
n o m e a s u r a b l e loss of energy c o m p r i s i n g :
Electron
48000
40000
L i ionization edge
32000
J p( l )
24000
16000
8000
7(
)2
16
J\
0
1
20
40
60
80
100
Figure 2
Energy-loss spectrum from a thin foil of pure lithium. The
Li ionization edge at 55 eV is magnified 16 (courtesy
of D-R. Liu)
(a)
t h o s e electrons t h a t d i d n o t i n t e r a c t with t h e
s a m p l e a t all,
(b)
(c)
In m a t e r i a l s a p p r o x i m a t i n g t o free-electron solids, t h e
low-loss s p e c t r u m s h o w s o n e o r m o r e G a u s s i a n
p e a k s , c o r r e s p o n d i n g t o q u a n t i z e d oscillations of t h e
free-electron g a s , t e r m e d " p l a s m o n s . " T w o s u c h
p e a k s , (Ip (1) a n d / p (2)), a r e visible in F i g . 2. I n n o n free-electron m a t e r i a l s , t h e low-loss region o f t h e
s p e c t r u m usually c o n t a i n s a single, b r o a d , p l a s m o n type p e a k a t a r o u n d 2 0 - 2 5 eV modified s u b s t a n t i a l l y
by t h e presence of single-electron (inter a n d i n t r a b a n d ) t r a n s i t i o n s . It is possible t o infer c o m p o s i t i o n a l
i n f o r m a t i o n from p l a s m o n p e a k shifts, b u t this tech
n i q u e is limited t o free-electron m e t a l s such a s a l u m i
n u m a n d m a g n e s i u m a n d their alloys. T h e specimen
thickness c a n also b e d e t e r m i n e d if t h e p l a s m o n m e a n
free p a t h is k n o w n . It is also possible t o e x t r a c t t h e
real a n d i m a g i n a r y p a r t s of t h e dielectric c o n s t a n t of
the s a m p l e b y p e r f o r m i n g a K r a m e r s - K r o n i g analysis
o n t h e low-loss s p e c t r u m . W h i l e this a p p r o a c h h a s
lower energy r e s o l u t i o n t h a n o t h e r t e c h n i q u e s for
dielectric c o n s t a n t m e a s u r e m e n t it h a s t h e a d v a n t a g e s
of high spatial r e s o l u t i o n (see Sect. 3) a n d a relatively
1 2
1 4
b r o a d frequency r a n g e from a r o u n d 1 0 - 1 0 H z .
I n t h e high-loss region of t h e s p e c t r u m b e y o n d a n y
p l a s m o n p e a k s , t h e intensity falls off r a p i d l y w i t h
Energy-Loss
Spectrometry
3. Spatial
Resolution
and Detectability
Limit
4.
Deconvolution
I n f o r m a t i o n in t h e s p e c t r u m c a n b e e x t r a c t e d with
m o r e c e r t a i n t y if m u l t i p l e - s c a t t e r i n g effects a r e
r e m o v e d . T h i s c a n b e c a r r i e d o u t using a variety of
d e c o n v o l u t i o n t e c h n i q u e s such a s F o u r i e r - r a t i o ,
F o u r i e r - l o g a n d digital filtering. F i g u r e 3 s h o w s spec
t r a from p u r e a l u m i n u m in b o t h t h e a s - r e c o r d e d state
a n d after F o u r i e r - l o g d e c o n v o l u t i o n . T h e d e c o n v o
l v e d s p e c t r u m s h o w s t h e first p l a s m o n p e a k b u t t h e
s e c o n d (multiple scattering) p l a s m o n p e a k (/ p(2)) h a s
been r e m o v e d (except for a m i n o r d o u b l e - p l a s m o n
p e a k ) leaving t h e t r u e " s i n g l e - s c a t t e r i n g " s p e c t r u m .
In a d d i t i o n , it c a n be seen t h a t t h e s h a p e of t h e
i o n i z a t i o n edge c h a n g e s significantly after d e c o n v o l u
tion. T h e r e f o r e , it is essential t o r e m o v e multiplescattering effects before a t t e m p t i n g t o interpret t h e
fine s t r u c t u r e (see Sect. 5) associated with t h e edge.
113
Electron
Energy-Loss
Spectrometry
23
ionization edge
6.
deconvolved
f as recorded
40
80
120
160
Figure 3
Energy-loss spectrum from pure aluminum shown as
recorded and after deconvolution. The Al L 2 3 ionization
edge at 73 eV is magnified 16 in both spectra (courtesy
of D-R. Liu)
D e c o n v o l u t i o n is i m p o r t a n t b o t h for t h e best q u a n t i
fication a n d for t h e K r a m e r s - K r o n i g analysis a l r e a d y
discussed. Alternatively, very t h i n ( < ~ 20 n m ) speci
m e n s w h i c h m i n i m i z e multiple scattering m a y b e used,
a l t h o u g h surface effects (such as surface p l a s m o n s
a n d oxide films) m a y modify t h e spectra.
5. Fine-Structure
7. Limitations
and Future
Development
M a j o r l i m i t a t i o n s t o E E L S arise b e c a u s e of t h e u s u a l
(serial) m e t h o d of d a t a collection. T h i s m e a n s t h a t
spectral acquisition m a y t a k e several m i n u t e s t o
satisfy statistical r e q u i r e m e n t s for analysis. D u r i n g
Effects
114
Imaging
Figure 4
Images of an Al/SiC composite: (a) STEM bright field;
(b) chemical image from Al edge; (c) chemical image
from Si edge (after Leapman et al. 1984.
Ultramicroscopy. North-Holland, Amsterdam.
Reproduced with permission)
Electron
Microprobe
Analysis
180
200
220
Energy loss (eV)
Figure 5
Portion of energy-loss spectrum showing the boron
edge; the spectrum was acquired in 0.1 s using parallel
collection (courtesy of O. Krivanek)
T h e electron m i c r o p r o b e analyzer ( E M A ) w a s d e
veloped in t h e early 1950s by C a s t a i n g a t t h e U n i v e r
sity of Paris. T h e i n s t r u m e n t uses a focused b e a m of
electrons t o locally excite rays from a region as small
as a few m i c r o m e t e r s o r less o n a specimen. T h e
w a v e l e n g t h d i s t r i b u t i o n of the e m i t t e d rays is
m e a s u r e d by m e a n s of o n e o r m o r e crystal-diffraction
s p e c t r o m e t e r s . E l e m e n t a l c o n s t i t u e n t s c a n t h e n be
identified with the aid of M o s e l e y ' s law which
u n i q u e l y relates t h e w a v e l e n g t h of each observed
spectral line t o a specific element t h r o u g h the
relationship
\lk =
k(Z-a)
0)
w h e r e is t h e x-ray w a v e l e n g t h , A: is a c o n s t a n t for
e a c h spectral-line series, is t h e a t o m i c n u m b e r of the
element from which t h e rays o r i g i n a t e a n d is a
c o n s t a n t associated with the a t o m i c screening effects.
I n a d d i t i o n t o qualitative analysis, q u a n t i t a t i v e analy
sis is also possible. T h i s is d o n e by c o n v e r t i n g
m e a s u r e d x-ray line intensities, n o r m a l i z e d by p u r e
e l e m e n t a l - s t a n d a r d intensities, t o c o m p o s i t i o n s using
a variety of r e a s o n a b l y well-developed f u n d a m e n t a l
p a r a m e t e r q u a n t i t a t i o n schemes. S a m p l e s for E M A
analysis a r e n o r m a l l y well-polished m e t a l l o g r a p h i c
sections. T h e regions t o be a n a l y z e d a r e selected by
m e a n s of a light m i c r o s c o p e m o u n t e d coaxially with
the electron optical system. In a d d i t i o n , a l m o s t all
E M A s h a v e s e c o n d a r y - e l e c t r o n d e t e c t o r s , electrondeflection systems a n d c a t h o d e - r a y - t u b e ( C R T ) dis
plays which allow t h e m t o be o p e r a t e d as s c a n n i n g
electron m i c r o s c o p e s ( S E M s ) (see Scanning
Electron
Microscopy).
T h i s feature is n o t only useful in identi
fying regions t o be a n a l y z e d b u t also m a k e s it possible
t o o b t a i n e l e m e n t a l - d i s t r i b u t i o n i n f o r m a t i o n in either
o n e d i m e n s i o n (line scans) o r in t w o d i m e n s i o n s (xray distribution maps).
Bibliography
Colliex C 1985 An illustrated review of the various factors
governing the high spatial resolution capabilities in EELS
microanalysis. Ultramicroscopy 18: 131-50
Egerton R F 1986 Electron Energy-Loss Spectroscopy in the
Electron Microscope. Plenum, New York
Isaacson 1987 Microcharacterization. Plenum, New York
Joy D C, Romig A D Jr, Goldstein J I (eds.) 1986 Principles
of Analytical Electron Microscopy. Plenum, New York
Leapman R D 1984 Electron energy loss microspectroscopy
and the characterization of solids. In: Kyser D F, Niedrig
H, Newbury D E, Shimizu R (eds.) 1984 Electron Beam
Interactions with Solids for Microscopy, Microanalysis and
Microlithography: Proc. 1st Pfefferkorn Conf Scanning
Electron Microscopy Inc., O'Hare, IL, pp. 217-33
Williams D 1984 Practical Analytical Electron Microscopy
in Materials Science. VCH, Deerfield Beach, FL
D . B. W i l l i a m s
[Lehigh University, B e t h l e h e m ,
Pennsylvania, USA]
1. General
Operating
Principles
115
Electron
Microprobe
Scanning coils
Analysis
^ \
Specimen
Figure 1
Electron microprobe analyzer
116
c o n t i n u o u s s p e c t r u m o r " c o n t i n u u m " w h i c h is t h e
principal s o u r c e of b a c k g r o u n d r a d i a t i o n .
I n t h e E M A , x-ray spectral m e a s u r e m e n t s a r e
principally p e r f o r m e d using crystal-diffraction spec
t r o m e t e r s ( C D S s ) . Energy-dispersive s p e c t r o m e t e r s
(widely used in s c a n n i n g electron m i c r o s c o p y ) a r e also
used (see Sect. 2). T h e basic c o m p o n e n t s of t h e C D S
as s h o w n in F i g . 1 include a n a n a l y z i n g crystal, a
d e t e c t o r a n d r e a d o u t electronics. T h e region of x-ray
excitation is essentially a p o i n t source with rays
travelling o u t in all directions. A small fraction of
these rays exit t h e electron optical c o l u m n a n d e n t e r
t h e s p e c t r o m e t e r w h e r e they i m p i n g e o n t h e a n a l y z i n g
crystal. T h i s is a thin r e c t a n g u l a r wafer w h i c h is c u t
such t h a t crystal p l a n e s of a preselected i n t e r p l a n a r
spacing a r e parallel t o its surface. A s t h e incident
angle is varied, a m a x i m u m in x-ray intensity o c c u r s
a t t h e d e t e c t o r w h e n B r a g g ' s law
= 2d sin
(2)
electron
removed
Ka
emission
- L electron
removed
La
Ma
M electron
removed
- electron
removed
Normal -
-^Valence
electron
removed
Figure 2
Simplified energy-level diagram illustrating some of the
major spectral transitions
Electron
" / /
Thin
window
Preamplifier
High
voltage (+ )
X rays
Figure 3
Flow proportional counter
dL/R
(3)
w h e r e R is t h e r a d i u s of c u r v a t u r e of t h e s p e c t r o m e t e r
a n d L is t h e d i s t a n c e from t h e specimen t o t h e
analyzing crystal. I n practice, s p e c t r o m e t e r s a r e
usually e q u i p p e d with multiple crystal h o l d e r s
because a series of i n t e r p l a n a r spacings a r e r e q u i r e d
to cover t h e w a v e l e n g t h r a n g e of interest. E x a m i n a
tion of E q n . (2) s h o w s t h a t since sin c a n never b e
greater t h a n o n e , t h e n for first-order reflections t h e
wavelengths m e a s u r e d c a n never exceed twice t h e
i n t e r p l a n a r spacing of t h e crystal. T h u s , a L i F crystal
with a 2d spacing of 0.4028 n m is n o t suitable for
m e a s u r i n g a l u m i n u m Ka, w i t h a w a v e l e n g t h of
0.8339 n m , b u t is well suited t o m e a s u r i n g c o p p e r KOL
at 0.1541 n m . A n a p p r o p r i a t e crystal for a l u m i n u m is
p e n t a e r y t h r i t o l ( P E T ) w i t h a 2d s p a c i n g of 0.8472 n m .
T h e m i n i m u m w a v e l e n g t h m e a s u r a b l e with a crystal
c a n be o b t a i n e d from E q n . (3) since there is a m i n i
m u m value of L d e t e r m i n e d b y physical c o n s t r a i n t s
o n the s p e c t r o m e t e r .
T h e x-ray d e t e c t o r m o s t c o m m o n l y used o n t h e
C D S is a p r o p o r t i o n a l c o u n t e r of t h e t y p e illustrated
in Fig. 3. It consists of a g r o u n d e d m e t a l cylinder with
a n electrically isolated thin m e t a l wire r u n n i n g u p t h e
center. T h e wire is c o n n e c t e d t o a h i g h - v o l t a g e p o w e r
supply ( 1 - 3 k V ) t h r o u g h a large c u r r e n t - l i m i t i n g resis
tor. It is also ac c o u p l e d t o a preamplifier m o u n t e d
close b y t o r e d u c e electrical-noise p i c k u p . T h e detec
t o r is filled with a m i x t u r e of a n inert gas a n d a small
p e r c e n t a g e of m e t h a n e . X rays from t h e a n a l y z i n g
crystal enter t h r o u g h a t h i n w i n d o w m o u n t e d o n the
side o r e n d of t h e m e t a l t u b e . T h e w i n d o w is c h o s e n t o
be thin e n o u g h t o r e d u c e x-ray a b s o r p t i o n , b u t it m u s t
be s t r o n g e n o u g h t o w i t h s t a n d a v a c u u m since t h e
s p e c t r o m e t e r m a y be e v a c u a t e d t o m i n i m i z e x-ray
a b s o r p t i o n in t h e p a t h from t h e s a m p l e t o t h e detec
tor. If a thin-film p o l y m e r w i n d o w is used so as t o
further r e d u c e x-ray a b s o r p t i o n , as is necessary in t h e
m e a s u r e m e n t of soft r a y s , t h e n a r g o n is t h e m o s t
Microprobe
Analysis
2. Energy-Dispersive
X-Ray
Detectors
117
Electron
Microprobe
Analysis
Dataoutput
device
Pileup
rejector
Electron
Cryostat
Computer
I Bios suppl7
LAL
Display
Specimen
X - ray signal
Figure 4
Energy-dispersive x-ray detector
118
3.
Applications
T h e E M A c a n be used t o p r o v i d e m i c r o s c o p i c elemen
tal c h a r a c t e r i z a t i o n of a wide variety of samples
e n c o u n t e r e d in m a n y disciplines including metallurgy,
ceramics, m i n e r a l o g y , biology, geology a n d medicine.
In a d d i t i o n t o qualitative analysis, which h a s a l r e a d y
been discussed, it is possible t o use q u a n t i t a t i v e p r o
c e d u r e s t o o b t a i n elemental c o m p o s i t i o n s with 2 - 5 %
relative a c c u r a c y for elements p r e s e n t a b o v e a level of
a few percent. M a t h e m a t i c a l m e t h o d s m a k e it p o s
sible t o p e r f o r m such analyses with a b a r e m i n i m u m
of s t a n d a r d s (for e x a m p l e , only p u r e elemental stan
d a r d s for e a c h c o m p o n e n t ) . A n e x a m p l e of a q u a n t i
tative step scan is given in F i g . 7. T h e s a m p l e is a
diffusion c o u p l e of C u - 1 0 w t % N i b o n d e d t o C u 80 w t % N i a n d a n n e a l e d a t 900 C for 100 h. T h e d a t a
Epoxy mount
Matrix
Carbides
Figure 5
Scanning electron micrograph of the cross section of a
high-temperature alloy. The sample sheet was etched for
5 min in a mixture of bromine and methanol to reveal
carbides
Electron
Microprobe
Analysis
90
80
70
ic
60
50
40
9
*-
/\
Ni + Ta
50
100
150
200
250
Distance in microns
300
350
40<
(/*m)
Figure 7
Diffusion-profile scans of Cu-10wt%Ni bonded to
Cu-80wt%Ni annealed for 100 h at 900 C: , copper;
, nitrogen (courtesy of N. Lewis, General Electric
Corporate Research and Development)
Br
Cr
Energy
Ni
(keV)
(b)
Figure 6
Energy-dispersive spectra obtained from matrix and
carbides in the treated temperature alloy of Fig. 5:
(a) spectrum from the matrix; and (b) spectrum from a
carbide (note that carbon is not seen because of
absorption in the beryllium window of the detector)
(courtesy of C. D. Robertson, General Electric Corporate
Research and Development)
d r i v e n c o n t i n u o u s l y u n d e r a static p r o b e while t h e
v a r i a t i o n in intensity of o n e o r m o r e elements is
m o n i t o r e d with t h e r a t e m e t e r s t r i p - r e c o r d e r c o m
b i n a t i o n . Line-scan i n f o r m a t i o n of a similar t y p e c a n
also be displayed o n the C R T i m a g i n g system b y
m a k i n g a c o m p o s i t e p i c t u r e of t h e s c a n n i n g electron
m i c r o g r a p h of t h e t a r g e t a r e a a n d t h e line of the
a c t u a l scan, a n d t h e n s u p e r i m p o s i n g the r a t e m e t e r
output.
X - r a y m a p s c a n be used t o s h o w t h e t w o - d i m e n
sional d i s t r i b u t i o n of o n e o r m o r e elements a n d t h e
c o r r e s p o n d i n g m i c r o s t r u c t u r e as seen b y t h e S E M .
F i g u r e 8 c o n t a i n s a n S E M i m a g e of a particle of B N
in a m a t r i x of d i a m o n d a n d t h e c o r r e s p o n d i n g d o t
m a p s for c a r b o n , n i t r o g e n a n d b o r o n . T h e m a p s a r e
o b t a i n e d b y c o u p l i n g t h e o u t p u t from t h e singlec h a n n e l a n a l y z e r t o t h e " Z " i n p u t (brightness) of the
C R T display. E a c h time a pulse is detected, it is
displayed as a d o t o n t h e C R T . A r e a s of high c o n c e n
t r a t i o n of a p a r t i c u l a r e l e m e n t a r e s h o w n as a n
increase in d o t density r a t h e r t h a n a c h a n g e in g r a y
scale. T h i s b i n a r y - m a p m o d e of p r e s e n t a t i o n is
r e q u i r e d b e c a u s e t h e x-ray signal level is m a n y o r d e r s
of m a g n i t u d e less t h a n t h a t of t h e c o r r e s p o n d i n g
s e c o n d a r y - e l e c t r o n signal. T h e e x a m p l e s h o w n in Fig.
8 also illustrates t h e ability of t h e C D S t o collect d a t a
f r o m l o w - a t o m i c - n u m b e r elements. W i n d o w l e s s E D S
systems a r e also b e i n g d e v e l o p e d , b u t their p o o r e r
energy r e s o l u t i o n will greatly restrict their use for xr a y m a p p i n g of these e l e m e n t s .
See also: Chemical Analysis of Solid Surfaces; Electron
Microscopy, Analytical; X-Ray Fluorescence Spectrometry
119
Electron
Microprobe
Analysis
Figure 8
X-ray maps of a BN crystal in diamond: (a) scanning electron micrograph, and the corresponding dot maps for
(b) carbon, (c) nitrogen and (d) oxygen (courtesy of M. D. McConnell, General Electric Corporate Research and
Development)
Bibliography
Goldstein J I et al. 1992 Scanning Electron Microscopy and
X-Ray Microanalysis: A Text for Biologists, Materials
Scientists, and Geologists. Plenum, New York
Heinrich F J 1981 Electron Beam X-Ray Microanalysis.
Van Nostrand Reinhold, New York
Heinrich F J et al. (eds.) 1981 Energy Dispersive Spec
trometry, NBS Special Publication 604. National Bureau
of Standards, Washington, DC
Maurice F, Meny L, Tixier R (eds.) 1978 Microanalysis and
Scanning Electron Microscopy. Editions De Physique,
Orsay, France
Reed S J 1975 Electron Microprobe Analysis. Cambridge
University Press, Cambridge
Wells C 1974 Scanning Electron Microscopy. McGrawHill, New York
E. Lifshin
[General Electric C o r p o r a t e R e s e a r c h
and Development, Schenectady,
New York, USA]
120
/.
Defect
Clusters
Electron
Microscope
Analysis
of Defect
Clusters,
Voids and
Bubbles
2.
Voids
V o i d s a r e gas-free cavities in a n i r r a d i a t e d m a t e r i a l
a n d a p p e a r a s light regions a g a i n s t a d a r k e r b a c k
g r o u n d in t h e electron m i c r o s c o p e i m a g e (see F i g . 2).
T h e s e large voids a r e o b s e r v e d t h r o u g h a b s o r p t i o n
c o n t r a s t , a s there is less electron a b s o r p t i o n w h e n t h e
electron b e a m passes t h r o u g h t h e void. Smaller voids
a r e n o r m a l l y i m a g e d in a n u n d e r - f o c u s c o n d i t i o n , in
w h i c h t h e b r i g h t Fresnel fringe a c c e n t u a t e s t h e void.
Figure 1
Transmission electron micrograph of defect clusters in
nickel irradiated with neutrons at ~ 330 to a dose of
5 x 10 23 neutrons m 2 (E> 1 MeV); the arrow indicates a
dislocation loop
Figure 2
Transmission electron micrograph of voids in nickel
neutron-irradiated at 800 to a dose of 5 x 10 23 neutrons
m - 2( > l M e V )
121
Electron
Microscope
Analysis
of Defect
Clusters,
Voids and
Bubbles
Figure 3
Transmission electron micrograph of a void lattice in
niobium irradiated with 7.5 MeV tantalum ions at 1070
to a dose of 5 10 20 ions m 2
Figure 4
Transmission electron micrograpoh of helium gas bubbles
in molybdenum bombarded with 200 keV particles at
1470
122
3.
Bubbles
B u b b l e s a r e i n t e r n a l cavities t h a t c o n t a i n gas a t o m s
such as h e l i u m o r k r y p t o n . A n e q u i l i b r i u m b u b b l e
c o n t a i n s e n o u g h gas t h a t t h e internal gas p r e s s u r e j u s t
b a l a n c e s t h e surface tension of t h e cavity. B u b b l e s
give t h e s a m e c o n t r a s t in t h e electron m i c r o s c o p e as
voids a n d , in this sense, voids a n d b u b b l e s a r e indis
tinguishable. T h e m a i n distinctive feature is t h a t
b u b b l e s form preferentially a t grain b o u n d a r i e s , dislo
c a t i o n s a n d o t h e r i n t e r n a l defects, w h e r e a s voids d o
n o t . Preferential f o r m a t i o n of h e l i u m b u b b l e s a t dislo
c a t i o n s in - b o m b a r d e d m o l y b d e n u m is illustrated in
Fig. 4. B u b b l e s c a n also a s s u m e a c r y s t a l l o g r a p h i c
s h a p e similar t o voids.
B u b b l e s result from t h e coalescence of gas f o r m e d
by transmutation reactions during neutron irradia-
Electron
Bibliography
Brager R, Perrin J S 1982 Effects of Radiation on
Materials, ASTM STP 782. American Society for Testing
and Materials, Philadelphia, PA
Corbett J W, Ianiello L C (eds.) 1971 Int. Conf. RadiationInduced Voids in Metals. National Technical Information
Service, Springfield, VA
Gittus J 1978 Irradiation Effects in Crystalline Solids.
Applied Science, London, Chaps. 2-4, pp. 37-166
Goodhew J 1988 Migration of bubbles, voids and inclu
sions in crystals. In: Cahn R W (ed.) 1988 Encyclopedia
of Materials Science and Engineering, Suppl. Vol. 1.
Pergamon, Oxford, pp. 318-22
Makin J (ed.) 1966 Report of Consultants Symposium on
the Nature of Small Defect Clusters, AERE Report N o .
R-5269. HMSO, London
Makin J 1971 The application of electron microscopy to
radiation damage studies. In: Valdre U (ed.) 1971 Elec
tron Microscopy in Materials Science. Academic Press,
London, pp. 388-461
Merkle L 1975 Defect production by energetic particle
bombardment. In: Peterson L, Harkness S D (eds.)
1975 Radiation Damage in Metals. ASM International,
Materials Park, OH
Nelson R S (ed.) 1975 Proc. Symposium Physics of Irradia
tion Produced Voids, AERE Report No. R-7934. HMSO,
London
Norris D I R 1972 Voids in irradiated metals. Radiat. Eff.
14: 1-37; 15: 1-35
Wiffen F W, Spitznagel J A (eds.) 1982 Advanced Techniques
for Characterizing Microstructures. Metallurgical Society
of AIME, Warrendale, PA
J. L. B r i m h a l l
[Battelle-Pacific N o r t h w e s t L a b o r a t o r i e s ,
Richland, Washington, U S A ]
Microscopy,
Analytical
1.
Instrumentation
T h e A E M is usually b a s e d o n t h e s c a n n i n g t r a n s m i s
sion electron m i c r o s c o p e ( S T E M ) , which scans a fine
p r o b e of electrons a c r o s s a thin-foil specimen. T w o
f o r m s exist: t h e so-called d e d i c a t e d S T E M s , which
c a n only o p e r a t e in s c a n n i n g m o d e a n d a r e similar in
Incident
electron probe
Primary
backscattered
electrons
Characteristic
rays
Thin specimen
Inelastically
scattered electrons
Figure 1
Schematic representation of the most common signals
available to the analytical electron microscopist
123
Electron
Microscopy,
Analytical
principle t o S E M s , a n d c o n v e r t e d T E M s ( T E M /
S T E M s ) . T h e latter form a r e c o n s i d e r a b l y m o r e
n u m e r o u s a n d in m a n y respects a r e m o r e versatile
i n s t r u m e n t s (see Fig. 2). W h e n the b e a m scans over
the desired a r e a of the specimen, a n y of the signals
generated in Fig. 1 c a n be detected, as s h o w n in Fig. 2,
a n d used t o m o d u l a t e a c a t h o d e r a y t u b e display, t h u s
forming a n i m a g e . It is u s u a l t o m a k e use of the
t r a n s m i t t e d a n d scattered electrons t o form images
equivalent t o bright-field a n d dark-field images in a
T E M . T o o b t a i n chemical i n f o r m a t i o n from a desired
region, it is necessary t o s t o p t h e s c a n n i n g p r o b e a n d
position it o n t h e region of interest, a n d t h e n switch
o n the x-ray o r electron energy-loss detector. T h e
c o m b i n a t i o n of a very fine ( < 10 n m ) electron p r o b e
a n d thin-foil specimen h a s t h e specific a d v a n t a g e t h a t
a n y i n f o r m a t i o n o b t a i n e d is from a very small v o l u m e
of the specimen, since b e a m - s p r e a d i n g t h r o u g h thin
foils is n o t very significant. Spatial r e s o l u t i o n of
chemical analysis is generally c o n s i d e r e d t o b e
< 50 n m in m o s t e l e c t r o n - t r a n s p a r e n t
material
specimens.
Electron source
Condenser I
Condenser
Double deflection
scan coils
Secondary electron
Backscattered
electron detection
X-rav detection
2. X-Ray
Microanalysis
in the A EM
124
^
^2^**
rV////A
Projector lens to
control detector
collection angle
Transmitted electron
detection (bright field]
Energy
analysis
or image
display
Figure 2
The electron optics of a TEM/STEM used as an analytical
microscope. The various signals generated at the specimen
(Fig. 1) are detected and displayed as shown. Diffraction
information is available in the back focal plane of the
objective lens (courtesy of Philips Electronics Instruments
Inc.)
Electron
Microscopy,
Analytical
Ni
looo
Cr
wy.u..
Ni
Ni
Cr
Energy
(keV)
Figure 3
Typical energy-dispersive x-ray spectrum obtained from an alloy of nickel-chromium-iron showing the principal
characteristic K a and K p peaks for these elements. The nickel L line is also present at ~ 1 keV. The presence of a small
amount of silicon is also indicated.
= kABIJIB
(1)
w h e r e t h e c o n c e n t r a t i o n C of elements A a n d is
directly related t o t h e characteristic x-ray intensity I,
t h r o u g h a factor A: AB w h i c h c a n b e either e x p e r i m e n
tally d e t e r m i n e d o r calculated from first principles.
U n d e r situations where absorption and
fluorescence
are n o t negligible, simple e q u a t i o n s exist t o a c c o u n t
for t h e effect ( G o l d s t e i n et al. 1977). A n e x a m p l e of
the use of E q n . (1) t o d e t e r m i n e t h e v a r i a t i o n in silver
c o m p o s i t i o n a c r o s s a g r a i n - b o u n d a r y precipitate-free
z o n e in a l u m i n u m - s i l v e r is s h o w n in Fig. 4.
T h e c o m b i n a t i o n of a fine p r o b e p r o d u c e d in
S T E M a n d limited electron scattering d u e t o t h e use
of thin specimens m e a n s t h a t t h e spatial r e s o l u t i o n of
microanalysis is m u c h b e t t e r t h a n t h e limit of x-ray
microanalysis of b u l k specimens, a r o u n d 1 (see
Electron Microprobe
Analysis).
Several theoretical
a n d e x p e r i m e n t a l t e c h n i q u e s exist t o e s t i m a t e t h e
a c t u a l spatial r e s o l u t i o n of m i c r o a n a l y s i s . T h e m o s t
sophisticated m e t h o d s use M o n t e C a r l o c o m p u t e r
s i m u l a t i o n s of electron trajectories ( K y s e r 1979), b u t
a simple e q u a t i o n d e v e l o p e d b y R e e d serves for m o s t
p u r p o s e s ( G o l d s t e i n et al. 1977). T h e b e a m s p r e a d i n g
b of a p o i n t s o u r c e of electrons of incident e n e r g y E0
in a specimen of a t o m i c n u m b e r Z , a t o m i c weight A,
density a n d thickness t is given b y
3. Microanalysis
Electrons
Using Inelastically
Scattered
125
Electron
Microscopy,
Analytical
(b)
stem
valves
extrapolated
G composition
I
I
-2
IPFZI
Distance
(10
nm )
Figure 4
(a) TEM image of a precipitate-free zone (PFZ) in Al-16 at.%Ag aged for 75 min at 250 C. Coarse equilibrium -phase
precipitates are present along the boundary which depletes the surrounding region of silver thus preventing precipitation
of either metastable GP zones (small spherical precipitates) or metastable y' (larger platelike particles), (b) Silver
composition profile across a precipitate-free zone (PFZ) in Fig. 4a obtained by quantification of EDS spectra from many
points on either side of the grain boundary (GB). Silver depletion within the PFZ is clearly visible and extrapolation to
the grain-boundary composition gives information about the phase diagram at 250 C (courtesy of S. Merchant)
126
4. Future
Developments
A E M h a s e x p a n d e d r a p i d l y i n t o all fields of m a t e r i a l s
science a n d will be t h e m a j o r m o d e of electron m i c r o
scope d e v e l o p m e n t in t h e foreseeable future. T h e use
of s c a n n i n g b e a m s a n d , therefore, electron d e t e c t o r s
a n d digital signals gives t h e user electronic access t o
all t h e d a t a . T h u s , on-line d a t a m a n i p u l a t i o n is n o w
possible w h i c h , c o m b i n e d w i t h c o m p u t e r h a n d l i n g of
d a t a a n d feedback c o n t r o l of t h e m i c r o s c o p e , p r o
mises t o revolutionize t h e a c q u i s i t i o n of s t r u c t u r a l
a n d chemical i n f o r m a t i o n from m a t e r i a l s ( R e z a n d
W i l l i a m s 1982). E D S t e c h n i q u e s in A E M a r e a l m o s t
Electron
Microscopy,
High-Resolution
Bibliography
Energy l<
Figure 5
TEM micrograph of a small precipitate particle in
stainless steel. The energy-loss spectrum below shows
peaks corresponding to ionization of the nitrogen shell
and titanium L shells, indicating that the precipitate is
TiN (courtesy of N. J. Zaluzec)
127
Electron
Microscopy,
High-Resolution
I.
Instrumentation
C o m m e r c i a l high-resolution electron m i c r o s c o p e s
( H R E M s ) in t h e 2 0 0 - 4 0 0 k e V p o t e n t i a l difference
r a n g e h a v e t h e s a m e external a p p e a r a n c e as c o n v e n
tional t r a n s m i s s i o n electron m i c r o s c o p e s a n d it is t h e
differences in their internal i n s t r u m e n t a t i o n t h a t allow
high resolutions t o be a t t a i n e d . E l e c t r o n sources in
H R E M s t e n d t o be either p o i n t e d t u n g s t e n filaments
or l a n t h a n u m h e x a b o r i d e ( L a B 6 ) filaments, b o t h of
which give high brightness a n d e n a b l e direct magnifi
c a t i o n s of over x 500 000 t o be usefully e m p l o y e d . A n
alternative to these t w o electron sources is the field
emission g u n with a t u n g s t e n c a t h o d e . T h i s c o m b i n e s
a low energy s p r e a d with a high brightness, b o t h of
which are very desirable characteristics, b u t the d r a w
b a c k s of a field emission g u n a r e t h a t it needs a high
10
v a c c u m of the o r d e r of 1 0 ~ t o r r a n d t h a t it is difficult
for it to p r o v i d e a u n i f o r m illumination of samples
over r e a s o n a b l y sized a r e a s .
T h e o t h e r m a i n difference in the i n s t r u m e n t a t i o n
between c o n v e n t i o n a l a n d high-resolution t r a n s m i s
sion electron m i c r o s c o p e s is in the design of the
objective lenses. In H R E M s the focal length of the
objective lens is k e p t as s h o r t as possible (typically less
t h a n 2 m m ) to minimize lens a b e r r a t i o n s (see Sect. 2).
In practice this m e a n s t h a t there is little r o o m in which
to p u t the specimen a n d , in the effort to a t t a i n high
resolution, c o m p r o m i s e s a r e usually m a d e in the
design of electron lenses t h a t limit t h e r a n g e of
specimen tilting t o typically 15. It is also vitally
i m p o r t a n t in a n H R E M t o m a i n t a i n a clean e n v i r o n
m e n t a r o u n d t h e specimen t o minimize specimen
c o n t a m i n a t i o n over p r o l o n g e d p e r i o d s of m i c r o s c o p e
usage. T h i s m e a n s t h a t effective a n t i c o n t a m i n a t i o n
128
2. Image
Formation
T h e r e a r e t w o principal i m a g i n g m o d e s which a r e
used t o f o r m H R E M images: t h e m a n y - b e a m axiali l l u m i n a t i o n m o d e , in w h i c h t h e undiffracted electron
b e a m is coincident with t h e o p t i c axis of t h e m i c r o
scope, a n d the t w o - b e a m tilted-illumination m o d e , in
which the undiffracted electron b e a m a n d a diffracted
b e a m a r e symmetrically disposed either side of t h e
o p t i c axis (see Fig. 1). In general, t h e axial m o d e of
high-resolution i m a g i n g is t h e o n e used o n the c u r r e n t
g e n e r a t i o n of H R E M s . T h e t i l t e d - b e a m m o d e , w h i c h
w a s used in t h e d e v e l o p m e n t of t h e t e c h n i q u e of highresolution electron m i c r o s c o p y , is n o w s e l d o m used,
a l t h o u g h if care is t a k e n this m o d e c a n give consider
able success.
I m a g e f o r m a t i o n in the H R E M c a n b e t r e a t e d
conveniently by s e p a r a t i n g t h e physical process of
forming a n i m a g e i n t o t w o s e p a r a t e stages m a t h e m a
tically. T h e first stage is t h e scattering b y t h e specimen
of t h e high-energy e l e c t r o n s p r o d u c e d by t h e electron
source. T h i s c a n be described b y t h e d y n a m i c a l t h e o r y
of electron diffraction in which the w a v e function of
Electron
Microscopy,
High-Resolution
T(u) = exp[iX(u)]E(u)
(2)
where
3
= ^ 4
x optic
(4)
= J jV(jc,j>)exp[27n(wx + vy)] dx dy
(3)
(w) = e x p ( - i 7 d A V )
beam
Figure 1
Imaging modes in an HREM: (a) the axial-illumination
mode and (b) the two-beam tilted-illumination mode. In
both (a) and (b) the outline of a suitable objective
aperture is shown
F(u) = F(u, ) =
axis
transmitted
+ /*
= nF(u)T(u)]
(5)
(1)
( ^ ) =
( , ^ ) [ - ^ ( ^ ) ]
= V0(x,y)[l
- ia<p(x,y)]
(6)
~ 1 + 2(^)*&{(
2
T(u)]}
(7)
129
Electron
Microscopy,
High-Resolution
a n d regions b e t w e e n a t o m c o l u m n s a r e i m a g e d as
bright c o n t r a s t regions.
In practice, h o w e v e r , t h e w e a k p h a s e object
a p p r o x i m a t i o n is of limited use. A l t h o u g h there is a
great t e m p t a t i o n t o interpret h i g h - r e s o l u t i o n images
intuitively in t e r m s of projected p o t e n t i a l s a n d u n d e r
circumstances of c o n t r a s t reversal (where a t o m s a r e
i m a g e d as b r i g h t regions) there is n o real s u b s t i t u t e
for detailed i m a g e s i m u l a t i o n s as a function of thick
ness a n d lens defocus. E v e n u n d e r such c o n d i t i o n s
ambiguities c a n still arise in t h e i n t e r p r e t a t i o n of highresolution images if t h e m a t e r i a l is t o o thick (in w h i c h
case inelastic scattering events m a y significantly affect
the form of t h e image) o r if the m a t e r i a l c o n t a i n s
n o n p e r i o d i c detail.
3. Microscope
Resolution
F r o m c o n s i d e r a t i o n of h o w the i m a g e is f o r m e d in a
t r a n s m i s s i o n electron m i c r o s c o p e it is clear t h a t the
function T(u) will c o n t a i n t e r m s t h a t a r e d e p e n d e n t o n
the electron optical p e r f o r m a n c e of a n R E M . H e n c e
the b e h a v i o r of T(u) as a function of u for different
defocus values c a n be used t o c h a r a c t e r i z e t h e electron
optical p e r f o r m a n c e of a p a r t i c u l a r R E M . I n p r a c
tice, it is c o m m o n t o p l o t t h e function ()
as a
function of u for different defocus values AF, with o r
w i t h o u t the envelope function E{u). T h e curves p r o
d u c e d in this m a n n e r a r e t e r m e d c o n t r a s t transfer
functions ( C T F s ) . T h e o p t i m u m o p e r a t i n g c o n d i t i o n s
for a p a r t i c u l a r H R E M are usually t a k e n t o be a t
values of defocus w h e r e the C T F h a s a r e a s o n a b l y
c o n s t a n t value over a wide r a n g e of spatial frequen
cies. Of p a r t i c u l a r i m p o r t a n c e a r e t h e values of defo
cus k n o w n as " e x t e n d e d Scherzer d e f o c u s , " a t w h i c h
AF = - 1.5*CSU*, a n d " e x t e n d e d s e c o n d b r o a d b a n d
d e f o c u s , " a t which AF= - 3.5*C SU*. T h e t e r m
" S c h e r z e r d e f o c u s " d e n o t e s a value of defocus AF
o f - C s U . Typical C T F s for a state-of-the-art
400 keV H R E M are s h o w n in Fig. 2.
T h e r e is n o simple definition of t h e " p o i n t - t o p o i n t " resolution of a n H R E M . T h e
instrumental
resolution c a n b e t a k e n t o be t h e inverse of t h e spatial
frequency a t w h i c h t h e value of t h e envelope function
2
E(u) falls t o e~ . T h i s i n s t r u m e n t a l r e s o l u t i o n will
often be far s u p e r i o r to 3^0.64 C SU*, the inverse of
the spatial frequency a t which t h e C T F crosses t h e
h o r i z o n t a l axis a t e x t e n d e d Scherzer defocus which is
often t a k e n as a m e a s u r e of t h e interpretable
resolu
tion of a m i c r o s c o p e , b e c a u s e of t h e difficulty of
interpreting accurately i n f o r m a t i o n within t h e s t r o n g
oscillations of t h e C T F a t high spatial frequencies.
O t h e r definitions of i n t e r p r e t a b l e r e s o l u t i o n use the
value ( 5 ~ 0 . 7 0 7 C S U * a t which t h e C T F crosses t h e
h o r i z o n t a l axis a t Scherzer defocus o r the value
(5 ~ 0.67 C SU* c o r r e s p o n d i n g t o t h e higher spatial fre
q u e n c y of the " p a s s b a n d " a t e x t e n d e d Scherzer defo
cus a t which sin h a s a value of 1 /yjl.
130
Figure 2
CTFs for a 400 keV microscope: (a) at extended Scherzer
defocus and (b) at a defocus of - 114 nm. The microscope
parameters used were a C $ of 1 mm. of 3 nm and of
20 mrad, for which extended Scherzer defocus is
-49.6nm
4. Experimental
Conditions
T h e c o n d i t i o n s c u r r e n t l y used in m o s t H R E M experi
m e n t s a r e t h o s e of axial i l l u m i n a t i o n . I n this m o d e t h e
specimen is tilted in such a w a y t h a t t h e a r e a u n d e r
investigation is o r i e n t e d so t h a t t h e incident electron
b e a m is a c c u r a t e l y aligned a l o n g a low index direc
tion. T h e b e a m tilt is t h e n adjusted t o m a k e t h e
incident electron b e a m c o m e d o w n t h e o p t i c axis of
t h e m i c r o s c o p e . F a i l u r e t o d o this a d j u s t m e n t a s
precisely as possible will h a v e t h e effect of i n t r o d u c i n g
a n t i s y m m e t r i c p h a s e shifts i n t o t h e diffracted b e a m s
Electron
a n d this c a n i n t r o d u c e c o n s i d e r a b l e s p u r i o u s detail
i n t o a n H R E M i m a g e as well as lowering t h e expected
s y m m e t r y of t h e i m a g e . It is u s u a l t o d o t h e b e a m
a l i g n m e n t in c o n j u n c t i o n w i t h t h e a s t i g m a t i s m c o r r e c
tion for the objective lens so t h a t w h e n these h a v e
been d o n e correctly the c o n t r a s t from a n y thin layers
of a m o r p h o u s c o n t a m i n a t i o n is extremely h a r d t o
observe a t G a u s s i a n focus (for w h i c h AF= 0), even if
a n i m a g e is seen o n a T V screen t h r o u g h a n i m a g e
intensifier system. It is also s t a n d a r d practice, p a r t i c u
larly for beam-sensitive m a t e r i a l s , t o d o these tilt a n d
astigmatism corrections on an area somewhat away
from the a r e a t o b e p h o t o g r a p h e d to m i n i m i z e speci
m e n c o n t a m i n a t i o n a n d d e g r a d a t i o n . Specimens used
for H R E M e x a m i n a t i o n h a v e t o be thin, even b y
t r a n s m i s s i o n electron m i c r o s c o p y s t a n d a r d s , a n d al
t h o u g h it is often possible t o o b t a i n g o o d q u a l i t y
H R E M i m a g e s from specimens 100 n m thick, it is
m o r e u s u a l to try a n d e x a m i n e specimens less t h a n
20 n m thick, if only b e c a u s e of t h e difficulties in
interpreting H R E M i m a g e s from thicker specimens.
In practice, this m e a n s t h a t t h e edges of specimens a r e
used for H R E M e x a m i n a t i o n a n d hence c a r e m u s t b e
t a k e n n o t t o i n t r o d u c e artifacts from specimen p r e p
a r a t i o n o r specimen e x a m i n a t i o n i n t o these a r e a s .
5.
Applications
F r o m t h e p r e c e d i n g discussion it is a p p a r e n t t h a t
t r a n s m i s s i o n electron m i c r o s c o p e s c a n readily p r o
duce images t h a t c o n t a i n i n f o r m a t i o n a t t h e a t o m i c
level, t h a t is, of t h e o r d e r of a t o m i c spacings within
b o t h crystalline a n d a m o r p h o u s m a t e r i a l . H o w e v e r , it
is also a p p a r e n t t h a t this i n f o r m a t i o n need n o t be
readily i n t e r p r e t a b l e in t e r m s of projected p o t e n t i a l s
of crystal s t r u c t u r e s , b e c a u s e of t h e w a y in w h i c h the
i n s t r u m e n t a l p a r a m e t e r s of t h e m i c r o s c o p e affect t h e
intensity d i s t r i b u t i o n within t h e H R E M i m a g e .
A g o o d e x a m p l e of this difficulty is t h e i n t e r p r e
t a t i o n of H R E M i m a g e s from [110] z o n e s in silicon.
Silicon h a s t h e d i a m o n d c u b i c s t r u c t u r e , in w h i c h
a t o m s a t (0,0,0) a n d (i,i,i) a r e 0.235 n m a p a r t . In a
[110] z o n e this m e a n s t h a t t h e m o s t closely spaced
a t o m c o l u m n s a r e 0.136 n m a p a r t . In the m a j o r i t y of
published [110] H R E M i m a g e s of silicon these a t o m
c o l u m n p a i r s a p p e a r t o g e t h e r either as b r i g h t b l o b s
( u n d e r c o n d i t i o n s of reversed c o n t r a s t ) o r as t h e d a r k
regions between b r i g h t b l o b s . H o w e v e r , in t h e late
1970s [110] images from silicon were published in
which these white blobs a p p e a r e d as d u m b b e l l s a n d
since the distance between the centers of the t w o p a r t s
of the d u m b b e l l s a p p e a r e d t o b e 0 . 1 3 6 n m , these im
ages were interpreted as being true " a t o m i c " images of
silicon in the [110] direction, even t h o u g h they were
p r o d u c e d in microscopes t h a t h a d interpretable p o i n t to-point resolutions of between 0.2 n m a n d 0.3 n m . It
was s o o n realized t h a t the distance between the centers
of the d u m b b e l l s varied as a function of specimen
Microscopy,
High-Resolution
131
Electron
Microscopy,
High-Resolution
Figure 3
[110] "atomic" image from silicon taken with a 400 keV HREM. This photograph has been enhanced by photographic
averaging in order to eliminate random noise from the image. The specimen thickness was 15 nm and the objective lens
defocus - 114 nm with a C s of 1 mm, of - 3 nm and of 20 mrad (courtesy of J. L. Hutchinson)
132
sequence of H R E M i m a g e s in t e r m s of a u n i q u e
s t r u c t u r a l m o d e l of t h e interface.
T h e s t r u c t u r e of m o d u l a t e d m a t e r i a l s c a n be use
fully o b s e r v e d in a n H R E M b y deliberately u s i n g
n o n a x i a l b r i g h t field i m a g i n g c o n d i t i o n s , in which t h e
b e a m s used t o f o r m t h e i m a g e a r e symmetrically
d i s p o s e d a b o u t t h e o p t i c axis. I n t h e e x a m p l e s h o w n
in F i g . 5, t h e 000, 002, 020 a n d 022 b e a m s from C u N i P d m u l t i l a y e r s of 4.4 n m w a v e l e n g t h h a v e b e e n
symmetrically disposed a b o u t t h e o p t i c axis. T h i s
results in a sequence of m i c r o g r a p h s in which there
a r e clear m o d u l a t e d fringe spacings in t h e [001] direc
tion, w h e r e a s for axial i l l u m i n a t i o n t h e periodicity of
t h e m o d u l a t i o n s is h i d d e n in t h e r a p i d oscillations of
t h e C T F . Intensity profiles from n o n a x i a l m i c r o
g r a p h s such as Fig. 5 c a n b e used t o assess t h e
variability of fringe spacings parallel a n d p e r p e n d i c u -
Electron
Microscopy,
Fringe
High-Resolution
number
1.5
a
(020)
Figure 4
High-resolution electron micrograph of two platelike
precipitates on (111) planes of the matrix aluminum in an
Al-Cu-Mg-Ag alloy. The electron beam is parallel to
[311] of the face-centered-cubic aluminum
Fringe
pixels
(b)
Figure 6
Deviations from the line of least-squares fit of fringe
positions measured from intensity profiles of the specimen
shown in Fig. 5: (a) parallel to the [001] growth direction
and (b) perpendicular to the [001] growth direction. The
mean spacings given in pixels are those of the (002) and
(020) lattice planes and would correspond to
approximately 0.18 nm in pure copper (courtesy of
C. S. Baxter)
6. Future
Figure 5
A nonaxial high-resolution image of a Cu-NiPd
multilayer sample showing modulated fringe spacings
(courtesy of C. S. Baxter)
number
Developments
133
Electron
Microscopy,
High-Resolution
Bibliography
Baxter C S, Stobbs W 1986 High-resolution lattice
imaging reveals a "phase transition" in Cu/NiPd multi
layers. Nature (London) 322: 814-16
Bovin J-O, Wallenberg R, Smith D J 1985 Imaging of
atomic clouds outside the surface of gold crystals by
electron microscopy. Nature (London) 317: 47-9
Clarke D R 1979 High-resolution techniques and applica
tions to nonoxide ceramics. / . Am. Ceram. Soc. 62: 23646
Cowley J M, Smith D J 1987 The present and future of highresolution electron microscopy. Acta Crystallogr. Sect. A
43: 737-51
Fujita F E, Hirabayashi 1986 High-resolution electron
microscopy. In: Gonser U (ed.) 1986 Microscopic Meth
ods in Metals. Springer, Berlin, pp. 29-74
Goodman P, Moodie A F 1974 Numerical evaluation of Nbeam wave functions in electron scattering by the multislice method. Acta Crystallogr. Sect. A 30: 280-90
Kilaas R, Gronsky R 1985 The effect of amorphous surface
layers on images of crystals in high-resolution electron
microscopy. Ultramicroscopy 16: 193-202
Self G, O'Keefe A, Buseck R, Spargo A C 1983
Practical computation of amplitudes and phases in elec
tron diffraction. Ultramicroscopy 11: 35-52
Smith D J 1989 Instrumentation and operation for highresolution electron microscopy. In: Mulvey T, Sheppard
C J R (eds.) 1989 Advances in Optical and Electron
Microscopy, Vol. 11. Academic Press, London, pp. 1-55
Smith D J, Saxton W O, O'Keefe A, Wood G J, Stobbs
W 1983 The importance of beam alignment and crystal
tilt in high-resolution electron microscopy. Ultramicros
copy 11: 263-82
Spence J C 1988 Experimental High-Resolution Electron
Microscopy, 2nd edn. Oxford University Press, Oxford
Stobbs W M, Saxton W 1988 Quantitative highresolution transmission electron microscopy: the need
for energy filtering and the advantages of energy-loss
imaging. J. Microsc. (Oxford) 151: 171-84
Stobbs W M, Wood G J, Smith D J 1985 The measurement
of boundary displacements in metals. Ultramicroscopy 14:
145-54
134
Electron
i m a g e i n f o r m a t i o n t h r o u g h t h e thickness of t h e s a m
ple. In very thick specimens t h e r e s o l u t i o n is l o w e r a s
a c o n s e q u e n c e , principally, of t h e loss in i m a g e c o n
trast i n t r o d u c e d b y electron-energy-loss processes
a l o n g t h e electron p a t h t h r o u g h t h e s a m p l e . A d d i t i o n
ally, a large (several centimeters) objective-lens p o l e piece g a p is desirable t o a c c o m m o d a t e t h e specimen
stages, a n d c o n s e q u e n t l y t h e coefficient of spherical
a b e r r a t i o n is increased a n d r e s o l u t i o n is decreased.
A t h i r d c o n s i d e r a t i o n is t h a t of r a d i a t i o n d a m a g e .
In n o n c o n d u c t i n g m a t e r i a l s , i o n i z a t i o n d a m a g e a t
low accelerating voltages c a n be severe; crystallinity
a n d m i c r o s t r u c t u r e c a n b e d e s t r o y e d so r a p i d l y t h a t
their s t u d y is extremely difficult. T h e severity of t h e
d a m a g e decreases as t h e i o n i z a t i o n cross sections of
the a t o m s in t h e s a m p l e decrease with increasing
e l e c t r o n - b e a m v o l t a g e . H o w e v e r , as t h e accelerating
voltage rises t h e increasing electron energy eventually
reaches a value w h e r e a n e l e c t r o n - a t o m collision c a n
result in t h e d i s p l a c e m e n t of t h e a t o m from its e q u i
librium site. T h i s f o r m of r a d i a t i o n d a m a g e is d i s a d
v a n t a g e o u s t o t h e s t u d y of m i c r o s t r u c t u r e a n d t o in
situ e x p e r i m e n t s b u t o p e n s u p t h e direct s t u d y of
displacement d a m a g e processes w h i c h c a n s i m u l a t e ,
for e x a m p l e , t h e processes w h i c h o c c u r in n u c l e a r
reactors.
1. The
Instrument
Microscopy,
High-
Voltage
2. Image
and Diffraction-Pattern
Formation
A g a i n t h e H V E M is essentially similar t o t h e c o n v e n
t i o n a l T E M in its f o r m a t i o n of i m a g e s a n d diffraction
p a t t e r n s . Because of the smaller electron wavelength,
t h e B r a g g angles for diffraction of t h e electrons from
crystal lattices a r e greatly r e d u c e d . T h i s h a s several
important consequences.
First, it is unlikely t h a t " t w o - b e a m " c o n d i t i o n s c a n
b e established. T h i s is t h e s i t u a t i o n w h e r e only o n e
diffracted b e a m is strongly excited in a d d i t i o n t o t h e
t r a n s m i t t e d electron b e a m . I n 100 k V i n s t r u m e n t s
w h e r e t h e B r a g g angles a r e m u c h larger this c o n d i t i o n
c a n readily b e achieved b y tilting t h e specimen t o set a
single set of p l a n e s t o t h e B r a g g angle a n d i n t e r p r e
t a t i o n of i m a g e c o n t r a s t is m a d e relatively straightfor
w a r d . I n h i g h - v o l t a g e m a c h i n e s t h e best t h a t c a n
usually b e m a n a g e d is t o set t h e tilt so t h a t a " s y s t e m
atic r o w " of diffraction m a x i m a a r e o b t a i n e d (i.e.
diffraction is s t r o n g l y excited from h k I, 2h 2k 21,
..., nhnknl p l a n e s ) . Diffraction c o n t r a s t is neces
sarily m o r e c o m p l e x a n d c o m p u t e r calculation of
c o n t r a s t is a d v i s a b l e for detailed i m a g e i n t e r p r e t a t i o n .
S e c o n d , diffracted intensities v a r y with t h e acceler
a t i n g p o t e n t i a l e m p l o y e d so t h a t t h e o r i e n t a t i o n s
yielding greatest t r a n s m i s s i o n ( a n d h e n c e p e n e t r a t i o n )
alter so t h a t t h e o r i e n t a t i o n c h o s e n for o p t i m u m
o b s e r v a t i o n m u s t be adjusted. A t s o m e "critical vol
t a g e " t h e diffracted intensity of a c h o s e n reflection
falls t o a m i n i m u m . T h i s critical voltage c a n be
a c c u r a t e l y m e a s u r e d a n d t h e value e m p l o y e d t o calcu
late t h e electron density in t h e specimen a n d hence,
for e x a m p l e , t h e electron scattering factors, a n d in
b i n a r y systems, t h e local chemical c o m p o s i t i o n .
135
Electron
Microscopy,
High-
Voltage
T h i r d , a n d of lesser i m p o r t a n c e , t h e diffracted
electron b e a m s m a k e smaller angles t o t h e m i c r o s c o p e
optical axis t h a n is t h e case a t lower voltages. T h u s
dark-field i m a g e s o b t a i n e d using these n o n a x i a l
b e a m s suffer m u c h r e d u c e d spherical a b e r r a t i o n a n d
c a n often be e m p l o y e d r a t h e r t h a n t h e " h i g h r e s o l u t i o n " dark-field i m a g e s o b t a i n e d b y tilting t h e
incident electron b e a m t o p r o d u c e a n axial diffracted
b e a m . Diffraction p a t t e r n s a r e physically smaller for a
given c a m e r a length in t h e m i c r o s c o p e , so p r o v i s i o n is
m a d e via t h e p r o j e c t o r lens system for increasing this
p a r a m e t e r a t high accelerating voltages t o p e r m i t
easier o b s e r v a t i o n .
3. High-Resolution
Electron
Microscopy
H i g h - r e s o l u t i o n h i g h - v o l t a g e electron m i c r o s c o p e s
a r e d e d i c a t e d i n s t r u m e n t s serving this function a l o n e .
T h e objective lens is a critical c o m p o n e n t of t h e
m i c r o s c o p e a n d is designed t o h a v e t h e m i n i m u m
pole-piece g a p a n d h e n c e m i n i m u m coefficient of
spherical a b e r r a t i o n c o n s i s t e n t w i t h t h e need t o
p r o v i d e space for t h e specimen a n d its tilting (the
latter facility is n e e d e d t o adjust t h e diffraction c o n
ditions u n d e r w h i c h t h e s a m p l e is i m a g e d ) . T h i s d o e s
n o t allow sufficient space for c o m p l e x e x p e r i m e n t a l
stages r e q u i r e d for in situ e x p e r i m e n t s a n d , in a n y
case, t h e specimen thickness r e q u i r e d for m a n y in situ
e x p e r i m e n t s w o u l d p r e c l u d e t h e a t t a i n m e n t of t h e
u l t i m a t e resolution.
T h e a d v a n t a g e , with r e g a r d t o r e s o l u t i o n , of d e
creasing electron w a v e l e n g t h w i t h increasing p o t e n t i a l
is b a l a n c e d against t h e p r o b l e m s of e n s u r i n g electron
source stability, t h e m e c h a n i c a l stability of t h e m i c r o
scope a n d t h e p r o b l e m s c a u s e d b y a t o m i c displace
m e n t s t a k i n g place as a result of e l e c t r o n - a t o m colli
sions. F o r these r e a s o n s , voltages u n d e r 1 M e V a r e
generally e m p l o y e d for t h e h i g h - r e s o l u t i o n studies.
R e s o l u t i o n b e t t e r t h a n 0.2 n m h a s b e e n achieved in
u l t r a t h i n specimens (less t h a n 20 n m thick). E l e c t r o n i c
stability of t h e electron s o u r c e a n d m e c h a n i c a l stabi
lity of the s a m p l e stage a n d t h e m i c r o s c o p e h a v e b e e n
i m p r o v e d t o t h e p o i n t w h e r e d y n a m i c events involv
ing small n u m b e r s of a t o m s c a n be i m a g e d a n d
r e c o r d e d . T h u s , for e x a m p l e , r e s t r u c t u r i n g of crystal
surfaces c a n be directly o b s e r v e d in t h e elec
t r o n m i c r o s c o p e (see Electron Microscopy,
HighResolution).
4. Examination
of Thick
Samples
136
Figure 1
In situ recrystallization r at a second-phase particle in a
deformed aluminum-silicon alloy; this representative
microstructure could only be observed in foils too thick
for examination by conventional TEM (courtesy of F. J.
Humphreys)
i m p o r t a n t influence o n t h e m e c h a n i c a l p r o p e r t i e s of
engineering m a t e r i a l s , a n d it is necessary t o b e able t o
identify t h e m a n d their m i c r o s t r u c t u r a l s u r r o u n d i n g s ,
including fine-scale features such as local dislocation
s u b s t r u c t u r e . T h e latter m a y be substantially altered
in foils t h i n e n o u g h for s t u d y a t 100 k V a s a result of
d i s l o c a t i o n r e a r r a n g e m e n t a n d loss t o t h e foil sur
faces. F i g u r e 1 illustrates t h e use of t h e H V E M for t h e
s t u d y of b o t h c o a r s e particles a n d dislocation s t r u c
tures. It s h o w s a d e f o r m e d alloy of a l u m i n u m w h e r e
t h e locally increased m i s o r i e n t a t i o n of t h e m a t r i x a t a
s e c o n d - p h a s e particle h a s c r e a t e d t h e c o n d i t i o n s for
t h e n u c l e a t i o n of recrystallization u p o n s u b s e q u e n t
annealing.
5. Radiation
Damage
Processes
and
Experiments
Electron
Figure 2
Time-lapse sequence of a diffraction pattern of Ni 3Al
showing the fading of {110} superlattice reflections
(arrowed) as electron-displacement damage destroys the
long-range order: (a) 0 s, (b) 50 s and (c) 250 s exposure to
the 1 MeV electron beam (courtesy of J. F. Waiting)
e x a m i n a t i o n of c e r a m i c a n d p o l y m e r i c engineering
m a t e r i a l s . I n metallic systems, t h e i o n i z a t i o n d a m a g e
is rapidly h e a l e d b y t h e s u p p l y of electrons f r o m t h e
c o n d u c t i o n b a n d a n d t h e a d v a n t a g e s of t h e V E M lie
in t h e ability t o e x a m i n e thick sections a n d t o c a r r y
o u t in situ e x p e r i m e n t s . I n t h e latter case (see Sect. 6)
c o n s i d e r a t i o n m u s t b e given t o t h e effects of a s e c o n d
electron i r r a d i a t i o n d a m a g e p r o c e s s t h a t of a t o m i c
displacement.
C o n s i d e r a t i o n of t h e R u t h e r f o r d collision p r o c e s s
involved leads t o t h e following e q u a t i o n for t h e
m a x i m u m energy transfer, Emax (eV), from a n incident
electron t o a t a r g e t a t o m :
m ax
= 2.148 x \03E(E
Microscopy,
High-
Voltage
p e r i o d s in n u c l e a r r e a c t o r s . T h e t w o processes a r e n o t
identical, h o w e v e r , a n d t h e differences m u s t b e c o n
sidered in e x t r a p o l a t i n g f r o m H V E M e x p e r i m e n t s t o
p r e d i c t i o n s for r e a c t o r b e h a v i o r . F o r e x a m p l e , colli
sion d a m a g e c a s c a d e s involving m u l t i p l e k n o c k - o n
events from o n e initial collision d o n o t o c c u r for
electron d a m a g e since t h e displaced a t o m h a s insuf
ficient e n e r g y t o c a u s e this a n d even t h e p r i m a r y
electron h a s a low p r o b a b i l i t y of p r o d u c i n g multiple
d i s p l a c e m e n t s ( a l t h o u g h this increases w i t h increasing
e l e c t r o n energy a b o v e t h e t h r e s h o l d for displace
m e n t ) . A l s o , t h e relative p r o x i m i t y of free surfaces
w h i c h a c t a s point-defect sinks m u s t b e t a k e n i n t o
a c c o u n t , since it will affect t h e m a g n i t u d e of t h e p o i n t defect c o n c e n t r a t i o n d e v e l o p e d d u r i n g i r r a d i a t i o n
a n d t h e p r o d u c t i o n of s e c o n d a r y defects such as
dislocation loops.
T h e temperature at which the experiments are
c o n d u c t e d is also critical since t h e m o b i l i t y of p o i n t
defects varies e x p o n e n t i a l l y w i t h t e m p e r a t u r e : p o i n t defect a n n i h i l a t i o n b y r e c o m b i n a t i o n a n d loss t o sinks
eventually reduces t h e c o n c e n t r a t i o n t o t h e t h e r m a l
e q u i l i b r i u m v a l u e a t a t e m p e r a t u r e w h i c h is a function
of t h e e l e c t r o n - b e a m flux density. T h i s is of consider
able i m p o r t a n c e in t h e i n t e r p r e t a t i o n of in situ experi
ments on phase transformations where displacement
d a m a g e itself a n d e n h a n c e d diffusivity p r o d u c e d b y it
c a n influence t h e stability of s e c o n d - p h a s e particles
a n d their rates of g r o w t h o r d i s s o l u t i o n .
+ 1.022)/M
w h e r e is t h e e l e c t r o n e n e r g y in M e V a n d is t h e
a t o m i c weight of t h e t a r g e t a t o m . A b o v e a critical
value of E, Emax will exceed t h e energy r e q u i r e d t o
displace a n a t o m from its e q u i l i b r i u m site. I n crystal
line m a t e r i a l s this e n e r g y will b e a function of crystall o g r a p h i c direction, a n d t h e o r i e n t a t i o n d e p e n d e n c e
c a n be m e a s u r e d b y in situ i r r a d i a t i o n e x p e r i m e n t s
involving v a r i a t i o n of t h e incident electron energy a n d
the crystal o r i e n t a t i o n relative t o t h e electron b e a m
a n d observing t h e p r o d u c t i o n of point-defect clusters.
A s a result of d i s p l a c e m e n t d a m a g e , large v a c a n c y
a n d interstitial c o n c e n t r a t i o n s c a n d e v e l o p a n d result
in t h e i n f o r m a t i o n of defect clusters a n d d i s l o c a t i o n
l o o p s , t h e degree of l o n g - r a n g e o r d e r c a n b e a l t e r e d
(see F i g . 2, for e x a m p l e ) , modification t o p r e c i p i t a t i o n
reactions c a n o c c u r a n d in e x t r e m e cases crystalline
material can be rendered a m o r p h o u s .
Because very high d i s p l a c e m e n t r a t e s c a n b e
achieved with relatively m o d e s t electron fluxes, t h e
H V E M c a n be used t o investigate t h e d i s p l a c e m e n t
d a m a g e processes w h i c h o c c u r o v e r m u c h l o n g e r t i m e
Figure 3
Time-lapse sequence showing the dissolution of '
particles (arrowed) in an aluminum-copper alloy at
370 C: (a) as the sample reaches temperature, (b) after
1250 s at temperature. Climbing dislocations (for example
at X) visible in the micrographs assist the dissolution
process. The interaction between the dissolution and climb
processes can only be determined by such in situ
experiments in the HVEM (courtesy of P. Hewitt)
137
Electron
Microscopy,
6. In Situ
High-
Voltage
Experiments
Lower pole
piece
Figure 4
Gas reaction cell designed for use in an HVEM: it fits in
the 20 mm objective lens pole-piece gap: in the illustration
a sample holder with a heating stage is shown in the cell
(courtesy of P. R. Swann)
138
Figure 5
Reduction of magnetite to iron, in situ, in an H 2-He
atmosphere in a gas reaction cell in an HVEM. The
porous iron is growing into the oxide along an irregular
growth front. The kinetics of the process can be
determined from time-lapse sequences. The porous iron
product is used as a catalyst in the synthesis of ammonia
(courtesy of G. M. Pennock)
from t h e m i c r o s c o p e c o l u m n . T h i s c h a m b e r is c o n
nected b y t w o further a p e r t u r e s t o t h e m i c r o s c o p e
v a c u u m itself. T h i s differential p u m p i n g system per
m i t s a p r e s s u r e u p t o a t m o s p h e r i c t o b e m a i n t a i n e d in
t h e specimen a r e a w i t h o u t significantly d e g r a d i n g the
microscope vacuum.
T h e specimen stage c a n be e q u i p p e d for tilting,
h e a t i n g , c o o l i n g o r straining t h e specimen a n d t h e
integral objective a p e r t u r e assembly p e r m i t s the use of
all s t a n d a r d i m a g i n g a n d diffraction t e c h n i q u e s . T h e
availability of this e n v i r o n m e n t a l cell h a s p e r m i t t e d a
wide r a n g e of h i g h - t e m p e r a t u r e o x i d a t i o n a n d r e d u c
tion r e a c t i o n s , including t h o s e which o c c u r d u r i n g t h e
p r o d u c t i o n a n d use of catalysts, t o b e studied directly
(Fig. 5).
A s with o t h e r in situ e x p e r i m e n t s , r a d i a t i o n d a m a g e
c a n affect t h e results a n d , since b o t h c o n d u c t o r s a n d
n o n c o n d u c t o r s a r e likely t o be p r e s e n t in these reac
tions, b o t h i o n i z a t i o n a n d d i s p l a c e m e n t d a m a g e m a y
be significant. A t low h o m o l o g o u s t e m p e r a t u r e s this
c a n be exploited t o e n h a n c e r e a c t i o n s w h i c h w o u l d
otherwise be very slow, such as t h o s e b e t w e e n m e t a l s
a n d w a t e r v a p o r . F i g u r e 6 illustrates the use of
e l e c t r o n - b e a m - e n h a n c e d reactivity t o aid the s t u d y of
h y d r o g e n e m b r i t t l e m e n t in a l u m i n u m alloys.
See also: Corrosion and Oxidation Study Techniques
Bibliography
Butler , Hale F 1981 Dynamic experiments in the
electron microscope. In: Glauert A (ed.) 1981 Practical
Electron
Spectroscopy
for Chemical
Analysis
1. Characteristics
Technique
of ESCA
as an
Analytical
T a b l e 1 lists a n u m b e r of t h e characteristics of E S C A
a s a n analytical t e c h n i q u e . A n u m b e r of these consti
t u t e p a r t i c u l a r s t r e n g t h s of t h e t e c h n i q u e , in t h a t
E S C A is r e g a r d e d b y m a n y as t h e m e t h o d of choice
for a p p l i c a t i o n s r e q u i r i n g t h o s e features, while o t h e r s
c o n s t i t u t e weaknesses.
M o r e specifically, t h e ability t o o b t a i n chemical
b o n d i n g i n f o r m a t i o n , t o a n a l y z e electrically insulat
ing m a t e r i a l s a s well as c o n d u c t o r s , t o p r o v i d e r e a s o n -
Table 1
Characteristics of ESCA as an analytical technique
Mean analysis depth (nm)
Elemental sensitivity (at.%)
Special features
1-4
0.01-0.1 (homogeneous
samples)
10" M 0 " 2 monolayers
(surface segregated
constituents)
0.02-100 (instrument
dependent)
all except hydrogen
~10"8
vacuum (pressure
<10" 5torr)
10-20% of relative
abundance
<5
-10
vapor pressure < 10" 5 ton*;
otherwise any solid (e.g.,
insulator, conductor,
powder, organic)
chemical information (i.e.,
chemical valence) can be
determined for many
elements
thickness of layers <10nm
can be determined
139
Electron
Spectroscopy
for Chemical
Analysis
ably g o o d q u a n t i t a t i v e i n f o r m a t i o n a n d t o d a m a g e
minimally t h e s a m p l e being studied a r e c o n s i d e r e d
strengths of t h e t e c h n i q u e . O n t h e o t h e r h a n d , its
relatively p o o r spatial resolution (as c o m p a r e d with
o t h e r surface t e c h n i q u e s such as A u g e r s p e c t r o s c o p y
o r s e c o n d a r y - i o n m a s s s p e c t r o m e t r y ( S I M S ) , which
h a v e s u b m i c r o m e t e r p r o b e sizes), its relatively low
d a t a o u t p u t r a t e a n d its limited sensitivity ( c o m p a r e d
with S I M S ) a r e u n d e s i r a b l e characteristics.
O n e a d d i t i o n a l a t t r i b u t e of the t e c h n i q u e , w h i c h it
shares with A u g e r spectroscopy, is t h e p r o p e r t y of
" c l o s u r e . " Since t h e detection limits for all elements
(except h y d r o g e n a n d helium) a r e within a b o u t a
d e c a d e of e a c h o t h e r , it is usually possible t o deter
m i n e w h a t elements a r e not p r e s e n t o n a surface,
hence p r o v i d i n g a c o m p l e t e (or closed) specification
of surface c o m p o s i t i o n .
2. History
of ESC A
T h e theoretical f o u n d a t i o n of E S C A b e g a n with
Einstein's i n t e r p r e t a t i o n of t h e p h o t o e l e c t r i c effect in
1905. T h i s w o r k describes t h e basic p r o c e s s b y w h i c h
a n x-ray p h o t o n is a b s o r b e d b y a n a t o m , leading t o
the s u b s e q u e n t emission of a n electron. Between 1915
a n d 1935 several e x p e r i m e n t a l investigations of t h e xray photoeffect were c o n d u c t e d , n o t a b l y b y R o b i n s o n
a n d c o w o r k e r s . T h e s e studies succeeded in s h o w i n g
t h a t p h o t o e m i s s i o n did o c c u r from inner-shell elec
t r o n s in solids, b u t t h a t m o s t electrons so p r o d u c e d
which escaped t h e surface h a d lost different a m o u n t s
of energy a n d therefore h a d n o analytical i m p o r t a n c e .
Little a d d i t i o n a l w o r k w a s d o n e o n t h e subject until
the 1950s, w h e n a g r o u p of investigators u n d e r the
direction of S i e g b a h n in Sweden b e g a n a systematic
s t u d y of the x-ray photoeffect using a h i g h - r e s o l u t i o n
s p e c t r o m e t e r t o energy-analyze t h e p h o t o e m i t t e d
electrons. T h e y f o u n d , c o n t r a r y t o t h e earlier lowresolution studies, t h a t a surprising n u m b e r of t h e
electrons e m i t t e d from near-surface a t o m s lost n o
energy a n d hence reflected accurately i n f o r m a t i o n
a b o u t t h e a t o m s from which they o r i g i n a t e d . T h e
g r o u p p r o d u c e d a b o o k describing their extensive
studies (Siegbahn et al. 1967) a n d coined the a c r o n y m
ESCA.
Since then, t h e field h a s been explored extensively,
b o t h as a tool for basic investigation of solids a n d as
a n analytical t e c h n i q u e . C o m m e r c i a l x-ray p h o t o e l e c
t r o n s p e c t r o m e t e r s b e c a m e available in 1969 a n d there
h a v e been n u m e r o u s s y m p o s i a a n d j o u r n a l s d e v o t e d
t o the basic a n d applied uses of E S C A . In 1983,
S i e g b a h n w o n t h e N o b e l Prize in physics for his
p i o n e e r i n g w o r k in this field.
4. Chemical
3. Basic
Theory
(1)
Shift
Information
O n e of t h e m o s t v a l u a b l e features of E S C A from a n
analytical p o i n t of view is its ability t o distinguish
different chemical b o n d i n g configurations as well as
different elements. It is possible, for e x a m p l e , t o
Electron
Spectroscopy
for Chemical
Analysis
Table 2
Binding energies (eV) (larger figures) and theoretical cross sections (smaller figures, line intensities, normalized to the carbon \s
line) of the ESCA lines for the first 30 elements of the periodic table, arranged by atomic orbital (courtesy of R. N. King,
University of Utah)
Atomic orbital
1*1/2 2*1/2
Atomic orbital
3d3/2
14
0.0002
He
25
55
111
188
284
399
532
686
867
1072
CI
Ar
0.486
1.00
1.80
5
7
9
24
7
31
9
45
18
63
31
89
52
118 74 73
149 100 99
189 136 135
4.43
Ne
6.30
Na
8.52
Mg
202
247
297
350
407
461
520
584
652
723
794
872
951
1044
200
245
294
347
402
455
513
575
641
710
779
855
931
1021
2.91
Ti
3.24
3.57
Cr
3.91
0.0478
0.296
Mn
4.23
0.103
0.1941
0.422
1.18
0.0193
0.210
0.955
Sc
0.0065
1
2
1
8
16
Fe
0.0064
4.57
Co
4.88
0.3335 0.0285
0.753 0.1811
Si
270
320
377
438
500
564
628
695
769
846
926
1008
1096
1194
2.59
0.0015
0.575
Al
Ca
0.0002
2.93 0.1405
1.11
2.27
0.1947
0.567
1.97
0.0568
Be
0.276
0.403
Ni
5.16
0.356 0.0535
0.541
0.0808
3
10
Cu
0.014
5.46
Zn
/2
1.43
1.69
0.0082
Li
2/>,
229 165 164
1*1/2 2*1/2
3d5/2
5.76
0.775
1.03
1.35
1.72
2.17
2.69
3.29
3.98
4.74
5.60
6.54
7.57
8.66
0.80
2/>3/2 3*1/2
16
0.1465
0.0774
18
25
34
44
54
59
66
74
84
95
101
112
120
137
7
12
18
26
32
34
38
43
49
56
60
68
74
87
3/7, i2
3/>32
3</3/2
/
1.51
0.1852 0.1433
2.01
0.227 0.2418
2.62
0.286 0.3619
3.35
0.351
0.507
4.21
0.411
0.650
0.0042
5.22
0.473
0.813
0.0136
6.37
0.538
0.996
0.0309
7.69
0.596
1.173
0.0651
9.17
0.674
1.423
0.1046
10.82
0.745
1.669
0.1711
12.62
0.818
1.930
0.2664
14.61
0.892
2.217
0.3979
16.73
0.957
2.478
0.589
18.92
1.04
2.828
0.81
3d5/2
5
1
3
2
2
4
6
3
4
2
9
c=o
I
C 0
Binding energy ( e V )
Figure 1
ESCA carbon spectrum of Mylar polymer with three
different carbon bonds
141
Electron
Spectroscopy
for Chemical
Analysis
5. Quantitative
Characteristics
of
ESCA
{){)
dz
(2)
1
dz
100ff,/Z,#,
(5)
w h e r e C, is t h e c o n c e n t r a t i o n of element / in a t . % .
T h i s simplifies t o
(6)
w h e r e k{= l/,,,,, a c o n s t a n t for a n y given a t o m i c
line.
T h u s , t o d e t e r m i n e t h e relative c o n c e n t r a t i o n s of
t h e surface c o n s t i t u e n t s of a s a m p l e , it is necessary
only t o m e a s u r e t h e n u m b e r of p h o t o e l e c t r o n s
detected in a n E S C A line of each element, multiply by
the a p p r o p r i a t e fc, for t h a t line (a c o n s t a n t which
includes t h e p h o t o e l e c t r o n cross section, escape d e p t h
a n d s p e c t r o m e t e r t r a n s m i s s i o n for t h e line in q u e s
tion) a n d t h e n n o r m a l i z e t o 1 0 0 % for all elements.
T h i s w o r k s very well in practice, for several rea
sons. First, there a r e few m a t r i x effects in E S C A , so
t h e k{ values a r e a function of t h e element involved
a n d t h e b i n d i n g energy of the line used, b u t n o t of the
chemical c o m p o s i t i o n of t h e s a m p l e . Second, since
E S C A c a n detect all elements except h y d r o g e n , t h e
n o r m a l i z a t i o n is meaningful if it is u n d e r s t o o d t h a t
h y d r o g e n is excluded. T h i r d , t h e values of kt c a n be
e s t i m a t e d r a t h e r accurately ( 1 0 - 2 0 % ) from theoret
ical c o n s i d e r a t i o n s o r c a n be d e t e r m i n e d empirically
from m o d e l c o m p o u n d s . F i g u r e 2 s h o w s a typical
E S C A survey s p e c t r u m of a piece of clean q u a r t z . I n
this spectral region, all elements in t h e periodic table
h a v e at least o n e line, so such a s p e c t r u m gives a
c o m p l e t e elemental c h a r a c t e r i z a t i o n of t h e surface
(except for h y d r o g e n ) . U s i n g t h e q u a n t i t a t i o n p r o c e d
u r e described, t h e relative a b u n d a n c e s of silicon,
c a r b o n a n d oxygen c a n be calculated: oxygen,
65 a t . % ; silicon, 33 a t . % ; c a r b o n , 2 a t . % . T h e silicon:
oxygen a t o m i c r a t i o is a b o u t 2 as expected; t h e c a r b o n
represents a s u b m o n o l a y e r c a r b o n a c e o u s surface c o n -
- 2
C,=
O(ls)
(3)
C(ls)
(4)
142
Binding energy
(eV)
Figure 2
ESCA survey spectrum of clean quartz
Si (2/?)
S i ( 2s ) |
Electron
t a m i n a n t . N o r m a l l y , surfaces e x p o s e d t o t h e e n v i r o n
m e n t h a v e several m o n o l a y e r s of such c o n t a m i n a t i o n .
T h e p e a k a t t h e e x t r e m e left is a n o x y g e n A u g e r line
which is excited by t h e x-ray b e a m .
Q u a n t i t a t i o n in E S C A h a s b e e n a p p l i e d m o s t suc
cessfully t o p o l y m e r s , i n s u l a t o r s a n d s e m i c o n d u c t o r
m a t e r i a l s , in w h i c h effects of c o n d u c t i o n electrons a r e
small. Q u a n t i t a t i o n is p a r t i c u l a r l y difficult in t r a n s i
tion m e t a l systems.
6.
Spectroscopy
for Chemical
Monochromator
-'crystal
Analysis
Hemispherical
analyzer
Electron
gun\
Instrumentation
Source
Vacuum enclosure
Detector
Figure 3
Schematic of a simple ESCA spectrometer
Figure 4
Schematic of an improved ESCA spectrometer
Spectrometer
143
Electron
Spectroscopy
for Chemical
Analysis
Technique
A s m e n t i o n e d earlier, for m e a s u r e m e n t s r e q u i r i n g
extremely low detection limits, S I M S is usually the
surface analysis m e t h o d of choice; for t h o s e r e q u i r i n g
extremely g o o d spatial resolution, A u g e r spectros
c o p y is generally used. E S C A is often the m e t h o d of
choice for insulating o r easily d a m a g e d m a t e r i a l s as
well as w h e r e chemical i n f o r m a t i o n o r g o o d q u a n t i
t a t i o n is desired. S o m e specific a p p l i c a t i o n s include a
study of p l a s m a - t r e a t e d p o l y m e r surfaces, t h e stoic h i o m e t r y of S i - N - O - c o n t a i n i n g ceramics, t h e evalu
a t i o n of processes used for w a s h i n g glassware, t h e
w e a t h e r i n g of m i n e r a l s , studies of active sites o n
catalysts, adhesive failures in c o m p o s i t e m a t e r i a l s a n d
passivation processes o n m e t a l surfaces. A n u m b e r of
j o u r n a l s currently r e p o r t o n such w o r k , n o t a b l y the
Journal of Electron Spectroscopy
a n d t h e Journal of
Vacuum Science and
Technology.
T o generalize a b o u t these a p p l i c a t i o n a r e a s , E S C A
h a s been used successfully in three m o d e s :
(a)
(b)
(a)
all a t o m s h a v i n g a n o d d n u m b e r of electrons;
(b)
(c)
(d)
(e)
(f)
d a n g l i n g b o n d s of dislocations in crystals t h a t
a r e covalently b o n d e d ;
as a m o n i t o r i n g t e c h n i q u e t o m e a s u r e the devi
a t i o n of s o m e well-defined p a r a m e t e r from a
norm; and
(g)
c o n d u c t i o n electrons in m e t a l s a n d s e m i c o n d u c
tors.
(c)
as a research tool t o p r o v i d e e x p e r i m e n t a l d a t a
used for c o m p a r i s o n with theories.
Since t h e mid-1970s, t h e a p p l i c a t i o n s in t h e first
t w o of these categories h a v e g r o w n t r e m e n d o u s l y .
Because of its generality, E S C A s h o u l d r e m a i n a
m a j o r analytical surface t e c h n i q u e for t h e foreseeable
future.
See also: Auger Electron Spectroscopy; Chemical Analysis
of Solid Surfaces; Secondary-Ion Mass Spectrometry
Bibliography
Briggs D, Seah 1983 Practical Surface Analysis. Wiley,
New York
Brundle C R, Baker A D 1981 Electron Spectroscopy:
Theory, Technique and Applications, Vol. 4. Academic
Press, London
Ghosh 1983 Introduction to Photoelectron Spectroscopy.
Wiley, New York
Siegbahn G et al. 1967 ESCA, Nova Acta Regiae
Societatis Scientiarum, Ser. IV, Vol. 20. Almqvist and
Wiksell, Boktryckeri, Uppsala, Sweden
144
gpBHMj
H e r e M3 is the m a g n e t i c q u a n t u m n u m b e r , Mj = /,
J+ 1, ..., J; a n d g is the L a n d e factor given b y
=
/ ( / + !) + ( + 1 ) - L ( L + 1)
2J(J+\)
w h e r e S a n d L a r e t h e spin a n d o r b i t a l m o m e n t u m
quantum numbers.
T h e m a g n e t i c field of e l e c t r o m a g n e t i c r a d i a t i o n
induces t h e m a g n e t i c dipole t r a n s i t i o n s o b e y i n g t h e
selection rule AM = 1. T h e c o n d i t i o n of equality of
t h e energy of t h e e l e c t r o m a g n e t i c q u a n t u m t o t h e
m a g n e t i c level splitting is
hco =
gpBH
Electron
T h e b e h a v i o r of p a r a m a g n e t i c centers in c o n
densed m a t t e r is m o r e c o m p l i c a t e d . First, t h e e x t e r n a l
field of t h e m e d i u m c o n t a i n i n g t h e particles as a rule
lifts t h e a n g u l a r m o m e n t u m d e g e n e r a c y , so t h a t t h e
simple expression s h o w n a b o v e for t h e g factor n o
longer h o l d s . S e c o n d , t h e m a g n e t i c m o m e n t of t h e
p a r a m a g n e t i c center interacts with t h e n u c l e a r m a g
netic m o m e n t of t h e p a r e n t a n d n e i g h b o r i n g nuclei.
A l t h o u g h this latter, hyperfine i n t e r a c t i o n is a w e a k
o n e , it greatly e x t e n d s t h e r a n g e of a p p l i c a t i o n s of
ESR.
7. Methods
of Observation
of ESR and
Relaxation
T h e r e s o n a n c e c o n d i t i o n s c a n b e m e t in t w o w a y s :
either by v a r y i n g t h e r a d i a t i o n frequency u n d e r a
c o n s t a n t external m a g n e t i c field o r by v a r y i n g t h e
m a g n e t i c field a t t h e fixed frequency. In t h e m e d i u m 6
l
strength m a g n e t i c field, 10 A m " , t h e r e s o n a n c e
condition corresponds to the microwave or superhigh
frequency ( S H F ) b a n d , 2& 40 G H z . K l y s t r o n s ,
usually used as S H F g e n e r a t o r s , c a n be t u n e d only
within a 10 % b a n d a r o u n d t h e n o m i n a l frequency. I n
view of this l i m i t a t i o n , w h i c h is d u e t o certain specific
features of w a v e g u i d e s a n d wide use of h i g h - Q S H F
cavities as a b s o r p t i o n cells, it is c o n v e n t i o n a l in t h e
o b s e r v a t i o n of E S R t o use a fixed-frequency regime
with a v a r y i n g m a g n e t i c field.
T h e simplest s e t u p of t h e E S R d e t e c t o r is d e p i c t e d
in Fig. 1. T h e a r r a n g e m e n t c o n t a i n s t h e m i c r o w a v e
generator supplemented by an attenuator to tune the
S H F power output and the frequency/wavelength
meter, t h e a b s o r p t i o n cell with t h e s a m p l e (usually a
cavity), t h e S H F receiver a n d t h e r e c o r d i n g system.
T h e a b s o r p t i o n cell is p l a c e d b e t w e e n t h e poles of t h e
e l e c t r o m a g n e t , w h i c h is s u p p l e m e n t e d by field sweep
a n d m o d u l a t i o n systems. W h e n t h e m a g n e t i c field
reaches t h e r e s o n a n c e value, t h e p a r a m a g n e t i c s a m p l e
Frequency modulator
of the magnetic field
Klystron
Receiver
Recorder
Wavemeter
Figure 1
Schematic layout of a simple electron spin resonance
spectrometer
Spin
Resonance
145
Electron
Spin
Resonance
r e s o n a n c e c o n d i t i o n . A s a result t h e o b s e r v e d E S R
line w o u l d be a s u p e r p o s i t i o n of a large n u m b e r of
c o m p o n e n t s ( " s p i n - p a c k e t s " ) , slightly shifted relative
t o each o t h e r . T h e final signal c o r r e s p o n d s t o t h e
envelope of this s u p e r p o s i t i o n . If t h e static a n d aver
aged m a g n e t i c fields acting o n different centers d o n o t
coincide, t h e b r o a d e n i n g is t e r m e d n o n u n i f o r m .
U n d e r u n i f o r m b r o a d e n i n g , t h e a v e r a g e d field o n
different centers coincides with t h e static o n e , b u t
local fields vary with time. U n i f o r m b r o a d e n i n g is
usually c h a r a c t e r i z e d b y t h e so-called s p i n - s p i n relax
a t i o n time T2.
T h e m a i n s o u r c e of u n i f o r m b r o a d e n i n g is t h e
d i p o l e - d i p o l e i n t e r a c t i o n s of t h e m a g n e t i c m o m e n t s
of p a r a m a g n e t i c centers. R e l a x a t i o n processes, c h a r
acterized by r e l a x a t i o n times Tx a n d T2, involve a n
i n t e r a c t i o n of p a r a m a g n e t i c centers with e a c h o t h e r
a n d also with o t h e r c o m p o n e n t s of t h e c o n d e n s e d
state, so t h a t a s t u d y of t h e p a r a m a g n e t i c r e l a x a t i o n
a n d of its d e p e n d e n c e o n external c o n d i t i o n s p r o v i d e s
a w e a l t h of i n f o r m a t i o n o n t h e n a t u r e of m a t e r i a l s
studied.
It m a y h a p p e n t h a t despite t h e r e l a x a t i o n processes
the high S H F field in t h e cavity equalizes t h e p o p u l a
tions of t h e energy levels, t h u s r e d u c i n g a b s o r p t i o n b y
t h e p a r a m a g n e t i c s a m p l e . T h i s is t h e so-called reso
n a n c e s a t u r a t i o n effect, w h i c h p u t s a n u p p e r b o u n d
o n t h e S H F p o w e r used in E S R studies. F o r the
n a r r o w lines these limitations m a y p r o v e essential. O n
the o t h e r h a n d , t h e s a t u r a t i o n effect e n a b l e s the
a m p l i t u d e of S H F m a g n e t i c field a t t h e s a m p l e loca
tion t o b e d e t e r m i n e d .
The
Hyperfine
146
= g*M* ( 8 * / 3 ) | V ( 0 ) | M 7 + H0 = AMj + H0
w h e r e M 7 is t h e n u c l e a r m a g n e t i c q u a n t u m n u m b e r ,
r u n n i n g from / t o + / . N u c l e a r m a g n e t i c m o m e n t s
m o v e m u c h slower t h a n t h e electron m o m e n t s ,
as t h e r e s o n a n c e frequencies of p r o t o n s a n d elec
t r o n s in t h e s a m e m a g n e t i c field a r e related b y
l
3
opDe~ = 1.5193 = 1 0 " . H e n c e , a n y s e p a r a t e electron
is in a n effective m a g n e t i c field H0 + AM,, w h e r e M 7
retains its value, e q u a l t o o n e of 21+ 1 possible
values, for a p e r i o d of time w h i c h exceeds t h e inverse
frequency of E S R b y a large factor. I n this case, t h e
E S R s p e c t r u m of a large system will be split i n t o
21 + 1 e q u i d i s t a n t c o m p o n e n t s .
In free radicals, u n p a i r e d electrons a r e only in r a r e
cases in o r b i t a l s (i.e., in p r a c t i c e they a r e localized in
t h a t p a r t of t h e molecule w h e r e t h e electrons needed
t o s a t u r a t e valency a r e missing). - O r b i t a l u n p a i r e d
electrons a r e strongly delocalized in the skeleton of
the molecule. I n this case, the density of u n p a i r e d
electrons o n e q u i v a l e n t a t o m s s h o u l d be identical, a n d
therefore a n identical H F I o c c u r s with equivalent
atoms. F o r nonequivalent atoms, the H F I constants
w o u l d be different.
T h e energy levels of a n u n p a i r e d electron o n t w o
e q u i v a l e n t a t o m s with n u c l e a r spin / = \ a r e s h o w n in
Fig. 2. T h e Z e e m a n splitting in t h e field is s h o w n in
(a); there a r e t w o levels c o r r e s p o n d i n g t o Ms = \. A
s t r u c t u r e of energy levels for H F I with o n e a t o m is
s h o w n in (b); every level splits i n t o t w o , c o r r e s p o n d
ing t o t h e n u c l e a r m a g n e t i c q u a n t u m n u m b e r
Mj= %. T h e effect of t h e second e q u i v a l e n t nucleus
is s h o w n in (c). E a c h of t h e four levels of (b) splits i n t o
t w o . A s hyperfine splitting is t h e s a m e for b o t h a t o m s ,
o n e o b t a i n s six levels, t h e c e n t r a l line in e a c h of t h e
triplets c o m p r i s i n g t w o states. T h e E S R t r a n s i t i o n s
1, AMj= 0) b e t w e e n levels a r e s h o w n b y
(AMS=
arrows.
T h e resulting s p e c t r u m consists of three lines, t h e
central o n e h a v i n g d o u b l e intensity. I n t h e general
case of e q u i v a l e n t nuclei of spin / , o n e o b t a i n s
2nl+ 1 lines in t h e E S R s p e c t r u m , with relative
intensities c o r r e s p o n d i n g t o P a s c a l ' s triangle. T h i s
e n a b l e s o n e t o d i s e n t a n g l e from t h e c o m p l e x E S R
spectra t h e sequence c o r r e s p o n d i n g t o e q u i v a l e n t
a t o m s . T h e n u m b e r of such sequences allows t h e
d e t e r m i n a t i o n of t h e n u m b e r of n o n e q u i v a l e n t a t o m s .
Electron
Spin
Resonance
aBA ^
Figure 2
A sequential picture of the formation of hyperfine splitting
in the case of an unpaired electron on two equivalent
atoms with nuclear spin / = \
Figure 3
Spectrum of energy levels of the triplet system
T h e a b s o l u t e value of hyperfine splitting e n a b l e s o n e
to d e t e r m i n e the relative density of u n p a i r e d electrons
o n g r o u p s of different a t o m s a n d , c o n s e q u e n t l y , t h e
orbital in w h i c h t h e electron is located.
T h e s i t u a t i o n is s o m e w h a t m o r e c o m p l i c a t e d in
crystalline s u b s t a n c e s c o n t a i n i n g free radicals. C o r
r e s p o n d i n g l y , even m o r e i n f o r m a t i o n is c o n t a i n e d in
their E S R spectra. I n m o n o c r y s t a l s i n t e r a c t i o n s a r e
usually a n i s o t r o p i c . A s a result t h e g factor (it is m o r e
precise t o s p e a k of a g t e n s o r ) a n d the hyperfine
splitting d e p e n d o n t h e relative o r i e n t a t i o n of t h e
crystal a n d t h e m a g n e t i c field.
A p a r t from free radicals, E S R is exhibited b y
molecules with a triplet spin state. If t w o electrons
o c c u p y different orbitals b u t still h a v e t h e d i p o l e dipole i n t e r a c t i o n , there c a n exist b o t h singlet S = 0
a n d t h e triplet S = 1 states. T h e triplet s t a t e is q u i t e a
general case; a p a r t from o r g a n i c s u b s t a n c e s , it is
possessed, for i n s t a n c e , b y m o l e c u l a r oxygen. N o t
only t h e g r o u n d - s t a t e triplets, b u t longlived excited
states also c o n t r i b u t e t o t h e E S R s p e c t r u m . T h i s
excitation m a y be either t h e r m a l w h e n t h e s i n g l e t triplet splitting is small, o r via i r r a d i a t i o n b y electro
m a g n e t i c q u a n t a if t h e splitting is larger.
A peculiar feature of E S R in t h e triplet s t a t e is a
s t r o n g a n i s o t r o p y of level p o s i t i o n s as a function of
o r i e n t a t i o n of the m a g n e t i c field with respect t o t h e
m o l e c u l a r axes a n d t h e persistence of splitting a t t h e
zero m a g n e t i c field. T h i s is d e m o n s t r a t e d b y t h e E S R
s p e c t r u m of the triplet system s h o w n in Fig. 3. I n
chaotically o r i e n t e d systems, this s t r o n g a n i s o t r o p y of
level p o s i t i o n s results in lines of a very c o m p l e x form.
In a w e a k m a g n e t i c field, c o n v e n t i o n a l | + 1>, |0> a n d
I - 1 > states of t h e triplet system a r e m i x e d b y t h e
s p i n - s p i n i n t e r a c t i o n . T h e c o n v e n t i o n a l selection rule
AM = 1 n o longer h o l d s , since o n e c a n n o t ascribe
definite values of t o the energy levels. I n a n S H F
m a g n e t i c field parallel t o t h e external u n i f o r m field,
the AM = 2 t r a n s i t i o n s b e c o m e allowed.
T h e p a r a m a g n e t i c o r g a n i c f o r m a t i o n s a r e of great
i m p o r t a n c e in biological processes, a n d it is therefore
n o t surprising t h a t E S R m e t h o d s h a v e a b r o a d spec
t r u m of a p p l i c a t i o n s in studies of these processes. O n e
of t h e p r o b l e m s e n c o u n t e r e d in these a p p l i c a t i o n s is
t h a t biological systems consist m o s t l y of w a t e r . T h i s
i m p o s e s severe c o n s t r a i n t s o n t h e s h a p e a n d size of
s a m p l e s a n d enforces the use of high-sensitivity E S R
spectrometers.
3. Transition
Metal
Ions:
The
Spin-Orbit
Interaction
S u b s t a n c e s c o n t a i n i n g t r a n s i t i o n m e t a l ions are
a m o n g t h o s e m o s t frequently studied b y E S R m e t h
o d s . A peculiar feature of these ions is the presence of
a n i n c o m p l e t e d o r / shell. In this case, E S R d a t a
e n a b l e o n e t o d e d u c e i n f o r m a t i o n o n t h e intracrystalline field, s p i n - o r b i t a l a n d hyperfine i n t e r a c t i o n s .
W i t h r e g a r d t o their s p i n - o r b i t i n t e r a c t i o n , t h e intracrystalline fields a r e classified as s t r o n g , m e d i u m a n d
weak.
A w e a k crystalline field is o b s e r v e d in the ions of
r a r e - e a r t h m e t a l s . H e r e / electrons a r e well screened
by o t h e r electrons a n d their i n t e r a c t i o n with the
s u r r o u n d i n g crystal is a w e a k o n e . T h e relevant level
2
_1
splitting energy is of t h e o r d e r of 1 0 c m
compared
with a s p i n - o r b i t a l i n t e r a c t i o n of t h e o r d e r of
4
- 1
1 0 c m . T h a n k s to the strong spin-orbit interaction
t h e m a g n e t i c b e h a v i o u r of the system is c o n t r o l l e d by
t h e t o t a l m o m e n t u m / . I n t h e crystalline field definite
j levels split i n t o d o u b l e t s 7 ( a n d singlet M3 = 0,
if J is a n integer). A s t h e influence of the crystalline
field is w e a k , t h e m a g n e t i c p r o p e r t i e s of r a r e - e a r t h
ions in different a g g r e g a t e states d o n o t differ m a r
kedly.
T h e d shell forms t h e o u t e r shells of these ions, so
147
Electron
Spin
Resonance
2A||A||and||D|| = A ||A||
H e r e 1111 is a t e n s o r a c c o u n t i n g for c o n t r i b u t i o n s of
the orbital m o m e n t a of d e g e n e r a t e states a n d is t h e
s p i n - o r b i t a l i n t e r a c t i o n c o n s t a n t . F o r spins S ^ 1 the
second t e r m is real. A similar c o n t r i b u t i o n c o m e s
from t h e s p i n - s p i n i n t e r a c t i o n . E x p e r i m e n t a l l y , it is
impossible t o decide which c o n t r i b u t i o n t o \\D\\ is
d u e t o the s p i n - s p i n i n t e r a c t i o n a n d which is d u e t o
the s p i n - o r b i t a l i n t e r a c t i o n . O n e often d e c o m p o s e s
S\ID\\S
singling o u t the t e r m
2
D[S z-iS(S+l)]
148
E(S x-S y)
where
D = DZZ-
Dxx
+ D
and E =
Dxx
Dyy
^
is a certain c o m b i n a t i o n of d i a g o n a l c o m p o n e n t s of
O n e uses t h e spin H a m i l t o n i a n as follows. First, t h e
q u a n t i t i e s like t h e g t e n s o r , zero-field splitting a n d
hyperfine s t r u c t u r e c o n s t a n t s a r e experimentally
m e a s u r e d . T h e n , o n e tries t o guess the m o d e l of a
crystalline field which w o u l d c o r r e s p o n d t o t h e spin
H a m i l t o n i a n w h i c h fits t h e observed p a r a m e t e r s .
4. Electron-Nuclear
Double
Resonance
In this a p p l i c a t i o n , E S R is e m p l o y e d t o s t u d y n u c l e a r
m a g n e t i s m . A s w a s m e n t i o n e d a b o v e , t h e E S R signal
d e p e n d s o n t h e difference of p o p u l a t i o n s of levels, a
t r a n s i t i o n b e t w e e n which c o r r e s p o n d s t o the o b s e r v e d
line. If t h e S H F i r r a d i a t i o n intensity is sufficiently
high, p o p u l a t i o n s b e c o m e e q u a l a n d t h e E S R signal
v a n i s h e s in a s t a t i o n a r y state. H o w e v e r , if a hyperfine
splitting o c c u r s , o n e c a n i n d u c e t h e radio-frequency
t r a n s i t i o n s b e t w e e n o n e of t h e levels c o r r e s p o n d i n g t o
E S R , a n d s o m e o t h e r H F I level, t h u s c h a n g i n g t h e
p o p u l a t i o n . T h i s induces a n a b s o r p t i o n a n d the rele
v a n t E S R signal. O n e c a n m a t c h t h e E S R s a t u r a t i o n
level so a s t o m a x i m i z e t h e influence of t h e r a d i o frequency field o n t h e E S R signal. T h e r e c o r d e d E S R
a b s o r p t i o n versus t h e frequency of t h e r a d i o frequency field g e n e r a t o r is called t h e s p e c t r u m of a n
e l e c t r o n - n u c l e a r d o u b l e r e s o n a n c e . T h e m e t h o d of
d o u b l e r e s o n a n c e is used in cases w h e n t h e sensitivity
of c o n v e n t i o n a l n u c l e a r m a g n e t i c r e s o n a n c e is n o t
sufficient t o o b s e r v e t h e desired signal.
T h e great versatility of E S R h a s gained for it a
b r o a d s p e c t r u m of a p p l i c a t i o n s in studies of objects
c o n t a i n i n g p a r a m a g n e t i c centers. T h e r e h a v e been
n u m e r o u s a p p l i c a t i o n s of t h e m e t h o d in studies of
i m p u r i t y centers in s e m i c o n d u c t o r s ; it h a s p r o v e d
possible t o o b s e r v e E S R signals from c o n d u c t i o n
electrons in certain m e t a l s , t h u s e n a b l i n g t h e s t u d y of
the spin-flip scattering of electrons. E S R is widely
used as a t o o l for the analysis of o r g a n i c s u b s t a n c e s
a n d in searches for i m p u r i t i e s .
See also: Nuclear Magnetic Resonance Spectroscopy; Nu
clear Magnetic Resonance Spectroscopy of Solids
Bibliography
Abragam A, Bleaney 1970 Electron Paramagnetic Reso
nance of Transition Ions. Clarendon, Oxford
Algers R S 1968 Electron Paramagnetic Resonance. Tech
niques and Application. Wiley, New York
Atkins W, Symons C R 1967 The Structure of Inorganic
Radicals. An Application of Electron Spin Resonance to the
Study of Molecular Structure. Elsevier, New York
Electron
Tunnelling
Spectroscopy
2. Experimental
If t w o c o n d u c t o r s a r e s e p a r a t e d by a thin i n s u l a t o r ,
typically 3 n m o r less in thickness, c u r r e n t m a y flow
by q u a n t u m - m e c h a n i c a l tunnelling of electrons. Elec
t r o n tunnelling s p e c t r o s c o p y studies v a r i a t i o n s in t h e
t u n n e l c u r r e n t as a function of applied v o l t a g e , t o
d e t e r m i n e b a n d s t r u c t u r e a n d excitation c h a r a c t e r i s
tics of t h e c o n d u c t o r s a n d t h e m a t e r i a l s in t h e insulat
ing g a p . Since t h e energy r e s o l u t i o n is limited only b y
t h e r m a l b r o a d e n i n g of the F e r m i level, m o s t m e a s u r e
m e n t s a r e carried o u t a t liquid h e l i u m t e m p e r a t u r e s .
A m a j o r use of the t e c h n i q u e is in c h a r a c t e r i z i n g
s u p e r c o n d u c t o r s . T h e m a i n a p p l i c a t i o n in n o r m a l
m a t e r i a l s is inelastic tunnelling s p e c t r o s c o p y , w h e r e
the characteristic energies of m o l e c u l a r v i b r a t i o n a l o r
electronic states, o r t h e energies of collective excita
tions ( p h o n o n s o r m a g n o n s for e x a m p l e ) m a y be
determined.
L Physical
Techniques
Basis
<7xexp(-^)j "
N(E)j^(f(E+eV))dE
Separation
Figure 1
Schematic of an ideal tunnel barrier between two metals
149
Electron
Tunnelling
Spectroscopy
3.
Applications
C h a r a c t e r i z a t i o n of s u p e r c o n d u c t o r s a n d s t u d y of t h e
J o s e p h s o n (two-electron tunnelling) effect h a v e been
m a j o r a p p l i c a t i o n s . D e s p i t e t h e need t o w o r k a t low
t e m p e r a t u r e s , inelastic tunnelling s p e c t r o s c o p y s h o w s
c o n s i d e r a b l e p r o m i s e . Characteristics of thin insulat
ing films such as silicon dioxide a n d L a n g m u i r Blodgett layers m a y b e d e t e r m i n e d . A s i d e from t h e
high resolution s p e c t r o s c o p y of a d s o r b e d molecules,
150
Bibliography
Adkins C J, Phillips W A 1985 Inelastic electron tunnelling
spectroscopy. J. Phys. C 18: 1313-46
Binnig G, Rohrer H, Gerber Ch, Weibel 1982 Surface
studies by scanning tunnelling microscopy. Phys. Rev.
Lett. 49: 57-61
Khanna S K, Lambe J 1983 Inelastic electron tunnelling
spectroscopy. Science 220: 1345-51
Lambe J, McCarthy S 1976 Light emission from inelastic
electron tunnelling. Phys. Rev. Lett. 37: 923-5
Sze S 1981 Physics of Semiconductor Devices, 2nd edn.
Wiley, New York
Wolf L 1984 Principles of Electron Tunnelling Spectros
copy. Oxford University Press, Oxford
J. B. Pethica
[University of O x f o r d , O x f o r d , U K ]
F
Field-Ion Microscopy: Atom-Probe
Microanalysis
T h e field-ion m i c r o s c o p e ( F I M ) is o n e of t h e few
t e c h n i q u e s t h a t r o u t i n e l y allows t h e i m a g i n g of indi
vidual a t o m s in direct lattice space. T h e F I M is a
p o i n t - p r o j e c t i o n m i c r o s c o p e a n d h e n c e n o lenses a r e
required for t h e f o r m a t i o n of a n i m a g e . T h e i m a g e is a
projection of t h e a t o m s w h i c h reside in the surface of
a sharply p o i n t e d specimen. W h e n a n F I M is c o m
bined with a m a s s s p e c t r o m e t e r (to f o r m a n " a t o m
p r o b e " ) , it is possible t o d e t e r m i n e t h e m a s s - t o - c h a r g e
r a t i o of individual a t o m s , o n e a t a time. I n v e n t e d by
E. W . Muller, t h e F I M a n d a t o m p r o b e h a v e b e e n
used extensively t o s t u d y , for e x a m p l e , p r e c i p i t a t i o n
p h e n o m e n a ( B r e n n e r 1978), surface diffusion of a d a t o m s ( a t o m s a d s o r b e d o n a surface) (Ehrlich 1980,
T s o n g 1980), r a d i a t i o n d a m a g e ( S e i d m a n 1978,
Herschitz a n d S e i d m a n 1984), p h a s e t r a n s f o r m a t i o n s
in steels (Miller et al. 1981), o r d e r - d i s o r d e r alloys
( Y a m a m o t o et al. 1972) a n d segregation ( H e r s c h i t z
a n d S e i d m a n 1985).
1. The Field-Ion
Microscope
2. Field
Ionization
W i t h t h e aid of a h i g h - v o l t a g e s u p p l y t h e specimen
3. Field
Evaporation
151
Field-Ion
Microscopy:
Atom-Probe
Microanalysis
Figure 1
An FIM image of gold: the (001) plane is in the center of
the image (note the fourfold symmetry about this plane);
specimen termperature 23 K; imaging gas, neon
a t o m a n d h e n c e t h e i o n t h e r e b y r e d u c i n g t h e dia
m e t e r of t h e pencil of i m a g i n g - g a s i o n s . I n practical
t e r m s this m e a n s t h a t t h e effective d i a m e t e r of the
i m a g e of a n a t o m is a function of t h e t e m p e r a t u r e of
t h e tip. T h e r e f o r e , t h e r e s o l u t i o n of t h e F I M is
t e m p e r a t u r e d e p e n d e n t (Chen a n d S e i d m a n 1971).
T h e r e s o l u t i o n of t h e F I M is also a function o f t h e
r a d i u s of t h e tip; t h e b l u n t e r t h e tip the p o o r e r is
t h e r e s o l u t i o n . T h e physical origin of this effect is t h e
a n g u l a r m o m e n t u m of t h e gas a t o m a t t h e i n s t a n t of
its i o n i z a t i o n . I n t h e central-field a p p r o x i m a t i o n t h e
a n g u l a r m o m e n t u m is p r o p o r t i o n a l t o t h e s q u a r e of
t h e r a d i u s of t h e tip. H e n c e , t h e d i a m e t e r of t h e pencil
of i m a g i n g gas i o n s increases with increasing r a d i u s
a n d c o n c o m i t a n t l y t h e r e s o l u t i o n decreases ( G o m e r
1961).
F r o m t h e p r e c e d i n g it is clear t h a t t h e best a t o m i c
r e s o l u t i o n is achieved e m p l o y i n g s h a r p tips ( < 20 n m )
a n d low t e m p e r a t u r e s ( < 20 K ) . T h u s , it is possible in
practice t o o b s e r v e individual a t o m s with i n t e r a t o m i c
distances a p p r o a c h i n g 0.2 n m ( M u l l e r a n d T s o n g
1969).
5. Atom-Probe
pulses. T h i s t e c h n i q u e , called pulse-field e v a p o r a t i o n ,
enables dissection o f a n a t o m i c p l a n e a t a r a t e o f o n e
to three a t o m s p e r pulse. T h u s , t h e a t o m s c o n t a i n e d
within the interior of the specimen c a n be i m a g e d
albeit a t t h e surfaceat a d e t e r m i n e d r a t e . T h e a r e a
of surface e x a m i n e d a t a n y i n s t a n t is a r o u n d 1 0 " 1 4 m 2 .
In practice, a r o u n d 1 0 ~ 23 m 3 of m e t a l c a n be e x a m i n e d
d u r i n g the c o u r s e of o n e d a y e m p l o y i n g t h e pulsefield-evaporation
t e c h n i q u e ; this c o r r e s p o n d s t o
- 6 x 10 5 a t o m s .
A simple physical picture of t h e process of field
e v a p o r a t i o n is o b t a i n e d with t h e aid of t h e ionic
m o d e l . In this m o d e l the applied electric field d e f o r m s
the p o t e n t i a l - e n e r g y c u r v e for a n ion o n t h e surface o f
the specimen a n d i n t r o d u c e s a S c h o t t k y barrier. T h e
ions t h e n e v a p o r a t e b y either j u m p i n g over a small
S c h o t t k y b a r r i e r a s a result of a t h e r m a l l y activated
s t e p o r b y tunnelling t h r o u g h t h e b a r r i e r ( M u l l e r
a n d T s o n g 1969, 1973).
4.
Resolution
T h e d i a m e t e r of t h e pencil of i m a g i n g ions e m a n a t i n g
from e a c h a t o m is a function of t h e t e m p e r a t u r e of t h e
tip. T h e p u r p o s e of cooling t h e specimen t o cryogenic
t e m p e r a t u r e s is to a c c o m m o d a t e thermally the imaginggas a t o m s t o t h e t e m p e r a t u r e of t h e tip, p r i o r t o t h e
field-ionization
event. T h i s t e m p e r a t u r e a c c o m m o d a
tion p r o c e s s reduces t h e transverse velocity of a gas
152
Field-Ion
Microscope
T h e time-of-flight ( T O F ) a t o m - p r o b e F I M consists of
a n F I M c o m b i n e d with a special T O F m a s s spec
t r o m e t e r (see F i g . 2). T h e a t o m p r o b e p e r m i t s t h e
identification of t h e c h e m i s t r y of a n y a t o m t h a t
a p p e a r s in a n F I M i m a g e . T h u s , it is possible t o
o b t a i n a n a t o m i c r e s o l u t i o n i m a g e of m i c r o s t r u c t u r a l
features a n d t o m e a s u r e t h e m a s s - t o - c h a r g e r a t i o
(m/q) of single a t o m s from preselected regions of a
specimen, with a lateral spatial r e s o l u t i o n (i.e., within
t h e surface) of a few t e n t h s of a n a n o m e t e r a n d a
d e p t h spatial r e s o l u t i o n t h a t is d e t e r m i n e d by t h e
i n t e r p l a n a r s p a c i n g of t h e region; the latter q u a n t i t y
c a n be h u n d r e d t h s of a n a n o m e t e r for a high-index
p l a n e . A n a t o m p r o b e with a straight T O F t u b e (Fig.
2) h a s a m a s s r e s o l u t i o n (m/Am) of a r o u n d 200,
w h e r e a s a n a t o m p r o b e with a P o s c h e n r i e d e r lens h a s
a n m/Am value of > 1000. A m a g n e t i c - s e c t o r a t o m
p r o b e h a s been c o n s t r u c t e d t o analyze t h e p r o d u c t s of
the field-evaporation p r o c e s s t h i s i n s t r u m e n t h a s a n
m/Am of a r o u n d 2000 ( M u l l e r a n d S a k u r a i 1974). Its
m a i n d i s a d v a n t a g e a t p r e s e n t is t h a t only a small
p o r t i o n of t h e p e r i o d i c table c a n b e e x a m i n e d a t o n e
time.
T h e o p e r a t i o n of a n a t o m p r o b e c a n be u n d e r s t o o d
with reference t o F i g . 2. W h e n a s h o r t ( < 25 ns) highvoltage pulse ( K p u l s)e is s u p e r p o s e d o n t h e s t e a d y - s t a t e
i m a g i n g v o l t a g e (Vdc), a t o m s o n t h e surface of t h e
specimen a r e field e v a p o r a t e d in t h e f o r m of ions. T h e
ions t h a t a r e projected i n t o t h e p r o b e hole, a t t h e
center of t h e i n t e r n a l image-intensification system,
pass d o w n t h e flight t u b e t o t h e c h e v r o n i o n d e t e c t o r .
T h i s d e t e c t o r consists of t w o C E M A s in series a n d h a s
Field-Ion
Chevron
detector
4-
Front - surfaced
glass mirror
Specimen
voltage
system
Nova 1220
computer
Start
TOF
data
Stop
Digital timer
Figure 2
Schematic diagram of a time-of-flight atom-probe field-ion
microscope
aFp
)(/ -
u l s e
t0) /d
6. Imaging
Atom-Probe
Mass
Spectroscopy
It is also possible t o p r o d u c e a n i m a g e of t h e a t o m s o n
the surface of a tip b y using t h e field-desorbed i o n s t o
create the i m a g e . T h i s c a n n o w be achieved r o u t i n e l y
e m p l o y i n g a c h e v r o n t o detect t h e individual fieldd e s o r b e d i o n s , w i t h a flight d i s t a n c e of 0.12 m
between t h e specimen a n d t h e c h e v r o n (the s h o r t
flight distance is necessary t o observe t h e entire sur
face a r e a of a tip). T o f o r m a field-desorption i m a g e of
a n ion with a specific m/q r a t i o , t h e c h e v r o n d e t e c t o r
is time-gated, so only t h a t r a t i o is detected. T o
o p e r a t e in this m o d e it is necessary t o e m p l o y a
c h e v r o n d e t e c t o r w i t h a spherical g e o m e t r y . T h i s
g e o m e t r y g u a r a n t e e s t h a t e a c h ion will h a v e t h e s a m e
flight distance, i n d e p e n d e n t of its p o s i t i o n o n t h e
surface of t h e specimen. A n i m a g i n g a t o m - p r o b e m a s s
s p e c t r o m e t e r c a n be used, for e x a m p l e , t o d e t e r m i n e
elemental m a p s of t h e d i s t r i b u t i o n of alloying ele
m e n t s in the vicinity of grain b o u n d a r i e s ( W a u g h a n d
S o u t h o n 1979).
Microscopy:
7. Pulsed-Laser
Atom-Probe
Atom-Probe
Field-Ion
Microanalysis
Microscope
K e l l o g g a n d T s o n g (1980) s h o w e d t h a t it is possible to
field-evaporate
a silicon specimen in a highly c o n
trolled m a n n e r b y i l l u m i n a t i n g it with 6 n s - w i d e
pulses of laser light, while m a i n t a i n i n g t h e specimen
a t a s t e a d y - s t a t e d c voltage. T h i s w o r k built o n the
earlier e x p e r i m e n t s of M e l m e d a n d c o w o r k e r s w h o
d e m o n s t r a t e d t h a t specimens of silicon, g e r m a n i u m
and G a A s had an enhanced
field-evaporation
rate
w h e n they were i r r a d i a t e d w i t h w h i t e light. Kellogg
a n d T s o n g m e a s u r e d t h e m a s s - t o - c h a r g e r a t i o s of the
silicon i s o t o p e s in a c o n v e n t i o n a l time-of-flight a t o m
p r o b e a n d d e m o n s t r a t e d t h a t t h e pulsed-laser a t o m
p r o b e achieved a m a s s r e s o l u t i o n t h a t is c o m p a r a b l e
t o t h a t for m e t a l s e m p l o y i n g h i g h - v o l t a g e pulses.
T h u s , t h e pulsed-laser a t o m - p r o b e field-ion m i c r o
scope c a n be useful for chemically a n a l y z i n g semicon
ducting materials.
See also: Field-Ion Microscopy: Observation of Radiation
Effects
Bibliography
Averback R S, Seidman D 1973 Neon gas imaging of gold
in the field-ion microscope. Surf. Sci. 40: 249-63
Brenner S S 1978 Application of field-ion microscopy
techniques to metallurgical problems. Surf. Sci. 70: 42757
Chen Y C, Seidman D 1971 On the atomic resolution of a
field-ion microscope. Surf. Sci. 26: 61-84
Ehrlich G 1980 Quantitative examination of individ
ual atomic events on solids. / . Vac. Sci. Technol. 17: 9 14
Gomer R 1961 Field Emission and Field Ionization. Harvard
University Press, Cambridge, MA
Herschitz R, Seidman D 1984 An atomic resolution study
of homogeneous radiation-induced precipitation in a neu
tron irradiated W-10at.%Re alloy. Acta Metall. 32:
1141-54
Herschitz R, Seidman D 1985 Atomic resolution observa
tions of solute atom segregation effects and twodimensional phase transitions in stacking faults in dilute
cobalt alloys. Acta Metall. 33: 1547-76
Hochman R F, Muller W, Ralph (eds.) 1969 Applica
tions of Field-ion Microscopy in Physical Metallurgy and
Corrosion. Georgia Institute of Technology Foundation,
Atlanta, GA
Hren J J, Ranganthan S (eds.) 1968 Field-Ion Microscopy.
Plenum, New York
Kellogg G L, Tsong 1980 Pulsed-laser atom-probe field
ion microscopy. J. Appl. Phys. 51:1184
Miller , Beavan A, Smith G D W 1981 A study of the
early stages of tempering of iron-carbon martensites by
atom probe field ion microscopy. Metall. Trans., A 12:
1197-204
Miller , Cerezo A, Hetherington G, Smith G D W
1992 Atom Probe Field-Ion Microscopy. Oxford Univer
sity Press, Oxford
Muller W, Sakurai 1974 A magnetic sector atom-probe
FIM. J. Vac. Sci. Technol. 11: 878-82
153
Field-Ion
Microscopy:
Atom-Probe
Microanalysis
2. Capabilities
FIM
7. Capabilities
and Advantages
of the FIM
T h e principal capabilities a n d a d v a n t a g e s of t h e F I M
technique are:
(a)
(b)
t h e c o n t r o l l e d dissection of a n i r r a d i a t e d F I M
specimen o n a n a t o m - b y - a t o m basis e m p l o y i n g
the pulse-field-evaporation t e c h n i q u e ;
(c)
(d)
t h e o b s e r v a t i o n a n d i r r a d i a t i o n of specimens a t
cryogenic t e m p e r a t u r e s a s l o w a s 4.2 K w h i c h
a r e below t h e onset of t h e l o n g - r a n g e m i g r a t i o n
of SIAs; a n d
(e)
t h e in situ i r r a d i a t i o n of F I M specimens a t
elevated t e m p e r a t u r e s ( u p t o at least 400 C
seems practical).
154
of the
Atom-Probe
T h e a t o m - p r o b e F I M h a s t h e following features
which m a k e it suitable for t h e s t u d y of t h e chemical
c h a n g e s associated with t h e effects of r a d i a t i o n :
(a)
(b)
(c)
(d)
(e)
(f)
and Advantages
t h e ability t o d e t e r m i n e t h e m a s s - t o - c h a r g e r a t i o
of a single a t o m t h a t a p p e a r s in a n F I M image;
t h e possibility of chemical identification of all t h e
elements in t h e periodic table, a s t h e m a s s - t o c h a r g e r a t i o is d e t e r m i n e d b y a time-of-flight
technique;
t h e easy identification of elements of low a t o m i c
n u m b e r ( Z < 11)in p a r t i c u l a r , t h e gases h y d r o
gen a n d helium c a n b e analyzed;
a m a s s r e s o l u t i o n m/Am of ~ 200 for a c o n v e n
tional a t o m - p r o b e F I M a n d ^ 1500 for o n e
e q u i p p e d with a P o s c h e n r i e d e r lens;
a spatial r e s o l u t i o n in t h e surface of ~ 0 . 3 0.5 n m t h a t is, t h e chemical identity of t w o
a t o m s s e p a r a t e d b y this d i s t a n c e c a n be deter
mined; a n d
a d e p t h r e s o l u t i o n , in t e r m s of chemistry, t h a t is
d e t e r m i n e d b y t h e i n t e r p l a n a r spacing of t h e
specific (hkl) p l a n e being analyzed (this c a n
c o r r e s p o n d t o < 0.1 n m ) .
T h e analytical c h e m i s t r y features of t h e a t o m - p r o b e
F I M c a n be c o m b i n e d with t h e i m a g i n g capability of
the F I M t o o b t a i n a c o m p o s i t i o n profile t h a t is
associated with a s t r u c t u r a l defect, for e x a m p l e , a
void in a n e u t r o n - i r r a d i a t e d alloy.
3. Some
Induced
Contrast
Defects
Effects
Caused
by
Radiation-
Field-Ion
4. Examples
of
Studies
T h e t h r e e - d i m e n s i o n a l spatial d i s t r i b u t i o n o f v a c a n
cies c o n t a i n e d within d i s p l a c e m e n t c a s c a d e s , c r e a t e d
by a wide r a n g e of different energetic c h a r g e d p a r t i
cles, h a s b e e n studied in t u n g s t e n a n d p l a t i n u m
(Beavan et al. 1971, S e i d m a n 1973, 1976, 1978). I n all
cases, each d i s p l a c e m e n t c a s c a d e w a s p r o d u c e d b y a
single projectile i o n , so t h e e x p e r i m e n t a l o b s e r v a t i o n s
were a direct reflection o f t h e m a n n e r in w h i c h a single
ion dissipated its energy elastically. S o m e of t h e
properties of each displacement cascade determined
were:
(a)
the a b s o l u t e n u m b e r o f vacancies;
(b)
(c)
(d)
(e)
t h e r a d i a l d i s t r i b u t i o n function o u t t o t h e n i n t h
nearest n e i g h b o r ; a n d
(f)
t h e direction of m a j o r e l o n g a t i o n .
Microscopy:
Observation
of Radiation
Effects
H e a n d H e a t o m s in t u n g s t e n , a t 60 K , w h e r e t h e
helium atoms h a d n o atomic mobility (Wagner a n d
S e i d m a n 1979a). T h e diffusive b e h a v i o r of i m p l a n t e d
3
4
H e a n d H e a t o m s w a s m e a s u r e d in t h e a b s e n c e of
p o i n t o r line defects a n d it w a s s h o w n t h a t t h e en
t h a l p y c h a n g e of m i g r a t i o n for b o t h isotopes w a s a p
-1
p r o x i m a t e l y 24 k J m o l ( A m a n o a n d S e i d m a n 1984).
T h e a t o m - p r o b e F I M w a s also used t o o b t a i n direct
evidence of t h e presence of c a r b o n inside a void
detected in a m o l y b d e n u m - t i t a n i u m alloy i r r a d i a t e d
2 6
2
t o a fluence of a p p r o x i m a t e l y 6 x 1 0 m " a t a b o u t
713 ( W a g n e r a n d S e i d m a n 1979b).
O t h e r a p p l i c a t i o n s include studies of sputtering,
reflection coefficients of light gas a t o m s , d i s o r d e r i n g
of o r d e r - d i s o r d e r alloys a n d d i s p l a c e m e n t cascades
p r o d u c e d b y i o n s a t several h u n d r e d k e V .
See also: Field-Ion Microscopy: Atom-Probe Microanalysis
Bibliography
3
155
Fractals
Fractals
Australian coast
S h a p e is o n e of t h e m o s t difficult characteristics of
real objects t o describe a n d quantify. Simple Euclid
ean shapes (squares a n d circles in t w o d i m e n s i o n s , o r
cubes a n d spheres in three) rarely occur. In fact m o s t
assemblages of real objects such as grains in a m e t a l ,
p o r e s in a ceramic, individual p a r t i c u l a t e s in a p o w d e r
or surface m a r k i n g s o n a fracture, are each u n i q u e , so
t h a t even t h e c o n c e p t of a n " a v e r a g e " s h a p e m a y b e
of d o u b t f u l utility. Y e t it is also o b v i o u s t h a t m a n y
aspects of m a t e r i a l s b e h a v i o r , such as the effect of
p r i o r history a n d processing o n p r o p e r t i e s , act
t h r o u g h the shape(s) of individual objects a n d their
interfaces.
1. Methods
of Shape
Analysis:
Fractals
Efforts to describe s h a p e s by c o m b i n a t i o n s of m e t r i c
p a r a m e t e r s , such as t h e aspect r a t i o (length divided by
2
b r e a d t h ) o r form factor (4 a r e a / p e r i m e t e r ) , i g n o r e
the o r g a n i z a t i o n of the irregularities o n the surface o r
outline of the object. In principle a c o m p l e t e descrip
tion of the s h a p e (at least for a t w o - d i m e n s i o n a l
profile) is c o n t a i n e d in the coefficients of a F o u r i e r
analysis of the " u n r o l l e d " s h a p e . H o w e v e r , r e e n t r a n t
shapes a r e n o t easily h a n d l e d with this t e c h n i q u e , a n d
in general the fact t h a t different classes of objects m a y
be m a t h e m a t i c a l l y distinguishable by t h e values of
p a r t i c u l a r h i g h - o r d e r coefficients seems to hide, r a t h e r
t h a n m a k e clear, the real differences in s h a p e which
are often visually evident t o t h e h u m a n observer.
W e desire tools t h a t deal m o r e directly with t h o s e
aspects of s h a p e t h a t we see a n d which m o r e m e a n i n g
fully describe the s h a p e of real lines, b o u n d a r i e s a n d
surfaces. A n i m p o r t a n t aspect of these is the fact t h a t
the a m o u n t of r o u g h n e s s a n d irregularity we c a n see is
generally limited by o u r resolution, which is n o t the
case for a Euclidean line o r surface. W e will consider a
line to be a b o u n d a r y between regions, which h a s n o
internal tension a n d d o e s n o t strive to be straight. T h e
c o n s t r a i n t t h a t the line be " s m o o t h " (that is, h a v e
derivatives a t every p o i n t ) is specifically relaxed, so
t h a t the line c a n be " c r i n k l e d . "
T h e extension of this a p p r o a c h to surfaces is
s t r a i g h t f o r w a r d . I n s t e a d of flat c o n t i n u o u s " E u c l i
d e a n " surfaces, we will be p a r t i c u l a r l y interested in
things t h a t c a n be crinkled u p in w a y s t h a t m a y b e t t e r
describe m a n y " r e a l " surfaces. T h e p a r t i c u l a r type of
crinkled-up b e h a v i o r t h a t is of m o s t interest t o us here
h a s a peculiar form called self-similarity. T h i s simply
m e a n s t h a t at a n y magnification at which we c h o o s e
to view the line o r surface, it l o o k s the s a m e . W h a t
ever m e a s u r e m e n t s we c a n m a k e t o describe t h e
r o u g h n e s s will be i n d e p e n d e n t of the scale. Interest
ingly, these k i n d s of s h a p e s are actually quite c o m
m o n in n a t u r e .
Of course, there a r e s o m e n a t u r a l surfaces t h a t
really a r e s m o o t h a n d Euclidean, particularly facets
156
o3
circle
South African coast
-
German land
"frontier (1900)
PortugaMand frontier
1.5
2.5
Figure 1
Richardson's plots of the lengths of various geographical
boundaries versus the distance used for measurement
(the length of the side of -the polygon used to fit the
boundaries)
t h a t d e v e l o p b e c a u s e of t h e c r y s t a l l o g r a p h i c a t o m i c
lattice, o r m e m b r a n e s t h a t a s s u m e a least-energy
configuration in r e s p o n s e t o surface tension. T h e r e
a r e also n a t u r a l surfaces t h a t a r e r o u g h a n d r a n d o m ,
b u t n o t in the p a r t i c u l a r self-similar w a y we describe
as " f r a c t a l . " In t h e limits as we a p p r o a c h a t o m i c
d i m e n s i o n s o r m a c r o s c o p i c o n e s , t h e n a t u r e of b o u n
daries will c h a n g e , b u t over a b r o a d r a n g e of sizes,
m a n y " r e a l " b o u n d a r i e s c a n be described in this w a y .
2. Richardson
Plots
and Fractal
Dimension
T h i s effect w a s first n o t e d in t w o d i m e n s i o n s , b y a
British m a t h e m a t i c i a n
named Richardson.
He
m e a s u r e d t h e b o r d e r s of several c o u n t r i e s a n d l a n d
masses, b u t the b e s t - k n o w n e x a m p l e is t h e west c o a s t
of Britain. If the length of t h e b o u n d a r y (the coast
line) w a s d e t e r m i n e d b y swinging a l o n g a m a p of t h e
c o u n t r y with dividers set a t s o m e a r b i t r a r y distance,
say 100 k m , a t o t a l length w a s o b t a i n e d . T h e n if t h e
divider distance, o r stride length, w a s reduced, a n d
the s a m e o p e r a t i o n r e p e a t e d , t h e m e a s u r e d length w a s
greater because the m e a s u r e m e n t w a s able t o follow
m o r e of the irregularities of t h e coastline. R e p e a t i n g
the o p e r a t i o n with finer a n d finer steps ( a n d m a p s of
a p p r o p r i a t e scale) w o u l d c a u s e t h e length t o c o n
tinuously increase so t h a t , in effect, the length of t h e
coastline w o u l d b e expected to b e c o m e infinite a t a
fine e n o u g h scale. F u r t h e r m o r e , R i c h a r d s o n n o t e d
t h a t over a c o n s i d e r a b l e r a n g e of stride lengths, a n d
for a variety of b o r d e r s , b o t h n a t u r a l a n d artificial,
the slope of the p l o t of m e a s u r e d length against stride
length w a s c o n s t a n t (see Fig. 1) o n a log scale.
A n e x a m p l e of increasing p e r i m e t e r w i t h o u t
increasing a r e a is s h o w n in Fig. 2. T h i s type of feature
is called a K o c h island, after the m a t h e m a t i c i a n w h o
p r o p o s e d t h e m . All the features a r e d r a w n with t h e
s a m e area; i m a g i n e t h a t in each of the different i m a g e s
Fractals
Figure 2
A Koch island with a perimeter whose fractal dimension is
1.5
y o u r i m a g e r e s o l u t i o n h a s i m p r o v e d by a factor of
four t o distinguish smaller details. T h e p e r i m e t e r o n
each successive feature is increased b e c a u s e of t h e
p a t t e r n e d irregularities i n t r o d u c e d o n e a c h straightline s e g m e n t of t h e b o u n d a r y . T h e a m o u n t of peri
m e t e r increases b y a factor of 1.5 from e a c h feature t o
t h e next a n d there is n o limit t o h o w far we m i g h t
extend this p r o c e s s , so t h e length of t h e p e r i m e t e r is
undefined. T h e m a t h e m a t i c i a n s w h o c o n s i d e r e d
shapes like these w e r e horrified a t t h e b e h a v i o r of
such lines a n d s h a p e s b e c a u s e w i t h o u t s m o o t h , c o n
t i n u o u s derivatives they c o u l d n o t easily b e h a n d l e d
by c o n v e n t i o n a l t e c h n i q u e s .
If t h e increase in m e a s u r e d length w i t h i m p r o v e
m e n t in m e a s u r i n g r e s o l u t i o n is u n i f o r m (a s t r a i g h t
line o n a log p l o t , a s s h o w n in R i c h a r d s o n ' s d a t a ) , t h e
feature is said t o b e self-similar. T h e c o n s e q u e n c e is
t h a t it is n o t really possible t o s t a t e w h a t t h e a m o u n t
of b o u n d a r y o r surface a r e a is. F o r t h e K o c h island
s h o w n in t h e figure, t h e fact t h a t t h e p e r i m e t e r in
creases b y a factor of 1.5 for e a c h h a l v i n g of t h e
m e a s u r e m e n t d i s t a n c e h a s led M a n d e l b r o t (1982) t o
describe this p a r t i c u l a r b o u n d a r y line as h a v i n g a
d i m e n s i o n n o t of 1 (a s t r a i g h t line) o r 2 (a p l a n e ) b u t
1.5. I n o t h e r w o r d s , t h e line h a s a fractional d i m e n
sion which reflects its t e n d e n c y t o fill a p l a n e , a n d
hence it is called a fractal.
D e p e n d i n g o n t h e n a t u r e of t h e irregularity i n t r o
d u c e d o n t h e K o c h island, t h e r a t e a t w h i c h t h e
p e r i m e t e r increases w i t h e a c h step c a n vary. F i g u r e 3
shows several possibilities. I n e a c h case, t h e a r e a of
the feature is u n c h a n g e d as e a c h straight-line s e g m e n t
in the feature b o u n d a r y is replaced, a n d t h e n t h e
sequence r e p e a t e d a t a finer scale, b u t t h e r a t e a t
which t h e p e r i m e t e r increases is given b y t h e v a l u e
s h o w n . T h e s e values a r e related t o t h e slopes of t h e
R i c h a r d s o n p l o t t h a t o n e w o u l d o b t a i n for these
features. H i g h e r fractal d i m e n s i o n s reflect t h e fact
t h a t as t h e s u b s t i t u t i o n s of finer scale irregularities a r e
3. Practical
Measurement
of Fractal
Dimension
T o m e a s u r e t h e fractal d i m e n s i o n of real s t r u c t u r e s ,
such as p a r t i c u l a t e s w h o s e surface a r e a m a y be im
p o r t a n t (as a s u b s t r a t e for chemical r e a c t i o n s o r a site
1.5
1.661
Figure 3
Irregularities that can be used on the Koch island with
different fractal dimensions
157
Fractals
slope m-
-D
log [ / m a x i m u m Feret's d i a m e t e r ]
Figure 5
Schematic Richardson plot for a closed outline
Figure 4
Random fractal outlines generated as described in the
text, with varying fractal dimensions
158
Fractals
4. Extension
to
Surfaces
Figure 6
A generated fractal surface (dimension 2.18) intersected by
a plane; the intersection contour has a fractal dimension
of 1.18
E m m e t t - T e l l e r ( B E T ) m e a s u r e m e n t s of surface a r e a
u s i n g different m o l e c u l a r species (with v a r y i n g sizes).
H o w e v e r , for t h e general case, n o direct m e t h o d for
m e a s u r i n g surface a r e a is really suitable.
A s for m a n y stereological r e l a t i o n s h i p s , it is p o s
sible t o p e r f o r m m e a s u r e m e n t s o n t w o - d i m e n s i o n a l
intersections t h r o u g h solids from w h i c h i n f o r m a t i o n
a b o u t t h e t h r e e - d i m e n s i o n a l s h a p e s c a n be o b t a i n e d .
F o r i n s t a n c e , t h e surface a r e a p e r u n i t v o l u m e 5 V m a y
be d e t e r m i n e d from t h e length of b o u n d a r i e s p e r u n i t
a r e a 2? A, o r even t h e n u m b e r of intersection p o i n t s p e r
length of line PL. It is similarly possible t o relate the
fractal d i m e n s i o n of a surface (a value b e t w e e n 2 a n d
3) t o t h a t of its intersection w i t h a p l a n e (an outline
with a fractal d i m e n s i o n b e t w e e n 1 a n d 2). C o n s i d e r
as a familiar case t h e shoreline a r o u n d a n island.
I s l a n d s t h a t a r e generally r a t h e r r o u g h a n d hilly
w o u l d b e expected t o h a v e a shoreline t h a t is m o r e
irregular t h a n islands t h a t h a v e m o r e g r a d u a l
topography.
F o r t h e ideal case, M a n d e l b r o t h a s s h o w n t h a t for
surfaces g e n e r a t e d using r a n d o m i z e d self-similar frac
tals with a d i m e n s i o n of t h e f o r m 2.D ( O ^ D ^ l ) ,
p l a n e sections t h r o u g h t h e surface p r o d u c e outlines
with a fractal d i m e n s i o n 1 .D. I n F i g . 6 t h e g e n e r a t e d
r a n d o m fractal surface is intersected with a p l a n e
("sea level"), p r o d u c i n g a n outline ( " s h o r e l i n e " )
w h o s e fractal d i m e n s i o n c a n b e m e a s u r e d . T h i s m e a n s
t h a t m e a s u r e m e n t s o n p l a n a r sections using t h e
m e t h o d s a l r e a d y described c a n be applied directly
t o describe surfaces. N o t e t h a t this applies only t o
sections t h r o u g h t h r e e - d i m e n s i o n a l features a n d n o t
projected o r s h a d o w i m a g e s a s a r e often viewed in t h e
t r a n s m i s s i o n light o r electron m i c r o s c o p e . F o r t h a t
case, t h e o u t l i n e will h a v e a value of D t h a t sets a
lower limit t o t h e value for t h e surface.
D i m e n s i o n a l analysis of t h e relationships between
surface a r e a , v o l u m e a n d length a r e s o m e w h a t dif
ferent with these n o n - E u c l i d e a n b o u n d a r i e s t h a n
t h o s e w i t h w h i c h w e a r e generally familiar. In general,
159
Fractals
1/3
1 /2
we w o u l d expect a n y r a t i o of v o l u m e , a r e a
and
length t o be dimensionless. F o r E u c l i d e a n s h a p e s , this
1 /3
m i g h t t a k e the f o r m of expecting v o l u m e
to be
1 /2
p r o p o r t i o n a l t o (surface a r e a )
for a series of
features. H o w e v e r , very different relationships a r e
actually observed in the real w o r l d .
5. Real-World
Examples
1 /3
F o r m a m m a l i a n b r a i n s , v o l u m e is p r o p o r t i o n a l t o
1 / 2 1 6
surface a r e a
. T h i s is a n o t h e r w a y of saying t h a t the
surface of t h e b r a i n h a s a fractal d i m e n s i o n of 2.76,
which w o u l d be revealed by section outlines with a
fractal d i m e n s i o n of 1.76. M a n y o t h e r similar rela
tionships h a v e been quantified for living things,
usually by m a k i n g l o g - l o g plots of p a r a m e t e r s with
very different d i m e n s i o n s a n d units a n d finding
straight-line relationships. S o m e d o n o t fit t h e simple
slopes expected from E u c l i d e a n g e o m e t r y , which in
this c i r c u m s t a n c e is described a s t h e ideal allometric
behavior. T h e d e v i a n t cases m a y involve fractal b e h a
vior for such things as b e n d i n g b e h a v i o r of trees
(which h a v e fractal b r a n c h i n g p a t t e r n s ) a n d speed
against size for s w i m m i n g fish (the b o u n d a r y layer,
which c o n t r i b u t e s m o s t of t h e resistance, m a y h a v e a
fractal n a t u r e ) .
E x a m p l e s from o t h e r fields a r e also available. F o r
instance, consider the r e l a t i o n s h i p between the length
of a river system (which will d e p e n d o n the length of
the yardstick used t o m e a s u r e it) a n d t h e a r e a of t h e
d r a i n a g e basin (which h a s c o n v e n t i o n a l units of a r e a
a n d is n o t sensitive t o the scale of m e a s u r e m e n t ) . It
h a s been s h o w n t h a t t h e s q u a r e r o o t of the basin a r e a
is p r o p o r t i o n a l t o the straight-line distance from
source to m o u t h , b u t t h a t t h e length of t h e river is
p r o p o r t i o n a l t o t h e a r e a raised t o t h e p o w e r 0.6
( r a t h e r t h a n t h e expected 0.5). T h i s is equivalent t o
stating t h a t t h e fractal d i m e n s i o n of typical rivers
is 1.2.
T h e similar use of a r e a versus v o l u m e relationships
for particles viewed in the m i c r o s c o p e is often a m o r e
efficient w a y t o d e t e r m i n e the fractal d i m e n s i o n of the
surface t h a n direct m e a s u r e m e n t of section profiles.
A s a practical e x a m p l e of alternative w a y s t o deter
m i n e t h e fractal d i m e n s i o n of objects, Fig. 7 s h o w s a
plot of the m e a s u r e d m a s s (weight) of clusters of
aggregate particles against the m a x i m u m d i m e n s i o n
of the a g g r e g a t e . B o t h axes a r e n o r m a l i z e d t o a n
individual particle (which m e a n s t h a t the vertical axis
is actually the n u m b e r of particles in t h e aggregate),
b u t this d o e s n o t c h a n g e the overall i n t e r p r e t a t i o n .
D e p e n d i n g o n the c o n d i t i o n s u n d e r which t h e
aggregates form (e.g., t h r e e - d i m e n s i o n a l clusters as
o p p o s e d to t w o - d i m e n s i o n a l g r o w t h o n a s u b s t r a t e )
a n d possible c o n s t r a i n t s o n the w a y t h a t individual
particles c a n m i g r a t e t o w a r d o r a t t a c h t o the aggre
gate, t h e surface ruggedness c a n vary widely (consider
b r a n c h i n g , dendritic s t r u c t u r e s a n d perfectly faceted
160
Figure 7
Plot of number of identical particles in an aggregate
against its maximum dimension has a slope equal to the
fractal dimension of the aggregate surface
Fractals
F r a c t a l analysis h a s been a p p l i e d t o t h e d e s c r i p t i o n of
fracture surfaces in t w o different w a y s . U n d e r w o o d
a n d Banerji (1986) h a v e sectioned p e r p e n d i c u l a r l y
t h r o u g h t h e p l a n e of fracture t o digitize a n d m e a s u r e
the line profile of t h e r o u g h surface. M e c h o l s k y a n d
Passoja (1985) h a v e p l a t e d t h e surface w i t h a c o n t r a s t
ing m a t e r i a l a n d polished parallel t o t h e m a j o r orien
t a t i o n . I n t h e latter case, islands a r e p r o d u c e d (similar
t o F i g . 6) w h o s e outlines c a n be m e a s u r e d . I n b o t h
cases, t h e fractal d i m e n s i o n is of t h e f o r m 1 .D a n d is
a s s u m e d t o be related t o t h e surface 2.D value.
C o r r e l a t i o n s of surface r o u g h n e s s with t e m p e r a t u r e
e m b r i t t l e m e n t in steels a n d with m e a s u r e d fracture
r o u g h n e s s in glass c e r a m i c s a n d a l u m i n a h a v e been
d e m o n s t r a t e d . A t t e m p t s t o m o d e l fracture p r o p a g a
tion a n d t h e g r o w t h of d e p o s i t e d aggregates u s i n g
r a n d o m fractals ( L a i b o w i t z et al. 1985) a r e n o w being
performed.
W o r k with fractals is q u i t e n e w a n d t h e r e is s o m e
tendency a t t h e p r e s e n t time t o a p p l y fractal i n t e r p r e
t a t i o n s t o t o o m a n y real p h e n o m e n a . H o w e v e r , this
will be self-correcting a s m o r e w o r k is d o n e . F u r t h e r
d e v e l o p m e n t s in b o t h t h e o r y a n d i n t e r p r e t a t i o n m a y
be a n t i c i p a t e d .
Bibliography
Kaye 1984 Multifractal description of a rugged fineparticle profile. Part. Characteriz. 1: 14-21
Laibowitz R B, Mandelbrot , Passoja D 1985 Fractal
Aspects of Materials (extended abstracts). Materials
Research Society, Pittsburgh, PA
Mandelbrot 1982 The Fractal Geometry of Nature.
Freeman, New York
Mecholsky J J, Passoja D 1985 Fractals and brittle
fracture. In: Laibowitz et al. 1985, pp. 117-20
Sander L 1986 Fractal growth processes. Nature (Lon
don) 322: 789-93
Underwood , Banerji 1986 Fractals in fractography.
Mater. Sci. Eng. 80: 1-14
J. C. R u s s
[ N o r t h C a r o l i n a State University,
Raleigh, N o r t h C a r o l i n a , U S A ]
161
G
Gamma Radiography
G a m m a r a d i o g r a p h y is a p r o c e d u r e for t h e n o n
destructive e x a m i n a t i o n of industrial m a t e r i a l s , utiliz
ing t h e p e n e t r a t i n g r a d i a t i o n e m i t t e d by r a d i o a c t i v e
sources. G a m m a rays a n d rays of a n y given energy,
b o t h being e l e c t r o m a g n e t i c r a d i a t i o n , a r e indis
tinguishable except for their origin; g a m m a rays
represent t h e release of energy from t h e a t o m i c n u c
leus, while rays result from t h e r e a r r a n g e m e n t of t h e
electron s t r u c t u r e s u r r o u n d i n g t h e nucleus. M o s t
g a m m a r a d i o g r a p h y is c o n d u c t e d with g a m m a rays
h a v i n g energies in t h e m e g a v o l t r a n g e , p r i m a r i l y
because m o s t r a d i o a c t i v e sources e m i t c o p i o u s r a d i
a t i o n at these energies. By c o n t r a s t , m o s t r a d i o g
r a p h y is p e r f o r m e d a t x-ray t u b e p o t e n t i a l s u p t o
h u n d r e d s of kilovolts.
G a m m a r a d i o g r a p h y is used principally for t h e
inspection of welds a n d castings in s t r u c t u r e s such as
steel t a n k s a n d pipelines w h e r e sections a r e thick
e n o u g h to r e q u i r e m e g a v o l t r a d i a t i o n t o p e n e t r a t e
t h e m , o r w h e r e it is a d v a n t a g e o u s t o m a k e use of t h e
p o r t a b i l i t y offered by g a m m a r a d i o g r a p h y e q u i p
m e n t . A n u m b e r of a p p l i c a t i o n s t a k e a d v a n t a g e of the
small size of r a d i o a c t i v e sources t o r a d i o g r a p h objects
from t h e inside, such as t h e walls of s m a l l - d i a m e t e r
pipes. T h i s t e c h n i q u e p e r m i t s a single e x p o s u r e t o
p r o d u c e a r a d i o g r a p h of a n entire circumferential
weld a n d often c o n s i d e r a b l y simplifies t h e i n t e r p r e
t a t i o n of r a d i o g r a p h s of c o m p l i c a t e d s t r u c t u r e s such
as aircraft jet engines w h e r e film w r a p p e d a r o u n d t h e
7. Radiographic
Sources
Table 1
Gamma radiography isotopes
Isotope
Half-life
^Co
,37
Cs
5.26 y
30.2 y
74.0 d
1 9 2 I cr
,70
Tm
1 6 9 Y cb
125 d
30.7 d
Effective
gamma
energies (keV)
1250
662
310
457
603
53 (x ray)
84
52 (x ray)
117
191
302
Gamma
intensities a
(rhm per Ci)
1.30
0.32
0.249 |
0.144 =0.46
0.063 J
0.015 |
0 30
0.012 I
0.090 \
0.018
Uy i
0.056
0.022 J
Typical
maximum
source
strength (Ci)
Minimum
thickness ofb
steel (mm)
1000
10
25
18
200
12
50
50
192
a rhm = roentgens per hour at 1 meter b For 2% radiography c The 30 gamma rays of Ir can be represented by
3 monoenergic radiations. For
,70
historical reasons, US industry uses 0.55 rhm per Ci d Because of the low yield of rays and gamma rays from Tm the lcontinuous
radiation
69
generated by the 1 MeV beta rays is an appreciable contaminant that hardens the emitted spectrum e The 24 gamma rays of Yb can be represented
by 3 monoenergetic radiations
163
Gamma
Radiography
Projector
( )
Expose
Drive
Hand
cable
crank
tig
-Source
Snout
I 7
Guide t u b e s
(b)
Source
/
Control
cable
Retra
(c:
Source
\-
Snout
(radiographic
focal p o i n t )
Figure 1
Principle of operation of a typical radiographic exposure device: (a) the source in its stored position, (b) the source in
transit and (c) the source at the radiographic site
N o t all r a d i o a c t i v e isotopes d e c a y by g a m m a - r a y
emission a n d n o t all t h a t d o so a r e useful for g a m m a
r a d i o g r a p h y . I m p o r t a n t factors a r e t h e efficiency of
p r o d u c t i o n of t h e i s o t o p e , its r a t e of d e c a y a n d t h e
a m o u n t of g a m m a r a d i a t i o n t h a t it releases. O n l y five
isotopes (excluding r a d i u m ) h a v e f o u n d m u c h utility
in g a m m a r a d i o g r a p h y (see T a b l e 1), a n d of these,
only c o b a l t , iridium a n d y t t e r b i u m a r e in a p p r e c i a b l e
use t o d a y . O n c e , cesium w a s e m p l o y e d extensively,
particularly in E u r o p e , b u t its low specific activity
_1
(25Cig
m a x i m u m ) severely limits t h e achievable
resolution. W i t h i m p r o v e d m e t h o d s for r e p l a c e m e n t
of spent sources, y t t e r b i u m h a s effectively t a k e n over
the role o n c e played b y t h u l i u m as a low-energy
emitter, since y t t e r b i u m c a n b e p r o d u c e d in consider
ably greater s t r e n g t h s .
137
Except for C s , a fission p r o d u c t , all r a d i o g r a p h i c
isotopes a r e m a d e b y i r r a d i a t i n g t h e element with
t h e r m a l n e u t r o n s in high-flux n u c l e a r r e a c t o r s . Pellets
of metallic c o b a l t o r iridium o r sintered t h u l i u m o r
y t t e r b i u m oxide a r e installed in capsules specially
designed t o avoid excessive self-absorption in t h e
target m a t e r i a l a n d subjected t o fluxes of t h e o r d e r of
15
-2
1
c m s " for times t h a t will m a x i m i z e t h e yield.
Because s o m e of t h e desired r a d i o a c t i v e a t o m s a r e lost
by d e c a y a n d by c a p t u r e of further n e u t r o n s d u r i n g
i r r a d i a t i o n , t h e o p t i m u m times in t h e r e a c t o r a r e
generally less t h a n a half-life of t h e i s o t o p e .
R a d i o g r a p h i c sources a r e m a n u f a c t u r e d b y l o a d i n g
the r a d i o a c t i v e m a t e r i a l i n t o stainless steel capsules
t h a t a r e hermetically sealed b y welding. F o r metallic
164
2. Exposure
Devices
T h e c o m m o n e s t f o r m of e x p o s u r e device in t h e U S A
t o d a y consists of a f o o t b a l l - s h a p e d lead o r depletedu r a n i u m shield c o n t a i n i n g a n S-shaped t u b e . A s
s h o w n in F i g . 1, t h e sealed s o u r c e , a t t a c h e d t o a s h o r t
" p i g t a i l , " n o r m a l l y resides a t the center of t h e shield;
after a t t a c h i n g a cable drive system t o the pigtail a t
t h e r e a r of t h e shield, t h e r e m o t e l y located o p e r a t o r
c a n drive t h e s o u r c e o u t of t h e shield a n d a l o n g t h e
guide tube to a prepositioned radiography location by
m e a n s of a h a n d c r a n k . T h e source is later w i t h d r a w n
t o its s t o r a g e p o s i t i o n a t t h e e n d of t h e r a d i o g r a p h i c
e x p o s u r e . R a d i a t i o n from t h e s t o r e d s o u r c e is c o n
fined t o t h e shield by t h e S c u r v e of the internal t u b e .
3
T h e high a t o m i c n u m b e r , high density (18.7 g c m " )
a n d r e a d y availability of depleted u r a n i u m h a s led t o
its a l m o s t exclusive use as a p r i m a r y shielding m a t e r
192
ial in e x p o s u r e devices a n d s o u r c e c h a n g e r s . A n
Ir
Gamma-Ray
Diffractometry
3. Exposure
Techniques
E x p o s u r e t e c h n i q u e s for g a m m a r a d i o g r a p h y a r e
similar t o t h o s e for r a d i o g r a p h y , except t h a t e x p o
sure times a r e generally m e a s u r e d in m i n u t e s r a t h e r
t h a n seconds a n d t h e energy a n d hence p e n e t r a b i l i t y
of t h e r a d i a t i o n c a n be varied only by using different
isotopic sources. T h e variables affecting e x p o s u r e
include, besides t h e e x p o s u r e time, t h e s o u r c e s t r e n g t h
a n d distance from t h e film, t h e thickness of t h e section
t o be p e n e t r a t e d a n d t h e sensitivity of t h e d e t e c t o r
system. T h e r a d i o g r a p h e r usually w o r k s with a m i n i
m u m source-film d i s t a n c e consistent with a c c e p t a b l e
geometric d i s t o r t i o n a n d r e s o l u t i o n in o r d e r t o m i n i
mize e x p o s u r e time.
M i n i m u m thicknesses of steel for w h i c h flaw detec
tion c a n be carried o u t successfully a r e given in
T a b l e 1. G a m m a r a d i o g r a p h y is nevertheless useful in
t h i n n e r sections w h e r e t h e p u r p o s e is t o display t h e
presence of relatively large objects, such as reinforcing
b a r s in c o n c r e t e slabs o r h i d d e n i n t e r n a l p a r t s in
c o m p l i c a t e d assemblies.
I n general, e x p o s u r e t e c h n i q u e s for g a m m a r a d i o g
r a p h y a r e similar t o t h o s e for high-energy r a y s
g e n e r a t e d a t p e a k voltages a p p r o x i m a t e l y d o u b l e t h e
p h o t o n energies. T h u s , a b s o r p t i o n curves for ^ C o
r a d i a t i o n in steel a r e similar t o t h o s e for 2.5 M V p
radiation.
See also: Neutron Radiography
Gamma-Ray Diffractometry
T h e very low a t t e n u a t i o n of g a m m a rays in m a t t e r
allows their use t o s t u d y t h e lattice perfection of thick
crystals. A n e x a m i n a t i o n of s a m p l e s in a furnace,
c r y o s t a t o r u l t r a h i g h - v a c u u m ( U H V ) device is also
possible a n d c a n p r o v i d e i n f o r m a t i o n a b o u t b u l k
p h a s e t r a n s i t i o n s . W h e n u s i n g t h e 468 k e V r a d i a t i o n
192
of I r t h e a t t e n u a t i o n coefficient of nickel a m o u n t s t o
1
only " ~ 0 . 8 c m . T h e B r a g g angles a r e of the o r d e r
of . T h u s t h e m e a s u r e d r o c k i n g curves a r e only
affected by lattice tilts a n d small-angle grain b o u n d
aries. T h e i n t e g r a t e d B r a g g diffraction intensity of
nearly perfect crystals is c o r r e l a t e d with t h e disloca
tion density in these crystals.
1. The Gamma-Ray
Diffractometer
T h e essential c o m p o n e n t s of t h e g a m m a - r a y diffract
o m e t e r a r e s h o w n in Fig. 1. T h e s e a r e g a m m a - r a y
s o u r c e , a c o l l i m a t o r for p r e p a r i n g a b e a m with small
a n g u l a r divergence, a s a m p l e fixed o n a g o n i o m e t e r
a n d a n N a l scintillation c o u n t e r for detecting
t h e direct a n d diffracted b e a m s . T h e g a m m a - r a y
source
consists
of
a
small
iridium
sheet
(0.2 m m x 4 m m x 10 m m ) shielded by a u r a n i u m b o x
a n d m a d e r a d i o a c t i v e by n e u t r o n a c t i v a t i o n t o a n
activity of a b o u t 1 T B q (100 Ci). T h e r a d i o i s o t o p e
*^Ir t h u s g e n e r a t e d decays w i t h a half-life of 74 d a y s
Bibliography
Clarke 1959 Isotope radiation sources. In: McMaster R
C (ed.) 1959 Nondestructive Testing Handbook. Ronald
Press, New York, Sect. 15
Clarke 1976 Radiographing the Liberty Bell. Foundry
Trade J. 141 (Aug): 223-8
Clarke 1980 Radiography of the Cape Hatteras light
house. Technol. Conserv. 5(1): 20-4
Clarke , Coenraads C 1967 Radiographic Characteris
tics of Ytterbium 169, Report ORNL-IIC-10. Oak
Ridge National Laboratory, Oak Ridge, TN
Evans R D 1955 The Atomic Nucleus. McGraw-Hill, New
York
Glasgow G P, Dillman L 1979 Specific gamma ray
constant and exposure rate constant of iridium-192. Med.
Phys. 6(1): 49-52
Graham R L, Wolfson J L, Bell R 1952 The disintegration
of thulium-170. Can. J. Phys. 30: 459-75
Hatziandreou L, Ladopoulos G 1980 Use of radiography
for solution of diagnostic problems existing in marble
monuments. Materialprufung 22: 298-300
-2m-
Detector
--r
'
i
ill .
jl I
j-fe "
1
Source
Collimator
Furnace
Sample space
Figure 1
Experimental setup of a gamma-ray diffractometer
165
Gamma-Ray
Diffractometry
where 7 U is t h e b a c k g r o u n d intensity a n d IT is t h e
intensity of the t r a n s m i t t e d b e a m . T h e integral Rm =
J rjjco) dco, called t h e m e a s u r e d i n t e g r a t e d reflecting
p o w e r , d e p e n d s only o n t h e p r o p e r t i e s of t h e crystal
a n d n o t o n t h e incident intensity. O w i n g t o t h e high
energy of t h e g a m m a r a y s , s a m p l e s a r e always ex
a m i n e d in t r a n s m i s s i o n g e o m e t r y ( L a u e case). Small
4
v a r i a t i o n s of t h e lattice p a r a m e t e r (1 in 10 ) a r e
usually negligible.
2. Gamma-Ray
Diffraction
Theory
In t h e t h e o r y of x-ray a n d g a m m a - r a y diffraction t w o
limiting cases h a v e t o b e considered: t h e k i n e m a t i c a l
a n d t h e d y n a m i c a l regimes ( Z a c h a r i a s e n 1945).
W h i c h case is t o b e applied d e p e n d s o n t h e w a v e
length of t h e r a d i a t i o n used, t h e diffraction angle a n d
the crystal perfection (dislocation density) ( F r e u n d
1973). W h e n w o r k i n g with small w a v e l e n g t h s a n d
imperfect crystals t h e k i n e m a t i c a l a p p r o a c h , which
will b e discussed in t h e following, is valid.
T h e basic a s s u m p t i o n of t h e k i n e m a t i c a l t h e o r y is
D a r w i n ' s m o s a i c m o d e l ( D a r w i n 1922) in which t h e
crystal is a s s u m e d t o b e divided i n t o m a n y , slightly
misoriented, small perfect crystal blocks (see Fig. 2).
T h e t o t a l diffracted intensity is t h e s u m o f t h e intensit
ies t h a t e a c h block diffracts. T h e lattice tilts b e t w e e n
the blocks a r e described b y t h e m o s a i c d i s t r i b u t i o n
function W(co), which in t h e ideal case will b e a
G a u s s i a n function (Schneider 1981). I t s full w i d t h a t
half m a x i m u m ( F W H M ) is t h e m o s a i c angle . T h e
reflectivity d i s t r i b u t i o n function r k i n(a>) is given b y
Figure 2
Schematic representation of the diffraction process in a
mosaic crystal
k m
e xt
3.1 Crystal
Growth
166
r0X\FH]
cos
is
0BJ
exp(-M)
w h e r e r 0 is t h e classical electron r a d i u s , FH is t h e
s t r u c t u r e factor, exp( - M) is t h e D e b y e - W a l l e r fac
t o r , V is t h e v o l u m e of t h e e l e m e n t a r y cell a n d / e xt is
t h e " e x t i n c t i o n l e n g t h . " Rkin represents a n u p p e r limit
for t h e i n t e g r a t e d reflecting p o w e r . If Rm = Rkin a
crystal is called ideally imperfect. I n m o s t cases t h e
relation Rdya < Rm< R^ is valid, w h e r e Rdyn is deter
m i n e d from d y n a m i c a l t h e o r y .
W h e t h e r t h e crystals diffract in a d y n a m i c a l o r
k i n e m a t i c a l m a n n e r d e p e n d s o n t h e extinction length
text defined in E q n . (3) a n d o n t h e size t0 of the defectfree d o m a i n s s h o w n in F i g . 2. F o r t0 > i e xt (perfect
crystal) d y n a m i c a l t h e o r y is applied, a n d for t0 < text
k i n e m a t i c a l t h e o r y is applied. O n e o b t a i n s , for in
stance, a value of / e xt = 73 for t h e diffraction o f
2.65 p m g a m m a r a d i a t i o n a t a (222) reflection o f a
c o p p e r crystal. W i t h dislocation densities larger t h a n
2
- 2
1 0 m m , t h e a v e r a g e m o s a i c block w i d t h c o r r e s
p o n d i n g t o t h e a v e r a g e d i s t a n c e b e t w e e n dislocations
is m u c h smaller t h a n t h e extinction length, resulting in
k i n e m a t i c a l diffraction b e h a v i o u r .
3. Applications
20R
Rkin = $ rkin(co)dco
of Gamma-Ray
Perfection
Analysis
Diffractometry
During
Crystal
A vertical S t o b e r - t y p e crystal g r o w t h u n i t w a s
designed a n d placed in t h e g a m m a - r a y b e a m . C o p p e r
crystals (6 m m in d i a m e t e r b y 120 m m ) were g r o w n in
Gamma-Ray
Diffractometry
Figure 3
(a) Time dependence of the integrated intensity of the (111) reflection; (b) growing crystal in the gamma-ray beam
tr/v
By d e t e r m i n i n g a t different p o s i t i o n s in t h e
growing crystal, t h e t e m p e r a t u r e field T{z) c a n b e
estimated.
_ A\ ~ * A 1
w h e r e r A1 is t h e p r o b a b i l i t y t h a t a n Al a t o m site is
filled b y a n Al a t o m a n d FM is t h e a t o m i c fraction of
Al in t h e alloy. S varies b e t w e e n 0 ( c o m p l e t e d i s o r d e r )
a n d 1 ( c o m p l e t e o r d e r ) . I n t h e case of g a m m a - r a y
diffraction t h e v a l u e for S c a n be o b t a i n e d from the
relationship
_* > ex
( -
2MP>)
flJTl/A.
3 / N i|
R^exp(-2M^)e^\fM-fNi\'
w h e r e e x p ( - M) is the D e b y e - W a l l e r factor a n d y j is
t h e a t o m i c scattering factor. T h e v a r i a t i o n of the
i n t e g r a t e d intensity with t e m p e r a t u r e for a nearly
s t o i c h i o m e t r i c N i 3 A l single crystal is s h o w n in Fig. 5.
T h e (200) reflection intensity decreases o w i n g t o t h e
D e b y e - W a l l e r factor. T h e (100) B r a g g diffraction
167
Gamma-Ray
Diffractometry
Figure 4
Series of gamma-ray rocking curves measured along growth direction (z axis) during a crystal growth experiment
intensity is n e a r l y i n d e p e n d e n t of t e m p e r a t u r e b e l o w
1300 C, b u t t h e n declines a t 1 3 3 0 C i n d i c a t i n g t h e
existence of a n o r d e r - d i s o r d e r t r a n s i t i o n a t a t e m p e r
a t u r e slightly below t h e m e l t i n g p o i n t .
(200) fundamental
ray
-0.03 A
Temperature *0
Figure 5
Temperature dependence of the (200)-fundamental and
(lOO)-superlattice reflections of a nearly stoichiometric
Ni 3Al single crystal indicating an order-disorder transition
at 1330 C
168
Si substrate'
^ TaSi2 film
Figure 6
Experimental setup for determining the radius of
curvature
5001-
-*
Chromatography
30
F . J. B r e m e r a n d H . Bleichert
[ K F A Julich, Julich, G e r m a n y ]
Figure 7
Radius of curvature for different film conditions:
(a) substrate without film; (b) multilayer tantalum 1.1 nm,
silicon 2.4 nm; (c) TaSi 2 after annealing at 900 C
p o s i t i o n (1) t h e r o c k i n g c u r v e of t h e silicon s u b s t r a t e
is m e a s u r e d . T h e n t h e s a m p l e is t r a n s l a t e d b y a n d
the r o c k i n g c u r v e is m e a s u r e d a g a i n a t t h e n e w
p o s i t i o n (2). A n y b e n d i n g o f lattice p l a n e s b e t w e e n
t h e t w o p o s i t i o n s s h o w s u p a s a shift of t h e a n g u l a r
p o s i t i o n o f t h e crystal a t t h e B r a g g p e a k . T h e r a d i u s
of c u r v a t u r e c a n b e c a l c u l a t e d b y r = / , w h e r e
is t h e a n g u l a r shift. If t h e s u b s t r a t e thickness ts is
m u c h smaller t h a n t h e r a d i u s o f c u r v a t u r e r o f t h e
s u b s t r a t e a n d m u c h larger t h a n t h e film thickness t{,
t h e film stress c a n b e c a l c u l a t e d from t h e e q u a t i o n
I
*U
6 1 - tf r
where a n d are Y o u n g ' s modulus a n d Poisson's
r a t i o for t h e s u b s t r a t e ( H o f f m a n n 1966). F r o m F i g . 7
9
we o b t a i n , for e x a m p l e , = 1.68 10 P a , w h i c h
is in g o o d a g r e e m e n t w i t h results o f o t h e r a u t h o r s
(Retajczyk a n d S i n h a 1980). T h e b e n d i n g a n d t h e
residual high stress is d u e t o t h e difference in t h e r m a l
s h r i n k a g e o f s u b s t r a t e a n d film d u r i n g c o o l i n g .
W i t h t h e m e t h o d described, o n e c a n m e a s u r e radii o f
c u r v a t u r e u p t o 500 m , d e p e n d i n g o n t h e s u b s t r a t e
quality.
See also: X-Ray Powder Diffraction
7. Gas
(a)
a s o u r c e of clean c a r r i e r g a s (helium, h y d r o g e n ,
n i t r o g e n o r o t h e r s ) t h a t h a s a precisely regulated
flow r a t e ;
(b)
(c)
Bibliography
Cullity D 1978 Elements of X-ray Diffraction, 2nd edn.
Addison-Wesley, Reading, MA
Darwin C G 1922 The reflexion of x-rays from imperfect
crystals. Philos. Mag. 43: 800-29
Freund A 1973 Untersuchung des Einflusses von Versetzungen auf die Beugung von Rontgen- und Gammastrahlen
an Kupfereinkristallen. Dissertation, Technische Universitat Munchen
Chromatography
T h e g a s c h r o m a t o g r a p h offers a m e t h o d of s e p a r a t i n g
t h e volatile c o m p o n e n t s of a m i x t u r e . T h e p r i m a r y
result is t h e c h r o m a t o g r a m , w h i c h is a p l o t of t h e
intensity of d e t e c t o r r e s p o n s e a g a i n s t time. T h e time
from injecting t h e s a m p l e t o w h e n a s e p a r a t e d c o m
p o n e n t of t h e m i x t u r e a p p e a r s a t t h e d e t e c t o r is called
t h e r e t e n t i o n t i m e . T h i s t i m e is characteristic of a
p a r t i c u l a r c o m p o u n d ( u n d e r fixed i n s t r u m e n t a l c o n
d i t i o n s ) a n d c a n b e used t o infer t h e presence o r
a b s e n c e of a p a r t i c u l a r c o m p o u n d in a m i x t u r e .
R e t e n t i o n times generally increase w i t h increasing
boiling p o i n t of t h e c o m p o n e n t . A typical c h r o m a t o
g r a p h (See F i g . 1) consists o f several p a r t s :
169
Chromatography
Flow control
Detector (s)
Strip-chart
Figure 1
Block diagram of a typical gas chromatograph
c o n t a i n i n g t h e p a c k i n g m a t e r i a l a n d m o u n t e d in
a t e m p e r a t u r e - c o n t r o l l e d c o l u m n oven;
(d)
o n e o r m o r e d e t e c t o r s t o sense t h e a p p e a r a n c e of
t h e s e p a r a t e d c o m p o n e n t s a t t h e outlet of t h e
column; and
(e)
a n electronic i n t e g r a t o r , o r strip-chart r e c o r d e r ,
t o display the c h r o m a t o g r a m as a n i n t e n s i t y time plot.
170
Chromatography
Table 1
Gas-chromatography packing materials
Stationary
phase
Apiezon L
OV-17
Dexsil-300
Carbowax 20M
FFAP
DEGS
OV-275
Carbowax
20M + KOH
Tenax-GC
Molecular Sieve 5A
Porapak Q
Temperature
limit
Composition
Application
hydrocarbon
50% phenyl, methyl silicone
carboranemethylsilicone
polyethylene glycol
carbowax +
nitroterephthalic
diethylene glycol succinate
dicyanoallyl silicone
general nonpolar
general medium polar
high-temperature phase
275
350
450
general-purpose polar
free fatty acids, polar
225
250
fatty-acid esters
highly polar, pesticides
amines
200
250
225
resolution ( u p t o 3000 p l a t e s p e r m e t e r ) c a n be
o b t a i n e d u s i n g capillary c o l u m n s of stainless steel,
glass o r fused silica. C a p i l l a r y c o l u m n s a r e of t w o
general types: (a) w a l l - c o a t e d o p e n t u b u l a r ( W C O T )
c o l u m n s with a n i n t e r n a l d i a m e t e r r a n g e of 0 . 2 0.3 m m with t h e inside wall c o a t e d with a 0 . 1 - 1 . 0
layer of a liquid p h a s e , a n d (b) s u p p o r t - c o a t e d o p e n
t u b u l a r ( S C O T ) c o l u m n s w h e r e a t h i n layer of a solid
s u p p o r t is c o a t e d o n t h e walls of t h e capillary a n d
followed with t h e l i q u i d - p h a s e l o a d i n g . T h e S C O T
c o l u m n s h a v e a higher level of liquid p h a s e a n d
c o n s e q u e n t l y a higher s a m p l e c a p a c i t y (0.011 g)
w h e r e a s t h e W C O T c o l u m n s c a n h a n d l e efficiently
only very small a m o u n t s of s a m p l e ( 1 0 - 1 0 0 ng) a n d
t h u s require t h e use of m o r e sensitive d e t e c t o r s . B o t h
types of c o l u m n r e q u i r e special injection t e c h n i q u e s
o r e q u i p m e n t such a s o n - c o l u m n m i c r o s y r i n g e injec
t o r s o r splitters t h a t divert t h e g r e a t e r p a r t of t h e
injected s a m p l e t o w a s t e . C a p i l l a r y c o l u m n s of fused
silica h a v e f o u n d increasing use b e c a u s e of their
chemical inertness a n d i n h e r e n t r u g g e d n e s s a n d ease
of h a n d l i n g . H o w e v e r , they a r e limited in t h a t they a r e
n o t c u r r e n t l y available w i t h s o m e of t h e m o r e p o l a r
liquid-phase m a t e r i a l s . A typical capillary s e p a r a t i o n
using a fused-silica c o l u m n is s h o w n in Fig. 2. T h i s is
the s a m e m i x t u r e used for t h e e x a m p l e in F i g . 3. N o t e
the increased r e s o l u t i o n possible with capillary
c o l u m n s with n o increase in t h e analysis time.
1.2
Detectors
G a s c h r o m a t o g r a p h y utilizes a wide a r r a y of general
a n d specific d e t e c t o r s . Specific d e t e c t o r s t e n d t o b e
very sensitive a n d their selectivity for p a r t i c u l a r types
of molecules (e.g., t h o s e c o n t a i n i n g h a l o g e n s , sulfur,
CO
375
350
250
n i t r o g e n o r p h o s p h o r u s ) m a k e s t h e m especially useful
in s i t u a t i o n s w h e r e t h e s a m p l e molecules a r e in a
c o m p l e x m i x t u r e of h y d r o c a r b o n s . T h e m o s t c o m m o n
detectors are the thermal-conductivity
detector
( T C D ) a n d t h e flame-ionization d e t e c t o r ( F I D o r
H F I D ) . T h e T C D senses t h e s a m p l e b y c o m p a r i n g t h e
t h e r m a l loss from a h o t filament in t h e effluent from
t h e c o l u m n with t h e loss from a n identical filament in
t h e effluent from a b a l a n c i n g c o l u m n c a r r y i n g only
t h e carrier gas. T h i s d e t e c t o r is a l m o s t universal
(detecting fixed gases a n d i n o r g a n i c s as well as or
g a n i c molecules) b u t h a s only m o d e r a t e sensitivity.
T h e F I D b u r n s t h e s a m p l e in a h y d r o g e n flame
b e t w e e n t w o electrodes, o n e of w h i c h is t h e flame
s u p p o r t . A high p o t e n t i a l difference is a p p l i e d t o t h e
electrodes a n d t h e sensor electronics detect c u r r e n t
flow w h e n t h e b u r n i n g of c a r b o n - c o n t a i n i n g species
increases t h e c o n d u c t i v i t y of t h e flame. T h i s d e t e c t o r
is a n excellent choice for o r g a n i c c o m p o u n d s , for
w h i c h it h a s high sensitivity. T h e F I D h a s n o r e s p o n s e
t o fixed gases a n d is useful for c a r b o n m o n o x i d e only
w h e n t h a t g a s is catalytically c o n v e r t e d t o m e t h a n e in
a m e t h a n i z e r . T h e e l e c t r o n - c a p t u r e d e t e c t o r (used for
t h e e x a m p l e s in Figs. 2 a n d 3) is p a r t i c u l a r l y sensitive
t o h a l o g e n a t e d o r g a n i c s a n d h a s f o u n d extensive use
in pesticide analysis.
Less c o m m o n l y u s e d d e t e c t o r s include t h e flame
p h o t o m e t r i c d e t e c t o r ( F P D ) , t h e H a l l electrolyticc o n d u c t i v i t y d e t e c t o r ( H E C D ) , infrared d e t e c t o r s a n d
t h e m a s s s p e c t r o m e t e r . I n t h e F P D , t h e s a m p l e is
b u r n e d in a h y d r o g e n flame a n d emission from excited
sulfur o r p h o s p h o r u s species is detected b y a p h o t o
multiplier after being a p p r o p r i a t e l y filtered. T h i s is
a very specific d e t e c t o r with a r e s p o n s e r a t i o for
6
c a r b o n : sulfur o r c a r b o n : p h o s p h o r u s of a b o u t 10 .
171
Chromatography
10
15
20
25
30
35
40
45
Time
(min)
L
50
Figure 3
Packed column gas chromatogram of a polychlorinated
biphenyl mixture. Column: 2.0 m 4 mm internal
diameter glass packed with 1.5% OV-17 and 1.95% QF-1
on 60/80 mesh Gas-Chrom
Q. Temperature program:
1
150-250 C at 2 C m i n . Detector: electron capture.
1
Carrier gas: 5% methane in argon ,at 60 ml m i n .
Sample: Aroclor 1260 at 1 0 g m , 1 injection
Figure 2
Capillary gas chromatogram of a polychlorinated biphenyl
mixture. Column: 30 m fused silica with bonded liquid1
phase. Temperature program:
40-80 C at 10 C m i n ,
1
80-225 C at 1 " C m i n . Detection: electron capture.
Carrier gas: helium (make-up, with nitrogen).
Sample: Aroclor at 1 g m , splitless injection
m a s s s p e c t r u m of e a c h c o m p o n e n t as it elutes from
t h e G C c o l u m n . T h e m a s s s p e c t r u m is a p l o t of the
m a s s : c h a r g e r a t i o (usually t h e c h a r g e is unity) for t h e
s a m p l e m o l e c u l a r ion a n d t h e characteristic fragments
it p r o d u c e s in t h e ion source. T h e i n f o r m a t i o n is
s t o r e d in c o m p u t e r files for s u b s e q u e n t analysis a n d
g r a p h i c display. T h e m a s s s p e c t r u m defines t h e m o l e
c u l a r weight a n d p r o b a b l e f o r m u l a s of the u n k n o w n
p e a k s o r enables c o m p a r i s o n with t h e m a s s spectra of
k n o w n s t a n d a r d s s t o r e d in c o m p u t e r files. T h e G C /
M S h a s f o u n d extensive use in t h e analysis of e n v i r o n
m e n t a l s a m p l e s w h e r e its sensitivity a n d specificity a r e
a great a d v a n t a g e .
T h e H E C D c a n be configured so as t o b e h a l o g e n ,
n i t r o g e n o r sulfur specific. I n this detector, the col
u m n effluent is mixed with oxygen (for sulfur) o r
h y d r o g e n (for h a l o g e n s a n d n i t r o g e n ) a n d passed
t h r o u g h a r e a c t o r t u b e a t 7 0 0 - 9 0 0 C. After p a s s i n g
t h r o u g h s c r u b b e r s t o r e m o v e interfering c o m p o u n d s ,
the p r o d u c t s a r e detected as they c h a n g e the c o n d u c t i
vity of a circulating electrolyte. T h e c a r b o n : (halogen,
6
n i t r o g e n , sulfur) r a t i o s a r e also a r o u n d 10 . T h i s
quality is particularly useful w h e n a n a l y z i n g for
heteroatom-containing
compounds
in
complex
hydrocarbon mixtures.
Infrared d e t e c t o r s c a n be either simple single-beam
single-wavelength i n s t r u m e n t s set t o m o n i t o r a p a r
ticular functional g r o u p as t h e c o l u m n effluent passes
t h r o u g h a h e a t e d cell, o r sophisticated F o u r i e r t r a n s f o r m i n s t r u m e n t s t h a t c a n r e c o r d the entire
infrared s p e c t r u m as a p e a k elutes.
T h e m a s s s p e c t r o m e t e r is a very specific a n d sensi
tive detector. It is usually configured as a s t a n d - a l o n e
i n s t r u m e n t ( G C / M S ) a n d o p e r a t e s b y analyzing t h e
1.3 Sample
Introduction
T h e m o s t c o m m o n type of injector, t h e h e a t e d injec
tion p o r t , allows for the injection of s a m p l e solutions
via a syringe t h r o u g h a r u b b e r s e p t u m . R a p i d v a p o r i
z a t i o n of t h e solvent a n d s a m p l e at t e m p e r a t u r e s u p t o
300 C p r o v i d e for efficient t r a n s p o r t t o t h e s e p a r a t i n g
c o l u m n . T h i s p r o c e d u r e c a n be a u t o m a t e d a n d a u t o s a m p l e r s a r e available t h a t a r e c a p a b l e of h a n d l i n g as
m a n y as 100 s a m p l e s a n d injecting t h e m with g r e a t e r
precision t h a n is possible with m a n u a l injection. T h e
c o u p l i n g of a u t o s a m p l e r s with m i c r o p r o c e s s o r i n s t r u m e n t c o n t r o l s a n d data-collection devices p r o
vides for essentially c o m p l e t e a u t o m a t i o n of the G C
analysis. O t h e r types of specialized devices include
h e a d s p a c e s a m p l e r s t o analyze t h e v a p o r c o n t e n t s in
c o n t a i n e r s , p u r g e - a n d - t r a p s a m p l e r s w h i c h collect
a n d c o n c e n t r a t e o r g a n i c volatiles from w a t e r for
p o l l u t a n t analysis, a n d pyrolytic devices t h a t flashpyrolyze solid s a m p l e s from a p l a t i n u m coil o r r i b
b o n . T h i s latter device allows analysis of n o n v o l a t i l e
m a t e r i a l s such as p o l y m e r s a n d geological m a t e r i a l s
by the s t u d y of their t h e r m a l - f r a g m e n t a t i o n p r o d u c t s .
30
35
Time
172
40
45
(min)
Figure 4
Block diagram of a typical liquid chromatograph
2. Liquid
Chromatography
L i q u i d c h r o m a t o g r a p h y is a p p l i c a b l e t o m o s t types
of s a m p l e t h a t c a n b e s e p a r a t e d b y G C b u t , in
a d d i t i o n , h a s special a d v a n t a g e s in t h e h a n d l i n g of
n o n v o l a t i l e , t h e r m a l l y labile o r ionic m a t e r i a l s . A
block d i a g r a m of a typical liquid c h r o m a t o g r a p h is
s h o w n in F i g . 4. T h e single p u m p is fed b y a m i c r o
p r o c e s s o r - c o n t r o l l e d m i x i n g valve t o p r o d u c e solvent
m i x t u r e s o r c o n t i n u o u s l y v a r y i n g solvent c o m p o s i
tions (e.g., c h a n g i n g f r o m 5 0 % m e t h a n o l in w a t e r t o
1 0 0 % m e t h a n o l over a 3 0 m i n p e r i o d ) . O n s o m e
i n s t r u m e n t s , t w o o r m o r e p u m p s e a c h with its o w n
solvent supply m a y b e c o n t r o l l e d t o p r o d u c e solvent
g r a d i e n t s . Solvent p r o g r a m m i n g h a s similar effects in
L C t o t e m p e r a t u r e p r o g r a m m i n g in G C in t h a t it
s h o r t e n s analysis time a n d increases d e t e c t i o n limits
by s h a r p e n i n g p e a k s . T h e p u m p s a r e c o m m o n l y pis
t o n p u m p s a n d a r e c a p a b l e of p r o d u c i n g a c o n s t a n t
1
flow r a t e of 0 . 1 - 1 0 m l m i n ~ a t b a c k pressures of u p t o
400 a t m . Because of t h e p r e s s u r e s e n c o u n t e r e d , t h e
m a n u a l injectors a n d a u t o s a m p l e r s a r e b a s e d o n highpressure valve systems t h a t isolate t h e s a m p l e from
the system p r e s s u r e until t h e m o m e n t of injection.
2.1
Detectors
T h e d e t e c t o r s used for L C a r e very d e p e n d e n t o n t h e
characteristics of t h e s a m p l e t o b e a n a l y z e d . T w o of
the m o s t c o m m o n a r e t h e u l t r a v i o l e t - a b s o r b a n c e d e
tector a n d t h e differential-refractive-index d e t e c t o r
( D R I ) . T h e u v d e t e c t o r is usually a m i n i a t u r e d o u b l e -
Chromatography
Columns
173
Chromatography
In L S C , s a m p l e p o l a r i t y is of m a j o r i m p o r t a n c e in
d e t e r m i n i n g t h e o r d e r of elution. S a m p l e elution t a k e s
place m o r e rapidly as the p o l a r i t y of the m o b i l e p h a s e
is increased. L S C is related t o thin-layer c h r o m a t o g r a
p h y ( T L C ) in which the a d s o r b a n t is c o a t e d as a thin
layer o n a rigid s u b s t r a t e such as glass, a l u m i n u m o r
polyester.
I E C t a k e s place o n c o l u m n s p a c k e d with resin
particles t h a t h a v e ionic functional g r o u p s such as
q u a t e r n a r y a m m o n i u m salts o r sulfonic-acid g r o u p s
a t t a c h e d . T h e m o b i l e p h a s e c a n be acids, bases o r
buffer solutions. T h e s e p a r a t i o n m e c h a n i s m involves
v a r i a t i o n s in affinity of m o b i l e i o n s in solution t o the
b o u n d ions o n the s t a t i o n a r y p h a s e . I E C h a s been
extensively used in a m i n o - a c i d analysis a n d for the
s e p a r a t i o n of m e t a l i o n s , sugars a n d m a n y biological
molecules.
A v a r i a n t of I E C is ion c h r o m a t o g r a p h y (IC) in
which a n i o n - e x c h a n g e s e p a r a t i o n of a n i o n s o r
c a t i o n s is carried o u t o n a low-capacity i o n - e x c h a n g e
s e p a r a t i n g c o l u m n , followed b y a s u p p r e s s o r c o l u m n
t h a t neutralizes t h e acidic (for cations) o r basic (for
a n i o n s ) m o b i l e p h a s e . T h i s allows t h e s a m p l e i o n s of
interest to be detected by a c o n d u c t i v i t y d e t e c t o r
against a b a c k g r o u n d of deionized w a t e r . D e t e c t i o n
levels in t h e p p b r a n g e h a v e been d e m o n s t r a t e d for
chloride, fluoride a n d sulfate as well as for alkali a n d
alkaline-earth c a t i o n s . T h i s t e c h n i q u e is of p a r t i c u l a r
i m p o r t a n c e for a n i o n analysis since classical m e t h o d s
for these t e n d t o be t e d i o u s a n d limited in sensitivity.
In a d d i t i o n , I C c a n distinguish b e t w e e n different
o x i d a t i o n states of s o m e a n i o n s such as sulfate-sulfite
a n d n i t r a t e - n i t r i t e . C a t i o n analysis by ion c h r o m a t o
g r a p h y is n o t as frequently used as it c o m p e t e s with
a t o m i c a b s o r p t i o n ( A A ) which is a relatively sensitive
technique.
G P C c a n be carried o u t o n the s a m e i n s t r u m e n t s
as o t h e r L C techniques b u t differs from t h e m in
t h a t the s t a t i o n a r y p h a s e consists of a c o n t r o l l e d p o r o s i t y p o l y m e r n e t w o r k , a solvent-swelled gel o r a
c o n t r o l l e d - p o r o s i t y glass. T h e solvent carries t h e s a m
ple molecules a l o n g a n d they d i s t r i b u t e a c c o r d i n g t o
their size between t h e s t a t i o n a r y p h a s e a n d t h e m o b i l e
p h a s e . L a r g e r molecules such as h i g h - m o l e c u l a r weight p o l y m e r s t e n d n o t to p e n e t r a t e the p o r e s o r gel
a n d elute first. P r o p o r t i o n a t e l y smaller molecules
elute later. T h e c o l u m n s c a n be c a l i b r a t e d in t e r m s of
a certain r e t e n t i o n v o l u m e (retention time flow rate)
by using k n o w n - m o l e c u l a r - w e i g h t s t a n d a r d s . S t a n
d a r d i z a t i o n s by this m e t h o d give m o l e c u l a r weights
referenced t o t h e s t a n d a r d i z i n g p o l y m e r (usually
n a r r o w - d i s t r i b u t i o n polystyrene). O t h e r structurally
different p o l y m e r s m a y deviate significantly in reten
tion v o l u m e from polystyrenes of equivalent m o l e c u
lar weights. F i g u r e 5 s h o w s a c o m p o s i t e of t w o G P C
traces. T h e trace in the b a c k g r o u n d is from a n ex
p e r i m e n t a l p o l y m e r a n d s h o w s a fairly b r o a d
molecular-weight d i s t r i b u t i o n as well as the presence
of residual m o n o m e r a n d s o m e oligomeric m a t e r i a l .
174
10.93
15.41
19.89
Retention t i m e ( m i n )
Figure 5
Gel-permeation (size-exclusion) chromatogram. The upper
trace is from an experimental polymer, the lower
(superimposed) trace is from an analysis of a mixture of
narrow-molecular-weight-distribution polystyrene
standards (the molecular weights are labelled). The
chromatograph utilized four micro-Styragel columns.1
The solvent was chloroform at a rate of 2.0 ml m i n ,
uv detection was at 254 nm
T h e s u p e r i m p o s e d trace is of a m i x t u r e of p o l y s t y r e n e
s t a n d a r d s labelled with their m o l e c u l a r weights. M o s t
of t h e d e t e c t o r s useful for L C a r e also applicable t o
G P C . T h e low-angle laser-light-scattering ( L A L L S )
d e t e c t o r is specific to G P C . T h i s d e t e c t o r m e a s u r e s
the i n s t a n t a n e o u s weight-average m o l e c u l a r weight of
t h e c o l u m n eluent a n d calculates the d i s t r i b u t i o n
b a s e d o n a c o m b i n a t i o n of the L A L L S a n d a m a s s sensitive d e t e c t o r such as D R I . T h e use of this detec
t o r eliminates t h e need for c a l i b r a t i o n s for e a c h
specific p o l y m e r analyzed.
See also: Liquid Chromatography Mass Spectroscopy
Bibliography
Cazes J (ed.) 1977, 1980, 1981 Liquid Chromatography of
Polymers and Related Materials, Vols. 1-3. Dekker, New
York
Grob R L (ed.) 1977 Modern Practice of Gas Chromatog
raphy. Wiley, New York
Hagnauer G L 1982 Size exclusion chromatography. Anal.
Chem. 53: 265R-76R
Risby , Field L R, Yang F Y, Cram S 1982 Gas
chromatography. Anal. Chem. 53: 410R-28R
Simpson C F (ed.) 1976 Practical High Performance Liquid
Chromatography. Hey den, London
Gas Sensors,
Solid-State
EMF
h2h
C. C a r n a h a n J r
[ G e n e r a l Electric C o r p o r a t e R e s e a r c h
and Development, Schenectady,
New York, USA]
/.
Solid Electrolyte
Sensors
Inner electrode
Figure 1
Gas sensor to monitor oxygen content of exhaust gases
from car engines
t h e c a t i o n lattice t o d i s o r d e r ( R b A g J j ) , o r because
there a r e p l a n e s o r t u n n e l s in t h e m a t e r i a l t h r o u g h
w h i c h ionic species m a y m o v e ( N a 2 0 . 1 1 A l 2 0 3 o r
N a 1 + xZ r 2 S i j rP 3 _ J f0 1 2) . O t h e r solid electrolytes a r e
b a s e d u p o n p o l y m e r i c m a t e r i a l s (polyethylene oxide
a n d perfluorosulfonic acid). I n t h e p o t e n t i o m e t r i c
m o d e these sensors a r e b a s e d u p o n t h e very simple
thermodynamic concept that a concentration gradient
of a species a c r o s s a n ionic c o n d u c t o r results in a
p o t e n t i a l w h i c h c a n be detected b y a high i m p e d a n c e
v o l t m e t e r . A n oxygen sensor c a n be r e p r e s e n t e d b y
2
Pt, 0 2 | 0 ~ c o n d u c t o r IO2, P t
2
- ZEF=
P'
RT I n
(1)
p"
175
Gas Sensors,
Solid-State
2. Oxygen
Sensors
2;=2 + 0 2 ,
K=
P<
2
(2)
Sensors
T h e q u a n t i t a t i v e d e t e c t i o n of h y d r o g e n is of consider
able i m p o r t a n c e in a variety of industrial s i t u a t i o n s ,
176
electrolyte
Hole
Anode
Figure 2
Limiting-current-type oxygen sensor
such as t h e synthesis of a m m o n i a , m e t h a n o l a n d o t h e r
chemicals, p e t r o l e u m refining, s e m i c o n d u c t o r m a n u
facture, chemical r e d u c t i o n a n d c o r r o s i o n c o n t r o l .
U n f o r t u n a t e l y , there a r e n o satisfactory hight e m p e r a t u r e p r o t o n c o n d u c t o r s a n d the m a i n a p
p r o a c h h a s been t o use m a t e r i a l s such as N a f i o n
(perfluorosulfonic acid) a n d H U P ( h y d r o g e n u r a n y l
phosphate) which become proton conductors when
h y d r a t e d . T h e reference m a t e r i a l used h a s been either
h y d r o g e n gas, a m i x t u r e of h y d r i d e s o r a r e d o x
m i x t u r e . T h e s e sensors h a v e been used t o m e a s u r e
h y d r o g e n in gases a n d h y d r o g e n in solid steel gener
ated by corrosion reactions.
x 2
3. Hydrogen
Cathode
Gases
2 +
conductor) | H 2 , H 2S
=~^2
(3)
M o r e recently, in o r d e r t o c o m b a t t h e p o o r ionic
c o n d u c t i v i t y of calcium sulfide, m i x e d electrolytes of
calcium sulfide a n d stabilized zirconia h a v e been used
in w h i c h t h e r e a c t i o n o f t h e w o r k i n g electrode is
CaS + i O ^ C a O ( Z r 0 2) + i S 2 ,
K=
a
a
C Qa
P
^
CaS^0
l/2
(4)
Gas Sensors,
+ 0
+ 2e"
(5)
a n d the p o t e n t i a l c a n be expressed by
=^ l n ^ +^ l n ^
ZF
P0i
ZF
(6)
Pso;
6. Humidity
5. Gas Sensors
Electrical
Dependent
upon Changes
in
Conductivity
T h e s e sensors d e p e n d u p o n t h e electronic c o n d u c
tivity of certain s e m i c o n d u c t i n g oxides, such as T i 0 2 ,
N b 2 0 5 a n d C e 0 2 , c h a n g i n g with t h e o x y g e n p a r t i a l
pressure. In t h e case of T i 0 2 , t h e intrinsic electrical
c o n d u c t i v i t y is m a i n l y d u e t o o x y g e n lattice defects
a n d c a n be r e p r e s e n t e d b y t h e following e q u a t i o n :
x
O0
i 0
+ F
- 2 e "
(7)
w h e r e O* is a n o x y g e n ion o n a n a n i o n i c site of t h e
crystal, V0 is a positive v a c a n c y in t h e a n i o n sublattice
a n d e " r e p r e s e n t s a n electron d o n a t e d t o t h e c o n d u c
tion b a n d . F r o m E q n . (7), it c a n be seen t h a t d e c r e a s
ing t h e oxygen p a r t i a l p r e s s u r e leads t o a n increase in
vacancies a n d electrons. U s i n g the e l e c t r o n e u t r a l i t y
relationship and assuming thermodynamic equi
librium, t h e following e q u a t i o n c a n be o b t a i n e d :
n = Pol
/6
expi-E/kT)
(8)
w h e r e is t h e n u m b e r of free electrons g e n e r a t e d
a c c o r d i n g t o E q n . (7), is t h e energy of f o r m a t i o n of
a n oxygen v a c a n c y a n d k is t h e B o l t z m a n n c o n s t a n t .
1/4
I n fact, e x p e r i m e n t a l results s h o w a PQ2
relationship
with the c o n d u c t i v i t y o w i n g t o t h e presence of i m p u r i
ties in t h e crystal w h i c h c a u s e a relatively high c o n c e n
t r a t i o n of o x y g e n vacancies. A s a c o n s e q u e n c e , t h e
v a c a n c y c o n c e n t r a t i o n is virtually i n d e p e n d e n t of t h e
oxygen p a r t i a l p r e s s u r e a n d t h e d e p e n d e n c e of t h e
electrical c o n d u c t i v i t y is p r o p o r t i o n a l t o P\.
A c c o r d i n g t o E q n . (8), it c a n be e s t i m a t e d t h a t a
T i 0 2 resistor will exhibit a c h a n g e in c o n d u c t i v i t y of
four o r d e r s of m a g n i t u d e as t h e air-to-fuel r a t i o in a n
internal c o m b u s t i o n engine passes from being r e d u c
ing t o oxidizing. S u p e r i m p o s e d u p o n this c o n d u c t i v i t y
c h a n g e , there is also a c o n d u c t i v i t y c h a n g e d u e t o t h e
v a r i a t i o n in t e m p e r a t u r e , w h i c h c a n b e o v e r c o m e
either b y m a i n t a i n i n g t h e resistor a t a c o n s t a n t t e m
p e r a t u r e b y m e a n s of a h e a t e r o r b y interfacing a very
p o r o u s T i 0 2 pellet with a d e n s e T i 0 2 pellet. T h e
resistivity of b o t h pellets c h a n g e s with t e m p e r a t u r e
b u t only t h e resistance of t h e p o r o u s pellet c h a n g e s
with oxygen p r e s s u r e d u e t o t h e m u c h larger surface
Solid-State
Sensors
7. Gas-Sensitive
Resistors
8. Surface
Acoustic
Wave
Sensors
177
Gas Sensors,
Solid-State
Platinum wire
Support
Catalyst
Figure 3
Catalytic gas sensor bead
by a b s o r b e d
can absorb
detected b y
larly, a lead
detect nitric
9. Catalytic
Gas
Detectors
I n f l a m m a b l e gases c a n b e m o n i t o r e d by catalytic g a s
d e t e c t o r s which a r e m a d e from a p l a t i n u m coil u p o n
w h i c h is d e p o s i t e d a p o r o u s oxide m a t e r i a l , such as
a l u m i n a o r t h o r i a . A catalytic gas sensor b e a d is
s h o w n in F i g . 3. T h e a c t u a l d e t e c t o r consists of t w o
s u c h b e a d s , o n e of w h i c h is a c t i v a t e d w i t h catalyst
while t h e o t h e r h a s n o catalytic activity. I n t h e p r e s
ence of i n f l a m m a b l e gases a n d a t a t e m p e r a t u r e of
a p p r o x i m a t e l y 600 C, t h e catalytic b e a d causes t h e
inflammable gases t o react with t h e oxygen in air a n d
this raises t h e t e m p e r a t u r e a n d , t h u s , t h e resistance of
t h e p l a t i n u m coil. T h e inert b e a d , h a v i n g n o catalytic
activity, d o e s n o t increase in t e m p e r a t u r e a n d , t h e r e
fore, t h e coil resistance of this b e a d r e m a i n s c o n s t a n t .
T h e difference b e t w e e n t h e resistances of t h e t w o
b e a d s is related t o t h e c o n c e n t r a t i o n of t h e inflam
m a b l e gases present.
10. Semiconductor
Junction
Devices
178
Initial a t t e m p t s t o d e v e l o p a hydrogen-sensitive
p a l l a d i u m - s i l i c o n S c h o t t k y d i o d e failed b e c a u s e of
t h e f o r m a t i o n of a n i n t e r m e d i a t e silicide layer of
P d 2 S i . T h i s p r o b l e m w a s solved b y deliberately g r o w
ing a very t h i n layer of silica p r i o r t o t h e d e p o s i t i o n of
the p a l l a d i u m . T h i s very thin layer d o e s n o t affect
either t h e d i o d e characteristics of t h e s t r u c t u r e o r t h e
h y d r o g e n sensitivity. It is likely t h a t as well as the
f o r m a t i o n of a d i p o l e layer a t t h e p a l l a d i u m - s i l i c a
interface, t h e m o d u l a t i o n of t h e surface states a t t h e
silicon-silica interface a n d t h e c o r r e s p o n d i n g t u n n e l
ling of electrons b e t w e e n these surface states a n d t h e
p a l l a d i u m m a y also p l a y a n i m p o r t a n t role.
H y d r o g e n a t o m s diffuse t h r o u g h the thin p a l l a d i u m
layer a n d a r e a d s o r b e d a t t h e m e t a l - i n s u l a t o r inter
face. T h e h y d r o g e n a t o m s a r e p o l a r i z e d a n d give rise
t o a d i p o l e layer resulting in a voltage d r o p w h i c h is
a d d e d t o t h e externally a p p l i e d voltage. T h i s voltage
d r o p is d e p e n d e n t u p o n t h e c o n c e n t r a t i o n a n d it
s h o u l d b e n o t e d t h a t this c o n c e n t r a t i o n is n o t only a
function of t h e h y d r o g e n p r e s s u r e , b u t c a n also b e
influenced b y t h e presence of oxidizing gases w h i c h
can remove absorbed hydrogen. F o r n o n p o r o u s pal
l a d i u m films, t h e devices only r e s p o n d t o gases which
c a n dissociate i n t o h y d r o g e n .
L a n g m u i r - B l o d g e t t films, w h i c h a r e h o m o g e n e o u s
o r g a n i c films, o n e m o l e c u l e thick, c a n be used as a n
insulating layer b e t w e e n t h e g a t e a n d t h e c h a n n e l of a
silicon M O S F E T o r b e t w e e n t h e electrodes of a M O S
d i o d e . R e d o x o r c o m p l e x a t i o n r e a c t i o n s with t h e
active molecules of t h e L a n g m u i r - B l o d g e t t film
result in a shift of t h e flat b a n d v o l t a g e a n d a c h a n g e
in t h e low-frequency dielectric losses of t h e device.
It h a s b e e n f o u n d t h a t M O S s t r u c t u r e s c o n t a i n i n g a
L a n g m u i r - B l o d g e t t film of p h t h a l o c y a n i n e r e s p o n d
quickly t o a few p a r t s p e r million of N O x a t r o o m
temperature.
11.
Conclusions
F r o m a n i n d u s t r i a l viewpoint, there is a c o n s i d e r a b l e
Source
Q
Gate
9
Drain
Q
Metal
Oxide ( S i 0 2)
Channel
p- silicon
Figure 4
Metal-oxide-semiconductor field-effect transistor
(MOSFET)
Grain Size:
need for c o n t r o l in o r d e r t o m a i n t a i n a p e r m a n e n t
analysis of t h e p h y s i c o c h e m i c a l p a r a m e t e r s of m a n y
processes with t h e a i m of achieving q u a l i t y a n d r e p r o
ducibility. F u r t h e r m o r e , with t h e ever-increasing
pressure t o m i n i m i z e a t m o s p h e r i c p o l l u t i o n , t h e
m o n i t o r i n g of effluents is b e c o m i n g of p a r a m o u n t
i m p o r t a n c e . T h e increase in c o n s u m e r g o o d s , such as
cars a n d air c o n d i t i o n e r s , is responsible n o t only for
direct p o l l u t i o n of t h e e n v i r o n m e n t b u t also for
indirect p o l l u t i o n b y c o n s u m i n g electricity p r o d u c e d
by the c o m b u s t i o n of fossil fuels. A n y i m p r o v e m e n t s
in efficiency m a d e possible b y c o n t r o l will p a y divi
d e n d s b o t h in t e r m s of i m p r o v e d p r o d u c t i o n values
a n d decreased a t m o s p h e r i c p o l l u t i o n .
I n this article it h a s been d e m o n s t r a t e d t h a t there is
a wide variety of sensors b a s e d o n different physical
a n d chemical effects. T h e i n t e g r a t i o n of chemical
sensors, such as h u m i d i t y sensors, is m u c h m o r e
difficult t h a n with physical sensors b e c a u s e chemical
sensors m u s t be directly e x p o s e d t o t h e v a r i o u s en
v i r o n m e n t s a n d , therefore, they c a n n o t be totally
sealed.
A n o t h e r p r o b l e m for t h e i n t e g r a t i o n of chemical
sensors is t h e i n c o m p a t i b i l i t y of t h e m a t e r i a l s of t h e
sensing element a n d t h e i n t e g r a t e d circuits. H o w e v e r ,
c o n s i d e r a b l e effort is being p u t i n t o d e v e l o p i n g thin
film devices u s i n g s p u t t e r i n g , v a p o r d e p o s i t i o n a n d
silicon t e c h n o l o g y with a view t o i m p r o v i n g sensor
characteristics a n d lowering t h e overall cost.
Finally, it c a n be confidently s t a t e d t h a t t h e d e
m a n d for gas sensors will g r o w a n d t h a t research will
d e v e l o p n e w sensors a n d m a k e existing sensors m o r e
reliable.
See also: Gas and Liquid Chromatography
Nondestructive
Evaluation
1. Principle
of Ultrasonic
Techniques
In polycrystalline m a t e r i a l , t h e p r o p a g a t i o n of ultra
sonic waves is affected b y discontinuities in the c h a r
acteristic acoustic i m p e d a n c e pc (p is the density a n d c
is t h e p h a s e velocity) a t t h e g r a i n b o u n d a r i e s d u e t o
the c r y s t a l l o g r a p h i c a n i s o t r o p y of c. A t each grain
b o u n d a r y , the w a v e is p a r t l y reflected a n d p a r t l y
m o d e c o n v e r t e d b e t w e e n l o n g i t u d i n a l (L) a n d t r a n s
verse (T) waves. T h e c o n t r i b u t i o n t o a t t e n u a t i o n d u e
to g r a i n - b o u n d a r y scattering is t h e s u m of these
scattering e n c o u n t e r s over t h e m a n y grains traversed
d u r i n g p r o p a g a t i o n . T h i s subject h a s been reviewed
b y P a p a d a k i s (1968) a n d by G o e b b e l s (1980).
T h e u l t r a s o n i c a t t e n u a t i o n is t h e a m p l i t u d e decre
a
m e n t coefficient in waves of t h e form e~ *, w h e r e is
t h e space c o o r d i n a t e . T h e L a n d c o n t r i b u t i o n s to
s
a t t e n u a t i o n d u e t o grain scattering (a L a n d ca\) h a v e
b e e n calculated for t h e case w h e n a n i s o t r o p y is small,
m u l t i p l e scattering c a n b e i g n o r e d , grains are
e q u i a x e d a n d of single p h a s e , a n d texture c a n be
i g n o r e d . F o r Rayleigh scattering of b u l k waves in
cubic crystals, t h a t is, w h e n t h e w a v e l e n g t h
2
w h e r e D is t h e a v e r a g e grain d i a m e t e r ,
Bibliography
Aucouturier J-L, Cauhape J-S, Destriau M, Hagenmuller P,
Lucat C, Menil F, Portier J, Salardenne J (eds.) 1986
Proc. 2nd Int. Meeting Chemical Sensors, Bordeaux,
France
Edmonds (ed.) 1988 Chemical Sensors. Blackie, Glas
gow, UK
Fisher G 1986 Ceramic sensors: providing control through
chemical reactions. Ceram. Bull. 65: 622-9
Goto S 1988 Solid State Electrochemistry and its Applica
tions to Sensors and Electronic Devices. Elsevier, Amster
dam
Moseley , Tofield C (eds.) 1987 Solid State Gas
Sensors. Hilger, Bristol, UK
Williams D E, McGeehin 1984 Solid state sensors and
monitors. In: Pletcher D (ed.) 1984 Electrochemistry,
Vol. 9. The Royal Society of Chemistry, London,
pp. 246-90
D . J. F r a y
[University of C a m b r i d g e ,
Cambridge, UK]
, 2>
< / O =
Jo
0 /0
R"N(R)
dRI
Jo
N(R)
dR
179
Grain Size:
Nondestructive
Evaluation
&2
a n d t h e s h o r t w a v e l e n g t h (diffuse) region
w h e r e < 2nD a r e also k n o w n .
P a p a d a k i s ' s analysis indicates t h a t E q n s . (1) a n d (2)
a r e qualitatively c o r r e c t in s o far a s t h e a t t e n u a t i o n
4
follows a Vf l a w a n d t h a t they yield q u a n t i t a t i v e l y
a c c u r a t e results for t h e r a t i o [/. H o w e v e r , q u a n t i
s
tative a g r e e m e n t b e t w e e n a c t u a l values o f a L o r
predicted b y E q n s . (1) a n d (2) a n d e x p e r i m e n t a l
results is a t best w i t h i n a factor of 2. O w i n g t o this
lack of q u a n t i t a t i v e a g r e e m e n t , generalized e q u a t i o n s
34
s
3
s
((x L = kLd f
a n d oc j = k T d f \ w h e r e k L a n d kT a r e
empirically d e t e r m i n e d grain s c a t t e r i n g coefficients)
a r e used t o a n a l y z e e x p e r i m e n t a l results. I n m o s t
studies t h e statistical n a t u r e of t h e g r a i n size is s u p
pressed with V o r D simply being r e p l a c e d b y t h e c u b e
o r value, respectively, o f a n y o n e o f t h e m e t a l l o graphically d e t e r m i n e d a v e r a g e g r a i n d i a m e t e r s d.
Goebbels determined that measurements of grain
size s h o u l d b e m a d e in t h e region 0 . 0 3 < d j k < 0 . 3 .
F r e q u e n c i e s b e l o w 20 M H z h a v e been used o n m a t e r
ials with grain d i a m e t e r s o v e r 10 . A c c u r a c i e s o f n o
better t h a n 1 5 % , c o r r e s p o n d i n g t o 2 A S T M g r a i n
sizes, a r e claimed. M e a s u r e m e n t e r r o r arises from
factors such a s diffraction effects, s a m p l e g e o m e t r y ,
the presence of large isolated scatterers (inclusions),
the effects of t h e a c t u a l g r a i n size d i s t r i b u t i o n a n d ,
especially, t h e presence o f t h e small n u m b e r of rela
tively large g r a i n s .
F o r either L o r w a v e s , e x p e r i m e n t a l m e a s u r e
s
m e n t s d e t e r m i n e t h e t o t a l a t t e n u a t i o n a , o f w h i c h a is
only a p a r t . T h e r e m a i n d e r , referred t o a s t h e a b s o r p
a
tion a , is a t t r i b u t e d t o t h e excitation o f lattice defects
a n d t o t h e r m a l a n d m a g n e t i c d i s s i p a t i o n effects
a m o n g o t h e r m e c h a n i s m s . A b s o r p t i o n is m o d e l l e d b y
8
= / , w h e r e usually n= 1, 2 a n d t h e an a r e
phenomenological constants.
T h e r e a r e a t least t h r e e distinct t e c h n i q u e s for
d e t e r m i n i n g g r a i n size from m e a s u r e m e n t s o f t o t a l
attenuation,
a R = oc (f)
+ oc (d, / ) , in t h e
Rayleigh
region.
2. Single-Frequency
Ultrasonic
Technique
T h e a t t e n u a t i o n a R is d e t e r m i n e d a t a single frequency
for s a m p l e s identical except for g r a i n size. A leasts q u a r e s analysis o f t h e results of m e a s u r e m e n t s o n
s a m p l e s with k n o w n g r a i n size allows t h e d e t e r m i
a
n a t i o n of a a n d kL o r kT. W i t h these q u a n t i t i e s k n o w n
d c a n b e d e d u c e d from m e a s u r e m e n t s of a R in similar
a
samples. N o a s s u m p t i o n o n t h e f o r m of a is r e q u i r e d ,
a
b u t t h e t e c h n i q u e is sensitive t o differences in a
a m o n g the samples.
3.
Two-Frequency
Ultrasonic
Technique
T h e a t t e n u a t i o n a R is m e a s u r e d a t t w o frequencies,
a R 1 a t / j n e a r t h e l o n g a n d a R 2 a t f2 n e a r t h e s h o r t
180
w a v e l e n g t h p o r t i o n s of t h e R a y l e i g h region, a n d t h e
results a r e a n a l y z e d a c c o r d i n g t o E q n s . (1) a n d (2).
a
M o s t c o m m o n l y t h e a s s u m p t i o n a = axf is m a d e
3
4
leading t o k L Td = [ a R1 - a R 2/ 2 / / ; ] / [ / - / / ] ] , w h e r e
kLT r e p r e s e n t s either kL o r kT. R e g r e s s i o n analysis o f
m e a s u r e m e n t s from s a m p l e s o f k n o w n g r a i n size is
used t o d e t e r m i n e kLT a n d thereafter d for similar
s a m p l e s . T h i s t e c h n i q u e requires careful a t t e n t i o n t o
diffraction effects a n d , o w i n g t o t h e high o r d e r s in / ,
a c c u r a t e frequency d e t e r m i n a t i o n s . I t is also sensitive
4
t o d e v i a t i o n from t h e ( f \ f ) empirical m o d e l .
4. Backscatter
Ultrasonic
Technique
= b + i l n [ a ] - ( a + oc )X
A n a l y s i s o f b a c k s c a t t e r signals in c o m b i n a t i o n with
t e c h n i q u e s described in Sects. 2 a n d 3 p e r m i t s deter
s
mining a independent of sample geometry. This
c o m b i n e d t e c h n i q u e requires spatial a v e r a g i n g o v e r
large n u m b e r s of b a c k s c a t t e r w a v e f o r m s ( G o e b b e l s
1980).
W h i l e t h e p r e c e d i n g discussion deals with b u l k
w a v e s , it is also a p p l i c a b l e t o m e a s u r e m e n t s w i t h
surface w a v e s in t h e case of b o t h direct a t t e n u a t i o n
m e a s u r e m e n t s ( K e t t l e r et al. 1974) a n d b a c k s c a t t e r
m e a s u r e m e n t s ( H e c h t et al. 1981). T h e a b o v e m e n t i o n e d t e c h n i q u e s h a v e also b e e n used w i t h
m e a s u r e m e n t s in t h e diffuse region b y using a p p r o p r i
s
a
a t e f o r m s of a a n d a ( K e t t l e r et al. 1974). I n a d d i t i o n
t o grain-size m e a s u r e m e n t in b o t h b u l k a n d sheet
m e t a l s , a p p l i c a t i o n s h a v e been m a d e t o t h e d e t e r m i
n a t i o n of g r a i n - s i z e - d e p e n d e n t p r o p e r t i e s s u c h a s t h e
degree o f h e a t t r e a t m e n t o r s t a t e o f a n n e a l ( P a p a d a k i s
1968) a n d m e c h a n i c a l p r o p e r t i e s s u c h a s yield
s t r e n g t h ( K l i n m a n et a l . 1980).
5. Magnetic
Methods
E x p e r i m e n t a l evidence p o i n t s t o t h e influence o f g r a i n
size o n t h e m a g n e t i c p r o p e r t i e s o f steels ( L i t t m a n
1971). H o w e v e r , t h e f u n d a m e n t a l p h e n o m e n o l o g i c a l
r e l a t i o n s h i p s h a v e n o t been d e v e l o p e d . E m p i r i c a l
a p p r o a c h e s b a s e d o n linear regression analysis w i t h
coercive field, r e m a n e n t m a g n e t i z a t i o n , d e m a g n e t i z
ing field o r m a x i m u m p e r m e a b i l i t y a s i n d e p e n d e n t
v a r i a b l e s a n d either grain size o r a grain-size-related
p r o p e r t y a s d e p e n d e n t v a r i a b l e , h a v e achieved 1 5 %
accuracies in special cases. F a c t o r s such a s c h e m i c a l
Grain Size:
6. Barkhausen
Technique
T h e d i s c o n t i n u o u s m o v e m e n t of Bloch walls d u r i n g
d o m a i n g r o w t h g e n e r a t e s B a r k h a u s e n noise. Since
d o m a i n g r o w t h is influenced b y grain b o u n d a r y pin
ning sites, statistical analysis of B a r k h a u s e n noise
m u s t include g r a i n size as a p a r a m e t e r ( O t a l o a n d
S a y n a j a k a n g a s 1972). Because of t h e shielding of t h e
skin effect, i n t e r r o g a t i o n d e p t h is limited a n d a p p l i c a
tion is p r i m a r i l y t o sheet geometries for w h i c h g r a i n
size h a s been d e t e r m i n e d t o b e t t e r t h a n 1 A S T M
u n i t t o a s a m p l e d e p t h of a p p r o x i m a t e l y 0 . 4 m m .
A c c u r a c y is s t r o n g l y affected b y c r y s t a l l o g r a p h i c
texture, strain state, c h e m i s t r y a n d sheet thickness.
Bibliography
American Society for Testing and Materials 1980 Standard
method for estimating the average grain size of metals,
Nondestructive
Evaluation
181
Hardness Characterization
H a r d n e s s d e t e r m i n a t i o n s a r e a m o n g t h e m o s t fre
q u e n t l y used tests for t h e assessment of m e c h a n i c a l
p r o p e r t i e s . T h e value of t h e test d e p e n d s o n t h e fact
t h a t it affords a n inexpensive, n o n d e s t r u c t i v e m e a n s
of e v a l u a t i n g a n u m b e r of useful engineering p r o p e r
ties, such as tensile s t r e n g t h , h e a t t r e a t m e n t o r t h e
state of cold w o r k i n g in s t r u c t u r a l m e t a l s . T h e rela
t i o n s h i p b e t w e e n these p r o p e r t i e s a n d h a r d n e s s , while
n o t a n exact o n e , is close e n o u g h for a wide r a n g e of
industrial c o n t r o l s .
H a r d n e s s h a s been loosely defined as resistance t o
p e r m a n e n t i n d e n t a t i o n , b u t it is well k n o w n t h a t t h e
resistance is significantly affected by t h e s h a p e of t h e
tool used t o p r o d u c e t h e i n d e n t a t i o n ( T u c k e r m a n
1925). T h i s d e p e n d e n c e strongly suggests t h a t h a r d
ness is n o t a distinct p r o p e r t y b u t a c o m b i n a t i o n of a
n u m b e r of p r o p e r t i e s , such as yield s t r e n g t h in s h e a r
a n d b u l k m o d u l u s . T h e p e n e t r a t i o n of a n i n d e n t i n g
tool i n t o the surface of a m a t e r i a l is influenced by
these p r o p e r t i e s a c c o r d i n g t o t h e s h a p e of the tool. A
h a r d n e s s n u m b e r , a r a t i o of l o a d t o i m p r e s s i o n a r e a ,
is n o t a simple c o m p r e s s i o n stress, b u t a highly
c o m p l e x value in w h i c h a n u m b e r of basic p r o p e r t i e s
are s u m m e d in p r o p o r t i o n s d e p e n d e n t o n t h e s h a p e of
the i n d e n t i n g tool.
A l t h o u g h there is p r o b a b l y n o such p r o p e r t y as
" h a r d n e s s , " it is a c o n v e n i e n t generic t e r m . P r o p e r l y ,
the t e r m h a r d n e s s h a s m e a n i n g only in t e r m s of a
specific test. O n e m a y s p e a k of Brinell h a r d n e s s o r
Rockwell h a r d n e s s , b u t they s h o u l d n o t be c o n s i d e r e d
c o m m o n m e a s u r e s of t h e s a m e t h i n g .
A n u m b e r of different tests h a v e been d e v e l o p e d .
T h e y r a n g e from t h e simple M o h s scratch test, p r o
p o s e d in 1822 a n d still used as a basic, practical test
for the field m i n e r a l o g i s t , t o t h e highly s o p h i s t i c a t e d
m i c r o h a r d n e s s tests t h a t c a n e v a l u a t e individual crys
tal c o n s t i t u e n t s of a m e t a l m a t r i x . N e a r l y all of these
tests involve s o m e k i n d of i m p r e s s i o n m a d e in t h e
surface of a specimen. T h e i m p r e s s i o n m a y be in t h e
form of a scratch, a n i n d e n t a t i o n m a d e by a steel o r
d i a m o n d t o o l u n d e r static forces o r a d y n a m i c re
b o u n d test. A m o n g s u b s t a n c e s tested, m e t a l s h a v e
p r o b a b l y received t h e m o s t a t t e n t i o n , b u t r u b b e r a n d
m a n u f a c t u r e d plastics a r e also i m p o r t a n t a r e a s of
a p p l i c a t i o n . M e t h o d s a r e available t o test m i n e r a l s ,
glass, h a r d c a r b i d e s a n d c e r a m i c m a t e r i a l s . Tests o n
such diverse m a t e r i a l s as p a i n t a n d v a r n i s h c o a t i n g s
have proved valuable.
T h e following sections describe specific tests t h a t
h a v e gained general a c c e p t a n c e . F o r m o s t , s t a n d a r d
m e t h o d s a n d p r o c e d u r e s h a v e been a d o p t e d b y
various n a t i o n a l s t a n d a r d i z i n g o r g a n i z a t i o n s a n d b y
o r g a n i z a t i o n s such as the I n t e r n a t i o n a l O r g a n i z a t i o n
for S t a n d a r d i z a t i o n (ISO) a n d t h e I n t e r n a t i o n a l
O r g a n i z a t i o n for Legal M e t r o l o g y ( O I M L ) .
7. The Brinell
Hardness
Test
2 ]l2
nD[D-(D -d ) ]
w h e r e H B is t h e Brinell h a r d n e s s n u m b e r , F is the
i n d e n t i n g l o a d in kgf, D is the ball d i a m e t e r in m m
a n d d is the i m p r e s s i o n d i a m e t e r in m m . C o n v e n i e n t
tables c o n v e r t i n g i m p r e s s i o n d i a m e t e r s directly t o
Brinell n u m b e r s a r e available from m a n y sources, for
e x a m p l e the Standard Test Method for Brinell Hard
ness of Metallic Materials ( A S T M 10), issued by the
A m e r i c a n Society for T e s t i n g a n d M a t e r i a l s .
T h e r e q u i r e m e n t for t h e u n i q u e use of the milli
m e t e r a n d the k i l o g r a m - f o r c e i n t r o d u c e s a p r o b l e m
w h e n a c h a n g e is m a d e t o SI u n i t s . H e r e , the unit of
force b e c o m e s the n e w t o n a n d in s o m e jurisdictions
its use in preference t o the kilogram-force is m a n d a
t o r y . T h e t e n d e n c y in i n t e r n a t i o n a l s t a n d a r d s h a s
183
Hardness
Characterization
184
2. The Rockwell
Hardness
Test
T h e R o c k w e l l test w a s d e v e l o p e d a b o u t 1922 by
Stanley R o c k w e l l , a metallurgist, w h o saw t h e need
for a n i n s t r u m e n t c a p a b l e of testing the very h a r d
steels used in ball b e a r i n g races. T h e test is p e r f o r m e d
by a m a c h i n e t h a t initially forces a p e n e t r a t o r i n t o the
surface of t h e specimen u n d e r a light l o a d called t h e
minor load. A d e p t h - m e a s u r i n g i n d i c a t o r c o u p l e d t o
t h e p e n e t r a t o r is set t o a null reference a n d t h e l o a d o n
t h e p e n e t r a t o r is increased s m o o t h l y t o a higher value,
called t h e major load, a n d t h e n r e d u c e d a g a i n t o t h e
m i n o r l o a d value. T h e d e p t h m e a s u r i n g device t h e n
s h o w s t h e increased d e p t h of i n d e n t a t i o n c a u s e d b y
t h e a p p l i c a t i o n of the m a j o r l o a d . T h e scale is g r a d u
a t e d t o r e a d the h a r d n e s s n u m b e r directly.
T h e m i n o r l o a d is 10 kgf a n d the m a j o r l o a d m a y b e
either 60, 100 o r 150 kgf. T h e p e n e t r a t o r is a d i a m o n d
c o n e h a v i n g a n included angle of 120 with a spherical
p o i n t of 0.2 m m r a d i u s . F o r testing softer m e t a l s a n d
plastics a series of ball p e n e t r a t o r s of
--, i a n d \ in.
d i a m e t e r is available. E a c h c o m b i n a t i o n of p e n e t r a t o r
a n d m a j o r l o a d c o n s t i t u t e s a s e p a r a t e scale a n d a
R o c k w e l l h a r d n e s s n u m b e r is always q u o t e d with a
letter s y m b o l t o indicate t h e scale. O n e R o c k w e l l
n u m b e r , t h e smallest g r a d u a t i o n o n t h e i n d i c a t o r dial,
represents a n increase in d e p t h of 0.002 m m .
T h e R o c k w e l l test is extremely useful in the c o n t r o l
of sheet m a t e r i a l such as a l u m i n u m , b r a s s o r steel.
Because of the e c o n o m i c i m p o r t a n c e of very thin
sheet, a special tester k n o w n as t h e R o c k w e l l Super
ficial Tester w a s developed. I n this m a c h i n e , the
m i n o r l o a d is r e d u c e d from 10 kgf t o 3 kgf. T h e m a j o r
l o a d s a r e 15, 30 a n d 45 kgf. T h e sensitivity of the
d e p t h - m e a s u r i n g device is increased t o 0.001 m m p e r
division.
T h e Superficial T e s t e r uses t h e s a m e series of
i n d e n t e r s as t h e s t a n d a r d m a c h i n e a n d c a n success
fully test h a r d sheet m a t e r i a l s as thin as 0.125 m m .
T h e d e e p e r i m p r e s s i o n s in soft sheet require a g r e a t e r
thickness. M o s t p r o c e d u r a l s t a n d a r d s p r o v i d e tables
s h o w i n g m i n i m u m thickness limits for v a r i o u s scales
a n d h a r d n e s s e s . T h e general rule is t h a t n o bulge o r
o t h e r m a r k i n g s h o w i n g t h e effect of l o a d s h o u l d
be visible o n t h e side of t h e piece o p p o s i t e t h e
impression.
T h e R o c k w e l l test is r a p i d a n d d o e s n o t require
a skilled o p e r a t o r . T h e e q u i p m e n t c a n b e a d a p t e d
readily t o a u t o m a t i o n a n d use with d a t a acquisition
systems. D a i l y verification of t h e a c c u r a c y of t h e
tester is a c c o m p l i s h e d by c a l i b r a t e d test blocks avail
able from t h e m a n u f a c t u r e r s of t h e m a c h i n e s . I n t h e
U K a n d in s o m e E u r o p e a n c o u n t r i e s , test b l o c k s
certified b y official g o v e r n m e n t b o d i e s a r e available.
3. The Vickers
Hardness
Test
Hardness
F/D
w h e r e H V is t h e Vickers h a r d n e s s n u m b e r , F is t h e
i n d e n t i n g l o a d in kgf a n d D is t h e a v e r a g e d i a g o n a l
length in m m .
T h e Vickers test is well a d a p t e d t o testing very h a r d
steels a n d covers t h e r a n g e d o w n t o very soft m e t a l s in
a single scale of n u m b e r s . T h e i m p r e s s i o n s a r e small,
typically less t h a n 0.5 m m o n t h e d i a g o n a l , a n d n o t
readily a p p a r e n t t o t h e u n a i d e d eye. Because of this, a
m o r e e l a b o r a t e r e a d i n g m i c r o s c o p e is r e q u i r e d t h a n
for t h e Brinell test. U s u a l l y t h e m i c r o s c o p e is built
i n t o t h e testing m a c h i n e a n d a r r a n g e d so t h a t t h e
impression is a u t o m a t i c a l l y c e n t e r e d in t h e viewing
field for m e a s u r e m e n t . T h e m i c r o s c o p e h a s a magnifi
c a t i o n of t h e o r d e r of 100 a n d is usually e q u i p p e d w i t h
a m i c r o m e t e r eyepiece g r a d u a t e d t o r e a d directly t o
the nearest 0.001 m m . Because of t h e h i g h e r magnifi
c a t i o n , a m o r e careful p r e p a r a t i o n of t h e specimen
surface is r e q u i r e d t h a n for t h e Brinell o r R o c k w e l l
tests.
T h e test is c a p a b l e of resolving small differences in
h a r d n e s s a n d its a c c u r a c y is easily c o n t r o l l e d either b y
p r i m a r y s t a n d a r d i z a t i o n of l o a d a n d i n d e n t e r s h a p e
o r b y s t a n d a r d test b l o c k s . T h e test is widely used in
the U K a n d o n t h e C o n t i n e n t b u t h a s h a d less
p o p u l a r i t y in t h e U S A .
4. The Scleroscope
Characterization
Test
5. Microhardness
Tests
M i c r o h a r d n e s s tests a r e i n d e n t a t i o n h a r d n e s s tests
m a d e u n d e r u n u s u a l l y low i n d e n t i n g forces, usually in
t h e r a n g e from o n e g r a m - f o r c e t o o n e kilogram-force.
T h e resulting i n d e n t a t i o n is of m i c r o s c o p i c size, in the
r a n g e of 0.01 m m t o 0.10 m m , a n d h a r d l y visible to
t h e u n a i d e d eye. It is possible t o test such objects as
small w a t c h p i n i o n s , needle p o i n t s a n d even indi
v i d u a l crystals in a m e t a l m a t r i x .
Because of t h e p r o b l e m s of m a k i n g , locating a n d
m e a s u r i n g these small i m p r e s s i o n s , special testing
machines have been developed that permit the opera
t o r t o locate u n d e r t h e m i c r o s c o p e t h e p a r t i c u l a r a r e a
w h e r e t h e i n d e n t a t i o n is t o be m a d e , transfer it
automatically under the indenter, m a k e the impres
sion a n d r e t u r n it t o t h e center of t h e m i c r o s c o p e field
for m e a s u r e m e n t . T h e m e a s u r e m e n t s a r e usually
m a d e b y a m i c r o s c o p e e q u i p p e d with a vertical illumi
n a t o r a n d a filar m e a s u r i n g eyepiece. Very careful
p r e p a r a t i o n of t h e specimen is r e q u i r e d .
T h e i n d e n t e r is a d i a m o n d p y r a m i d , either t h e 136
Vickers i n d e n t e r o r t h e K n o o p i n d e n t e r . T h e Vickers
i n d e n t e r is preferred for testing m e t a l s since t h e test is
a l m o s t i n d e p e n d e n t of l o a d a n d t h e results a r e c o m
p a r a b l e t o Vickers tests m a d e u n d e r heavier l o a d s .
T h e K n o o p i n d e n t e r p e r m i t s tests t o b e m a d e o n
frangible m a t e r i a l s such as glass, g e m s t o n e s a n d h a r d
c a r b i d e s , w h i c h c o u l d n o t b e tested by o t h e r forms of
indenter.
T h e K n o o p i n d e n t e r w a s d e v e l o p e d a t the N a t i o n a l
B u r e a u of S t a n d a r d s in t h e U S A ( K n o o p et al. 1939).
It is a four-sided d i a m o n d p y r a m i d of e l o n g a t e d s h a p e
in w h i c h t h e angle b e t w e e n t w o o p p o s i t e edges is 172
30' a n d b e t w e e n t h e o t h e r t w o edges 130 0 \ T h e
i m p r e s s i o n left b y t h e i n d e n t e r is a r h o m b u s with o n e
185
Hardness
Characterization
F/D
6. Portable
Hardness
Testers
186
s t a n d a r d l o a d s a n d use the s t a n d a r d i n d e n t e r s b u t
o t h e r s d o n o t . T h e user is w a r n e d t h a t even t h o u g h a
n o n s t a n d a r d m a c h i n e m a y r e a d correctly o n a test
block, it m a y give a n incorrect result w h e n used with
a n o t h e r m a t e r i a l , p a r t i c u l a r l y if there is a h a r d n e s s
g r a d i e n t from t h e surface t o t h e interior.
O t h e r types of p o r t a b l e testers o p e r a t e o n principles
t h a t seem a t first t o be far r e m o v e d from the c o n v e n
tional i n d e n t a t i o n test. T h e e d d y c u r r e n t test, which
r e s p o n d s t o a c o m b i n a t i o n of the m a g n e t i c a n d elec
trical p r o p e r t i e s of the specimen, t h e S o n a d u r tester in
which a r o d t i p p e d by a d i a m o n d i n d e n t e r is l o a d e d
against t h e specimen a n d driven i n t o a n a t u r a l reso
n a n t frequency responsive t o t h e a r e a of c o n t a c t
b e t w e e n i n d e n t e r a n d specimen, a n d the E s e w a y tester
in which a n i n d e n t e r i m p a c t s the specimen surface a t a
fixed speed a n d t h e deceleration of the i n d e n t e r is
m e a s u r e d by a piezoelectric sensor are all examples of
n e w t e c h n i q u e s in t h e field. W h e t h e r o r n o t they will
be accepted in time as formal h a r d n e s s testing devices
r e m a i n s t o be seen, b u t they d o fulfill the basic
p r e m i s e b e h i n d all h a r d n e s s t e s t i n g t h e y s e p a r a t e
m a t e r i a l s b y a m e a n s t h a t correlates with a variety of
useful engineering p r o p e r t i e s .
7. Hardness
Conversion
Tables
Hydrogen
as a Metallurgical
Probe
Bibliography
American Society for Testing and Materials 1984 Annual
Book of ASTM Standards, Pt. 3. American Society for
Testing and Materials, Philadelphia, PA, pp. 16474.
Knoop F, Peters C G, Emerson W 1939 A sensitive
pyramidal diamond tool for indentation measurements.
J. Res. Natl. Bur. Stand. 23: 39-61
Lysaght V 1949 Indentation Hardness Testing. Reinhold,
New York
Lysaght V E, DeBellis A 1969 Hardness Testing Handbook.
American Chain and Cable Company, Bridgeport, CT
Mott W 1956 Micro-Indentation Hardness Testing. Butterworths, London
O'Neill 1967 Hardness Measurement of Metals and Alloys,
2nd edn. Chapman and Hall, London
Tabor D 1951 The Hardness of Metals. Clarendon Press,
Oxford
Tuckerman L 1925 Hardness and hardness testing. Mech.
Eng. 47: 53-5
Williams S R 1942 Hardness and Hardness Measurements.
American Society for Metals, Cleveland, OH
D . R. T a t e
[Rockville, M a r y l a n d , U S A ]
1. Density
of Sites
and Hydrogen
Distribution
-r.
n(E)
dE
,1 + exp[(E -
p)/kT]
(1)
w h e r e is t h e chemical p o t e n t i a l of h y d r o g e n , also
called t h e F e r m i level of h y d r o g e n . T h u s b y m e a s u r
ing t h e chemical p o t e n t i a l of h y d r o g e n at different
h y d r o g e n c o n c e n t r a t i o n s the D O S c a n be e v a l u a t e d
from E q n . (1). O w i n g t o t h e steplike b e h a v i o r of the
F e r m i - D i r a c function (the reciprocal of t h e d e n o m i
n a t o r in E q n . (1)) h y d r o g e n a t o m s a r e usually filled in
sites below t h e F e r m i level ( < ) a n d E q n . (1) is
simplified t o
-r -
(E) dE
or
= ()
(2)
00
Hydrogen
as a Metallurgical
Probe
2. Interaction
with Vacancies
and
Dislocations
188
5. Interaction
with Internal
Interfaces
G r a i n b o u n d a r i e s in p u r e m e t a l s d o n o t i n t e r a c t very
strongly with dissolved h y d r o g e n . H o w e v e r , in t h e
presence of o t h e r segregated impurities (e.g., p h o s
p h o r u s in iron) a s t r o n g i n t e r a c t i o n will occur,
because the e m b r i t t l e m e n t effect of s o m e elements is
Hydrogen
e n h a n c e d r e m a r k a b l y in t h e presence of h y d r o g e n .
The usual procedure to measure grain b o u n d a r y
segregation b y surface analytical t e c h n i q u e s after
i n t e r g r a n u l a r fracture fails for h y d r o g e n b e c a u s e
c o m m o n t e c h n i q u e s such as A u g e r electron s p e c t r o s
c o p y , electron s p e c t r o s c o p y for chemical analysis a n d
x-ray p h o t o e l e c t r o n s p e c t r o s c o p y d o n o t detect
hydrogen or because the previous grain b o u n d a r y
coverage by h y d r o g e n will be c h a n g e d after t h e e x p o
sure of t h e b o u n d a r y t o t h e high v a c u u m d u e t o t h e
a t t a i n m e n t of a n e w e q u i l i b r i u m c o r r e s p o n d i n g t o
surface segregation.
N a n o c r y s t a l l i n e m e t a l s (i.e., polycrystalline m e t a l s
with grain d i a m e t e r s of t h e o r d e r of n a n o m e t e r s )
c o n t a i n a large fraction of g r a i n b o u n d a r i e s a n d they
are, therefore, m o s t suitable for s t u d y i n g t h e i n t e r a c
tion of h y d r o g e n w i t h g r a i n b o u n d a r i e s . It h a s b e e n
s h o w n for n a n o c r y s t a l l i n e p a l l a d i u m ( M u t s c h e l e a n d
K i r c h h e i m 1987) t h a t t h e g r a i n b o u n d a r i e s p r o v i d e a
b r o a d s p e c t r u m of segregation energies ( D O S ) a s o n e
w o u l d expect from simple g e o m e t r i c a l c o n s i d e r a t i o n s .
T h e diffusion b e h a v i o r is peculiar b e c a u s e t h e diffu
sion coefficient in g r a i n b o u n d a r i e s is l o w e r t h a n t h a t
within t h e g r a i n s d u e t o a preferred o c c u p a t i o n of
low-energy sites a t low h y d r o g e n c o n c e n t r a t i o n s . T h e
diffusivity increases as sites of higher energy h a v e t o
be occupied by increasing t h e h y d r o g e n c o n c e n t r a
tion. A l t h o u g h t h e w i d t h of t h e D O S is a b o u t t h e
s a m e as in metallic glasses (see Sect. 4), t h e a v e r a g e
activation energy, calculated as t h e difference b e t w e e n
average site a n d s a d d l e - p o i n t energies, is r a t h e r small
in n a n o c r y s t a l l i n e p a l l a d i u m w h e n c o m p a r e d w i t h
metallic glasses, i n d i c a t i n g a m o r e o p e n s t r u c t u r e of
the grain b o u n d a r i e s in n a n o c r y s t a l l i n e m a t e r i a l s .
T h e (- p h a s e t r a n s f o r m a t i o n in t h e system of
h y d r o g e n a n d n a n o c r y s t a l l i n e p a l l a d i u m differs re
m a r k a b l y from t h a t in n o r m a l polycrystalline palla
d i u m (20 grain d i a m e t e r ) a n d it c a n be used t o
d e t e r m i n e t h e a v e r a g e thickness of g r a i n b o u n d a r i e s .
In polycrystalline p a l l a d i u m t h e v o l u m e fraction of
grain b o u n d a r i e s a n d its influence o n t h e p h a s e t r a n s
f o r m a t i o n is negligible. I n n a n o c r y s t a l l i n e p a l l a d i u m
the s a m e p h a s e is f o r m e d w i t h i n t h e grains b u t m u c h
less h y d r o g e n is n e e d e d for t h e c o m p l e t i o n of t h e
phase to phase transformation because the grain
b o u n d a r i e s d o n o t p a r t i c i p a t e in t h e p h a s e f o r m a t i o n .
F r o m t h e difference b e t w e e n t h e a m o u n t of h y d r o g e n
used for t h e p h a s e f o r m a t i o n in polycrystalline a n d
n a n o c r y s t a l l i n e p a l l a d i u m t h e v o l u m e fraction of t h e
grain b o u n d a r i e s is calculated s t r a i g h t f o r w a r d l y .
T h u s a v o l u m e fraction of 0.27 in a n a n o c r y s t a l l i n e
p a l l a d i u m s a m p l e w i t h a n a v e r a g e g r a i n d i a m e t e r d of
8 n m (from t r a n s m i s s i o n electron m i c r o g r a p h s ) w a s
d e t e r m i n e d w h i c h yields a n a v e r a g e thickness of t h e
grain b o u n d a r i e s = vd/3 = 0.7 n m . T h i s r e l a t i o n s h i p
is valid for grains of spherical o r cubic s h a p e w h i c h
a p p r o x i m a t e s well t o t h e case of n a n o c r y s t a l l i n e
palladium.
F r o m the i n t e r a c t i o n of h y d r o g e n w i t h P d - A l 2 0 3
as a Metallurgical
Probe
-6.0i-
-7.0
-7.5 -
-e.ol
-4.0
I
-3.5
I
-3.0
Log
I
-2.5
I
-2.0
Figure 1
Diffusion coefficient of hydrogen in palladium with A1 20 3
precipitates D as a function of hydrogen concentration c:
saturation of irreversible traps (free oxygen bonds at the
P d - A l 2 0 3 interface) and reversible traps (strained
interstices of palladium at the interface) (O), only
reversible trapping occurs ( ) , after annealing in
aluminum vapor the oxygen bonds at the interface are
saturated with aluminum and no irreversible trapping is
observed (-I-), and after a final annealing treatment in air
the oxygen atoms saturate the free aluminum bonds at the
interfaces but still have free bonds to cause irreversible
trapping of hydrogen ( ) . After saturation of all kinds
of traps the diffusivity of hydrogen in pure palladium
(log D = 6.4) is measured
(or P d - Z n O ) interfaces i n f o r m a t i o n o n t h e p h a s e
b o u n d a r y itself c a n b e e x t r a c t e d . T h e interfaces a r e
p r e p a r e d b y i n t e r n a l o x i d a t i o n of p a l l a d i u m - a l u m i
n u m ( p a l l a d i u m - z i n c ) alloys a t 1000 C in air with
leads t o t h e f o r m a t i o n of p r i s m a t i c precipitates of
A 1 2 0 3 ( Z n O ) h a v i n g edge lengths w i t h i n t h e s u b m i c r o m e t e r r a n g e . T h e diffusion coefficients of h y d r o
gen a t 295 a r e s h o w n in F i g . 1 as a function of
h y d r o g e n c o n c e n t r a t i o n . D u r i n g t h e first r u n a larger
t r a p c o n c e n t r a t i o n is o b s e r v e d c o m p a r e d t o t h e fol
lowing r u n s . Between e a c h r u n h y d r o g e n is r e m o v e d
b y a n o d i c p o l a r i z a t i o n . T h e difference in t r a p c o n c e n
t r a t i o n s is a t t r i b u t e d t o irreversible t r a p p i n g of h y d r o
gen a t t h e p a l l a d i u m - o x i d e p h a s e b o u n d a r y , w h e r e
t h e n u m b e r of irreversible t r a p sites c o r r e s p o n d s t o a
15
-2
(about
c o v e r a g e of 1.5 1 0 h y d r o g e n a t o m s c m
o n e m o n o l a y e r ) of t h e b o u n d a r y . T h e s e h y d r o g e n
a t o m s c a n n o t b e r e m o v e d either b y a n o d i c p o l a r i z a
tion o r b y a n n e a l i n g a t 800 C in high v a c u u m . T h u s ,
d u r i n g t h e first r u n of d o p i n g t h e s a m p l e s , b o t h k i n d s
of t r a p sites a r e s a t u r a t e d while, in t h e following r u n s ,
only reversible sites a r e filled.
T h e irreversible t r a p p i n g w a s a t t r i b u t e d t o t h e
f o r m a t i o n of o x y g e n - h y d r o g e n b o n d s a t t h e palla
d i u m - o x i d e interface a s s u m i n g t h a t u n s a t u r a t e d oxy
gen a t o m s from t h e t e r m i n a t i n g layer of the oxide
189
Hydrogen
as a Metallurgical
Probe
precipitates. T h i s a s s u m p t i o n is s u p p o r t e d b y direct
o b s e r v a t i o n s in a high-resolution electron m i c r o s c o p e
(Necker a n d M a d e r 1988). By a n n e a l i n g t r e a t m e n t s in
zinc o r a l u m i n u m v a p o r these oxygen a t o m s a r e
s a t u r a t e d with t h e c o r r e s p o n d i n g m e t a l a t o m s . T h e s e
form t h e t e r m i n a t i n g layer of t h e oxide a n d h a v e a
lower affinity t o h y d r o g e n ; therefore, t h e irreversible
t r a p p i n g of h y d r o g e n vanishes (see F i g . 1). T h e irre
versible t r a p s recover if t h e samples a r e r e a n n e a l e d in
air. T h e reversible t r a p p i n g of t h e h y d r o g e n c a n b e
described q u a n t i t a t i v e l y b y a two-level t r a p p i n g
m o d e l ( K i r c h h e i m 1982) with a free energy of t r a p
1
of h y d r o g e n .
p i n g AG = - 44 000 + 50rkJ m o l "
This t r a p p i n g m a y b e d u e t o t h e strain field a r o u n d
the precipitates because of misfit dislocations a n d / o r
the different t h e r m a l e x p a n s i o n coefficients of t h e
p a l l a d i u m a n d t h e oxides.
D u r i n g t h e internal o x i d a t i o n of P d - 3 a t . % A l
alloys a t 700 C in air, n o precipitates were detected
by c o n v e n t i o n a l t r a n s m i s s i o n electron m i c r o s c o p y
a n d only streaks were observed in t h e diffraction
p a t t e r n . A c c o r d i n g t o chemical analysis t h e s a m p l e
contained
3.0 0.05 a t . %
of
aluminum
and
4.9 0 . 1 5 at. % of oxygen, which c o r r e s p o n d s t o a n
excess of 0.4 0 . 2 a t . % of oxygen. T h i s value is in
g o o d a g r e e m e n t with t h e 0.5 a t . % of irreversible t r a p s
t h a t w a s d e t e r m i n e d for h y d r o g e n in this alloy. T h e
c o n c e n t r a t i o n of irreversible t r a p s is larger w h e n
c o m p a r e d with t h e samples oxidized a t 1000 C
because t h e interfacial a r e a is larger for t h e small
precipitates formed a t 700 C. T h u s , h y d r o g e n p r o
vides i n f o r m a t i o n o n t h e interfacial a r e a o r t h e
n u m b e r of u n s a t u r a t e d oxygen b o n d s . T h e interfacial
area c a n b e calculated, a s s u m i n g t h e s a m e coverage
15
as for irreversible t r a p p i n g of 1.5 10 h y d r o g e n
2
atoms c m " .
4. Behavior
in Crystalline
and Amorphous
Alloys
(^--^-,)
(3)
190
I.Op
()
T i 3 Ni tetrahedra
I
T i 2 N i 2tetrahedra
Log
Figure 3
Diffusion coefficient of hydrogen in amorphous Pd^S^
prepared by melt spinning ( ) , sputtering ( ) and the
double piston technique (O). The lines were calculated
from the DOS
-50
-40
-30
-20
-10
Figure 2
Measured density of sites dc/ for (a) amorphous Ni 3 5Ti 65
and (b) ^^, revealing the concentration and binding
energies of different tetrahedral sites
191
Hydrogen
as a Metallurgical
Probe
Bibliography
Alefeld G, Volkl J 1980 Hydrogen in Metals, Topics in
Applied Physics, Vol. 29. Springer, Berlin, pp. 20142
Bernstein I M, Thomson A W (eds.) 1981 Proc. 3rd Int.
Conf. Effects of Hydrogen on Behavior of Materials.
Metallurgical Society of AIME, New York
Feenstra R, Brower R, Griessen R 1988 Hydrogen as a local
probe of alloys: Nb^V,. Europhys. Lett. 7(5): 425-30
Harris J H, Curtin W A, Tenhover A 1987 Universal
features of hydrogen absorption in amorphous transition
metal alloys. Phys. Rev. 36: 5784^97
Kim J J, Stevenson D A 1988 Hydrogen permeation studies
of amorphous and crystallized Ni-Ti alloys. J. Non-Cryst.
Solids 101: 187-97
Kirchheim R 1982 Solubility, diffusivity and trapping of
hydrogen in dilute alloys, deformed and amorphous
metals. Acta Metall. 30: 1069
Kirchheim R, Huang X Y, Carstanjen H - D , Rush J J 1987
Inelastic neutron scattering and resistivity of hydrogen in
cold-worked palladium. In: Latanison R M, Jones R
(eds.) 1987 Chemistry and Physics of Fracture, NATO
ASI series. NATO, Brussels, p. 580
Kirchheim R, Stolz U 1985 Modelling tracer diffusion and
mobility of interstitials in disordered materials. J. NonCryst. Solids 70: 323
192
Infrared Spectroscopy
$avdv
1. Basic
Principles
Infrared s p e c t r a a r e usually p r e s e n t e d as a p l o t of
a b s o r p t i o n (in p e r c e n t t r a n s m i s s i o n ) as a function of
1
w a v e l e n g t h (in ) o r w a v e n u m b e r (in c m " ) . T h e
units a r e related as follows:
4
1 0 M v ac = v/n
(1)
w h e r e is the w a v e l e n g t h , is t h e w a v e n u m b e r a n d
is t h e refractive index of air.
Molecules in a n y s t a t e of m a t t e r c a n b e viewed
from a m e c h a n i c a l perspective as consisting of m a s s e s
( a t o m s ) c o n n e c t e d by springs (chemical b o n d s ) . A s in
a n y m e c h a n i c a l system, energy c a n be a b s o r b e d with
the result t h a t certain frequencies a r e excited. T h e
exact frequencies d e p e n d o n t h e m a s s e s of t h e a t o m s ,
the force c o n s t a n t s of t h e chemical b o n d s c o n n e c t i n g
t h e m a n d t o a lesser extent o n i n t e r a c t i o n s b e t w e e n
n o n b o n d e d atoms. In the simple-harmonic-oscillator
a p p r o x i m a t i o n , t h e frequency of v i b r a t i o n / of a
d i a t o m i c molecule with a t o m s of m a s s e s m a n d is
f=(2ny\k/Myi
(2)
w h e r e k is t h e force c o n s t a n t a n d is t h e r e d u c e d m a s s
(i.e., = mM/(m + M ) ) .
T h e v i b r a t i o n a l frequencies of a t o m s in molecules
c o r r e s p o n d t o t h e frequencies f o u n d in t h e ir region of
the e l e c t r o m a g n e t i c s p e c t r u m . In o r d e r for i n t e r a c t i o n
to occur, h o w e v e r , t h e v i b r a t i o n m u s t involve a n
oscillation in electric dipole m o m e n t . O n l y u n d e r
these c i r c u m s t a n c e s is ir r a d i a t i o n of t h e s a m e fre
q u e n c y a b s o r b e d a n d t h e v i b r a t i o n excited. T h e
a b s o r p t i o n intensity is
= (Nn/3c )(d7t/dQ)
(3)
w h e r e av is t h e a b s o r p t i o n coefficient a t frequency v, TV
3
is t h e n u m b e r of molecules p e r c m , Jt is the b o n d
m o m e n t a n d Q is the n o r m a l c o o r d i n a t e for the
vibration.
T h u s , m e t a l s a n d h o m o n u c l e a r gases d o n o t s h o w ir
a b s o r p t i o n p a t t e r n s because the v i b r a t i n g a t o m s d o
n o t give rise t o dipole oscillations. Strongly p o l a r
s u b s t a n c e s , such as w a t e r , a r e very s t r o n g a b s o r b e r s
of ir r a d i a t i o n w h e r e a s n o n p o l a r molecules, such as
h y d r o c a r b o n s , s h o w r a t h e r w e a k a b s o r p t i o n for m a n y
of their skeletal v i b r a t i o n s .
A n y defined a g g r e g a t i o n of a t o m s (i.e., a molecule)
h a s a finite n u m b e r of f u n d a m e n t a l v i b r a t i o n a l
a b s o r p t i o n s , e q u a l t o 37V 6 w h e r e is the n u m b e r
of a t o m s in t h e molecule (3 - 5 for linear m o l
ecules). O v e r t o n e a n d c o m b i n a t i o n b a n d s c a n also
a p p e a r , a n d the ir a b s o r p t i o n p a t t e r n for each m o l
ecular species is u n i q u e . A s m i g h t be expected, h o w
ever, structurally identical g r o u p s h a v e the s a m e o r
similar frequencies in different molecules. T h u s , the
1
a l i p h a t i c C H g r o u p always a b s o r b s n e a r 2960 c m " .
1
T h e c a r b o n y l ( C = 0 ) g r o u p a b s o r b s n e a r 1710 c m "
1
in o r g a n i c acids; n e a r 1720 c m " in k e t o n e s ; a n d
1
n e a r 1740 c m " in esters. ( E x a m p l e s of o t h e r " g r o u p
f r e q u e n c i e s " a r e given in T a b l e 1.) D e v i a t i o n s of
t h e a b s o r p t i o n s from their " n o r m a l " positions
c a n be utilized t o gain m o r e sophisticated s t r u c t u r a l
information.
2. The IR
Spectrometer
S p e c t r o s c o p y in t h e ir region p r e s e n t s several u n i q u e
difficulties. T h e region is intrinsically of low energy,
a n d t h u s the energy t r a n s m i s s i o n of the s p e c t r o m e t e r
must be maximized. M a n y materials that are trans
p a r e n t t o visible r a d i a t i o n d o n o t t r a n s m i t ir; optical
glass, for e x a m p l e , is i r - o p a q u e a n d so special m a t e r
ials such as single crystals of N a C l , K B r o r A g C l m u s t
be used for w i n d o w m a t e r i a l s . P r o p e r t i e s of s o m e
c o m m o n i r - t r a n s m i t t i n g m a t e r i a l s a r e given in T a b l e
2. W a t e r is strongly a b s o r b i n g a n d t h u s u n s u i t a b l e as
a solvent. Finally, b l a c k b o d y r a d i a t i o n originating
from the s p e c t r o m e t e r c o m p o n e n t s is a t its p e a k in the
m o s t c o m m o n l y used region a n d is responsible for a
high b a c k g r o u n d of stray r a d i a t i o n .
Dispersive
spectrometers
are the most c o m m o n
type. A typical optical system is s h o w n in Fig. 1.
Infrared r a d i a t i o n from t h e s o u r c e (a h o t ceramic r o d
o r N i c h r o m e coil) is directed by front-surface optics
t h r o u g h t h e s a m p l e c o m p a r t m e n t . A r o t a t i n g sector
m i r r o r alternately allows the s a m p l e a n d reference
b e a m s t o p a s s t h r o u g h t h e e n t r a n c e slit i n t o the
193
Infrared
Spectroscopy
Table 1
1
8
Some typical group frequencies (cm' ) in the infrared region
The N H - O H region
3460-3620 alcohol (solution)
3620-3590 phenol (solution)
3550-3330 primary amine (solution)
3450-3250 primary amine (solution)
2900-2800 aldehyde
2900-2865 - O C H ,
2805-2780 - N C H 3
2260-2100 acetylenes
2175-2160 thiocyanates
2150-2050 isothiocyanates
2150-2110 isonitriles
1750-1735
1740-1715
1740-1720
1735-1690
aliphatic ester
aromatic ester
aldehyde
carbamates
1725-1705
1690-1630
1680-1630
1660-1620
1415-1390
1200-1187
1210-1100
1150-1075
1075-1000
sulfate
sulfate
tertiary alcohol
secondary alcohol
primary alcohol
995-985
910-905
765-735
710-685
ketone
alkenes
secondary amide
primary amide (2 bands)
vinyl
vinyl
monosubstituted aromatic
monosubstituted aromatic
a For a more complete listing and discussion, see Colthup et al. (1975)
m o n o c h r o m a t o r , w h e r e t h e r a d i a t i o n is dispersed b y a
grating. (Older s p e c t r o m e t e r s m a y use a rock-salt
p r i s m instead of a grating.) T h e s p e c t r u m is s c a n n e d
by r o t a t i n g the g r a t i n g . T h e dispersed r a d i a t i o n scans
across a n exit slit, t h r o u g h a b a n d p a s s filter (to
eliminate o v e r l a p p i n g o r d e r s a n d stray light), a n d is
focused o n a detector, usually a tiny t h e r m o c o u p l e
Table 2
Properties of some ir-transmitting materials
Window
material
Quartz (Si0 2)
LiF
Sapphire (A1 20 3)
Fluorite (CaF 2)
Irtran I (MgF 2)
Servofrax (As 2S 3)
BaF 2
Rock salt (NaCl)
Irtran II (Zn2S)
Sylvite (KC1)
Irtran III (CaF 2)
Irtran IV (Zn2Se)
KBr
AgCl
Ge
Si
KRS-5 (Tl2BrI)
CsBr
Csl
0.2-3.6 (10)
0.2-6.2 (12)
0.2-5 (8)
0.2-7.8 (10)
2-6.4 (12)
1-11.1 (5)
0.2-11.5(9)
0.2-17(10)
1-10.7 (12)
0.3-2.1 (10)
0.2-8.7 (12)
1-15.2(12)
0.2-32 (4)
0.6-24 (5)
2-20
1.5-150
0.7-38 (5)
0.3^*0 (10)
0.3-55 (5)
a Thickness in mm in parenthesis
194
1.43
1.37
1.70
1.41
1.35
2.59
1.45
1.52
2.24
1.49
1.40
2.4
1.53
2.0
4.0
3.4
2.4
1.66
1.74
6
5
13
6
4
35
7
8
27
8
5
31
9
21
59
51
31
12
14
b Two surfaces
with a b l a c k e n e d t a r g e t a r e a . T h e t h e r m o c o u p l e is
e v a c u a t e d for g r e a t e r sensitivity.
T h e s a m p l e a n d reference b e a m s fall alternately o n
t h e d e t e c t o r (the r o t a t i o n a l frequency of t h e sector
m i r r o r is usually 10-15 H z ) a n d a n y difference in the
intensities of t h e t w o b e a m s (caused, for e x a m p l e , by
s a m p l e a b s o r p t i o n a t t h a t w a v e l e n g t h ) results in a n
a l t e r n a t i n g signal a t t h e d e t e c t o r . I n t h e c o m m o n
optical-null s p e c t r o m e t e r , this a l t e r n a t i n g signal a c
tivates a servosystem t h a t m o v e s a c o m b - s h a p e d
Remarks
brittle
hygroscopic
reacts with metal
brittle
brittle
toxic
soft
soft
Figure 1
Optical system of an optical-null grating spectrometer
(courtesy of Perkin-Elmer Corporation)
Infrared
optical w e d g e in o r o u t of t h e reference b e a m in such a
w a y as t o cancel t h e difference in t h e b e a m s . T h e
m o t i o n of t h e c o m b is r e c o r d e d as a function of
wavelength o r w a v e n u m b e r t o p r o d u c e t h e ir spec
t r u m of t h e s a m p l e .
T h e o p e r a t i n g p a r a m e t e r s m a y b e varied t o suit t h e
p u r p o s e of the s p e c t r u m d e t e r m i n a t i o n . T h e o p e r a t o r
can vary the slit w i d t h ; t h e s c a n n i n g speed of t h e
s p e c t r o m e t e r , w h i c h m u s t be c o m p a t i b l e with t h e
response speed of t h e p e n (the electrical signal is
filtered t o r e d u c e t h e noise o r r a n d o m p e n fluctua
tions); a n d t h e gain of t h e s e r v o l o o p driving the p e n .
T h u s , the three basic variables a r e r e s o l u t i o n (slit
width), scan speed (response time) a n d noise level
(gain). A n y t w o of these p a r a m e t e r s m a y be a r b i
trarily chosen; t h e t h i r d is t h e n fixed by t h a t choice.
T h e r e l a t i o n s h i p between these variables is:
1
r e s o l u t i o n = ct '\S/N)
11 2
= 1/w
(4)
Spectroscopy
Table 3
1
Absorption maxima (cm" ) for spectrometer calibration
Indene (undiluted)
(0.2 mm cell)
(1) 3927.2 0.5
(2) 3139.5 0 . 4
(3) 2770.9 0.4
(4) 1915.3 0.3
(5) 1553.2 0.2
Polystyrene (solid film)
(1) 3027.1 0.3
(2) 2850.7 0.3
(3) 1944.0 1
(4) 1801.6 0.3
(5) 1601.4 0.3
(0.025 mm cell)
(6) 1361.1 0.2
(7) 1205.1 0.2
(8) 1018.5 0.3
(9) 830.5 0.3
(10) 590.8
(11) 381.4
(6)
(7)
(8)
(9)
1583.1
1154.3
1028.0
906.7
0.3
0.3
0.3
0.3
Sampling
Rather
thin
layers
of
sampleapproximately
0.01 m m for liquids a n d s o l i d s a r e o p t i m u m for
g o o d q u a l i t y ir spectra. O p t i m u m s a m p l e thickness is
195
Infrared
Spectroscopy
lOOh-
40
,000
3500
3000
2500
2000
1800
1600
1400
1200
1000
400
800
200
Wovenumber (cm" )
4000
3500
3000
2000
1800
1600
Wovenumber
1400
1200 1000
800
600
400
(cm" )
Figure 2
Spectra showing calibration bands for infrared spectrometers: top, indene; bottom, polystyrene film. Numbered
absorption maxima correspond to those given in Table 3 (courtesy of Perkin-Elmer Corporation)
a t t a i n e d w h e n several b a n d s h a v e t r a n s m i s s i o n o f less
t h a n 3 0 - 4 0 % , b u t n o b a n d h a s less t h a n 5 - 1 0 %
transmission. T h e background in nonabsorbing re
gions s h o u l d b e relatively flat a t a b o u t t h e 9 0 - 9 5 %
Figure 3
Optical schematic for an interferometer spectrometer:
A, ir source; B, laser; C, white light; D , white-light
detector; E, laser detector; F, sample chamber; and G, ir
detector (reproduced with permission from IBM
Instruments, Inc.)
196
t r a n s m i s s i o n level. T h e s a m p l e s h o u l d b e u n i f o r m
over t h e a r e a t h a t intercepts t h e s a m p l e b e a m ; t h a t is,
it s h o u l d n o t b e w e d g e d o r s h o w holes. G a s e s a r e
usually s a m p l e d in cells 2 - 1 0 c m in length, a l t h o u g h
multireflection cells o f over 1 k m i n p a t h length h a v e
been used for t r a c e analysis. M a n y s a m p l i n g m e t h o d s
a r e available, o f w h i c h t h e m o s t p o p u l a r a r e : for
liquids, s o l u t i o n in a n inert solvent a n d liquid film; f o r
solids, s o l u t i o n in a n inert solvent, as a p o w d e r mulled
with m i n e r a l oil ( t o r e d u c e scattering o f t h e r a d i a
tion), p o w d e r s u s p e n d e d in a K B r m a t r i x t h a t h a s
been pressed i n t o a t r a n s p a r e n t pellet, a n d a t t e n u a t e d
t o t a l reflectance. E a c h s a m p l i n g m e t h o d h a s a d v a n
tages a n d d r a w b a c k s ; t h e m e t h o d s h o u l d b e m a t c h e d
to the problem.
L i q u i d films a r e p r e p a r e d b y placing a d r o p o f
liquid o n t h e salt w i n d o w a n d " w i p i n g " t h e w i n d o w
against a flat surface. Alternatively, a n o t h e r w i n d o w
m a y b e pressed o n t h e s a m p l e t o form a s a n d w i c h .
S o m e trial a n d e r r o r will b e necessary t o achieve a
s p e c t r u m h a v i n g t h e p r o p e r intensities.
Soluble liquids a n d solids (except a m i n e s ) m a y b e
dissolved in i r - t r a n s m i t t i n g solvents, such a s C C 1 4 o r
1
C 2 C 1 4 (used in t h e 4 0 0 0 - 1 3 4 0 c m " region) a n d C S 2
Infrared
-1
4. Qualitative
Sample
Figure 4
Schematic representation of the radiation path in a
single-reflection internal-reflection element (after Smith
1979. John Wiley and Sons, New York. Reproduced
with permission)
Spectroscopy
Analysis
A n ir s p e c t r u m c o n t a i n s a n e n o r m o u s a m o u n t of
i n f o r m a t i o n , b u t m u c h of it is n o t readily e x t r a c t a b l e .
W i t h s o m e experience, it is possible t o recognize
certain w e l l - k n o w n g r o u p frequencies ( T a b l e 1). C o r
relation c h a r t s t h a t s h o w b a n d locations for the m a j o r
chemical g r o u p s a r e often used t o suggest structures
for further s t u d y a n d c o r r o b o r a t i o n . Existence of a
chemical g r o u p is usually verified a t several places in
197
Infrared
Spectroscopy
Table 4
Specific materials applications of ir spectroscopy
Area of application
Specific uses
Air pollution
Biomedical materials
Catalysts
Chemicals
Coatings, paints, varnishes and
resins
Drugs and pharmaceuticals
Fibers and textiles
Inorganic materials
Metals
Petroleum
Polymers and elastomers
Semiconductors
Wood and paper
198
Analysis
Ion Backscattering
intensity of t h e t r a n s m i t t e d r a d i a t i o n a n d is t h e
t r a n s m i t t a n c e , t h e B o u g u e r - B e e r l a w states t h a t t h e
a b s o r b a n c e A is
A = log 1 0 0 / % = log / 0 / / = abc
(5)
H e r e is a p r o p o r t i o n a l i t y c o n s t a n t related t o t h e
a b s o r p t i v e p o w e r of t h e a n a l y t e , b is t h e s a m p l e
thickness a n d c is t h e a n a l y t e c o n c e n t r a t i o n . It s h o u l d
be n o t e d t h a t m o s t ir s p e c t r o m e t e r s r e c o r d b a n d
intensities linearly in p e r c e n t t r a n s m i s s i o n , w h i c h
is a l o g a r i t h m i c function of c o n c e n t r a t i o n . T h u s ,
m e a s u r e m e n t s in % m u s t be c o n v e r t e d t o a b s o r b
ance before c a l c u l a t i o n s of c o n c e n t r a t i o n c a n b e
done.
Analysis of m i x t u r e s is carried o u t by m e a s u r i n g
a s t r o n g a n d preferably isolated b a n d of e a c h c o m
ponent. Either peak absorbance or integrated b a n d
a r e a (on a linear a b s o r b a n c e o r d i n a t e ) m a y b e used,
with t h e latter giving b e t t e r precision. If m u t u a l
interference o c c u r s (i.e., o v e r l a p p i n g a b s o r p t i o n s ) ,
c o r r e c t i o n s c a n be m a d e for t h e interference as
follows.
T h e a b s o r b a n c e Av a t a n y frequency is t h e s u m o f
t h e a b s o r b a n c e s of t h e /th species a t t h a t frequency, o r
Av = axbxcx
+ a2b2c2
+ ... + aibici
(6)
T h e a b s o r p t i o n coefficients a{ a r e d e t e r m i n e d b y
m e a s u r e m e n t s o n t h e p u r e c o m p o n e n t s , a t frequencies
c h o s e n t o give m a x i m u m a b s o r b a n c e for o n e c o m
p o n e n t a n d m i n i m u m a b s o r b a n c e for t h e o t h e r s .
Mixtures are analyzed by making absorbance
m e a s u r e m e n t s a t t h e selected frequencies a n d u s i n g
t h e results in a set of s i m u l t a n e o u s e q u a t i o n s , w h i c h
c a n b e solved b y m a t r i x inversion t o give t h e indi
vidual c o n c e n t r a t i o n s :
c, = IZ*/vA
I
(7)
Analysis
c o n c e n t r a t i o n . It is g o o d p r a c t i c e t o derive statistical
m e a s u r e s of a c c u r a c y a n d precision by repetitively
a n a l y z i n g i n d e p e n d e n t s t a n d a r d s over a p e r i o d of
several d a y s .
6.
Applications
Bibliography
American Society for Testing and Materials, Committee
E-13 1979 Manual on Practices in Molecular Spectros
copy. American Society for Testing and Materials, Phila
delphia, PA
Colthup , Daly L H, Wiberley S 1975 Introduction to
Infrared and Raman Spectroscopy. Academic Press, New
York
Craver C D (ed.) 1977 The Coblentz Society Deskbook of
Infrared Spectra. Coblentz Society, Kirkwood, MO
Griffiths R 1975 Chemical Infrared Fourier Transform
Spectroscopy. Wiley, New York
Griffiths R, Dehaseth J A, Azzaraga L V 1983 Capillary
GC/FT-IR. Analyt. Chem. 55A: 1361-87
Haaland D M, Easterling R G, Vopicka D A 1985 Multi
variate least-squares methods applied to the quantitative
spectral analysis of multicomponent samples. Appl. Spectrosc. 39: 73-84
Harrick J 1967 Internal Reflection Spectroscopy. Interscience, New York
Haslam J, Willis A, Squirrell D C 1979 Identification
and Analysis of Plastics, 2nd edn. Heyden, London
Infrared Spectroscopic Committee of the Chicago Society
for Coatings Technology 1979 An Infrared Spectroscopic
Atlas for the Coatings Industry. Federation of Societies
for Coating Technology, Philadelphia, PA
Koenig J L 1980 Chemical Microstructure of Polymer
Chains. Wiley, New York
Pouchert C J 1975 The Aldrich Library of Infrared Spectra,
2nd edn. Aldrich Chemical Company, Milwaukee, WI
Smith A L 1979 Applied Infrared Spectroscopy: Fundamen
tals, Techniques and Analytical Problem-Solving. Wiley,
New York
A . L. S m i t h
[Dow Corning, Midland, Michigan, USA]
199
Ion Backscattering
Analysis
1. Rutherford
Backscattering
200
Detector
Figure 1
Schematic representation of the experimental geometry for
the backscattering technique
Ion Backscattering
incident
beam
Analysis
t h e r a t e of c h a n g e of loss p e r u n i t p a t h d o e s n o t
c h a n g e a p p r e c i a b l y , there is a linear relation between
energy loss AE a n d d e p t h t t h a t c a n be expressed as
E0
AE=[S]t
(2)
9x){dEldx)Em
+ (\/cose2)(dE/dx)Eoax
Scattered
energy
Figure 2
Schematic representation of the Rutherford backscattering
yield from a thick target with surface impurities
&
m cos 9 + (M -m
E' =
~E^
t0
(3)
s i n 0 ) 1/22
L
0)
[S] = NKMe(Em)
+ (7V7|cos 0 | ) e ( E o u )t
(4)
QQaNt
(5)
Ion Backscattering
Analysis
a n d t h e detailed formalism a n d a n u m e r i c a l m e t h o d
h a s been d e v e l o p e d b y Brice (1973). C o m p u t e r a n a l y
sis of c o m p l e x b a c k s c a t t e r i n g spectra h a s been
developed b y Ziegler et al. (1975b).
T h e r e a r e limitations t o b a c k s c a t t e r i n g s p e c t r o m
etry which m u s t b e b o r n e in m i n d w h e n c o n s i d e r i n g
t h e a p p l i c a t i o n o f t h e t e c h n i q u e t o specific p r o b l e m s .
T h e s a m p l e d e p t h t h a t c a n b e a n a l y z e d with 2 M e V
4
+
H e ions is a b o u t 1-2 . A l s o , t h e b a c k s c a t t e r i n g
t e c h n i q u e is n o t highly element specific, a n d for
h e a v y - m a s s e l e m e n t s it is difficult t o o b t a i n g o o d m a s s
resolution. I n this case, i o n - i n d u c e d rays c a n b e used
for element identification. A n o t h e r limitation is t h a t it
is n o t always possible t o completely identify t h e
chemical p h a s e s t h a t a r e p r e s e n t in a c o m p o u n d .
C o m p l e m e n t a r y t e c h n i q u e s like s e c o n d a r y - i o n m a s s
s p e c t r o s c o p y ( S I M S ) a n d x-ray diffraction in c o n j u n c
tion with b a c k s c a t t e r i n g studies p r o v i d e i n f o r m a t i o n
o n p h a s e f o r m a t i o n a n d r e a c t i o n kinetics. T h e sensi
tivity of t h e b a c k s c a t t e r i n g t e c h n i q u e for d e t e c t i o n of
low-mass elements o n a h i g h - m a s s s u b s t r a t e is p o o r ,
and nuclear reactions or resonance techniques must
be used t o o b t a i n q u a n t i t a t i v e i n f o r m a t i o n o n trace
a m o u n t s of these elements. T h e s e t e c h n i q u e s h a v e
been reviewed b y W o l i c k i (1975) a n d C h u et al.
(1978).
Energy ( M e V )
Channel number
Figure 3
4
+
Backscattered energy spectra for 2 MeV H e ions from
(a) lOOnm platinum sputter deposited on a silicon
substrate and (b) sintered at 375 C for 25 nm in an argon
atmosphere to form a Pt-Si layer 140 nm thick on a
silicon substrate
(^pJNsi)
2.
Applications
202
= (APt/Asi)(aPilasi)
(6)
is e q u a l t o u n i t y ( t o within 1%). A n o t h e r a d v a n t a g e
of these m e a s u r e m e n t s is t h a t t h e s t o i c h i o m e t r y c a n
generally b e d e t e r m i n e d directly from t h e spectra.
T h e c o m p o s i t i o n c a n also b e d e t e r m i n e d from t h e
heights of t h e p l a t i n u m a n d silicon p l a t e a u s in t h e
b a c k s c a t t e r i n g spectra a s
= ^sJoPt)(HPi/HSi)(AEPi/AEsi)
(7)
In F i g . 3 , t h e r a t i o AEPJAESi is 1.15 a n d t h e m e a s u r e d
r a t i o HPt/Hsi is 27.5. Inserting values of , AE a n d
in t h e a b o v e e q u a t i o n gives NPJNsi = 1 ( t o within
2 % ) . H e n c e , if t h e surface i m p u r i t y is of high m a s s o n
a l o w - m a s s s u b s t r a t e , t h e precise values of Q a n d
need n o t b e k n o w n .
M e t a l l i z a t i o n plays a large role in t h e success o r
failure of integrated-circuit t e c h n o l o g y . I n o r d e r t o
m a k e electrical c o n n e c t i o n s b e t w e e n t h e devices a n d
the o u t s i d e w o r l d , it is necessary t o d e p o s i t thin m e t a l
layers for c o n d u c t i n g p a t h s . T h e r e a r e a h o s t of
p r o b l e m s associated with t h e metallization process,
all of which stem from t h e fact t h a t thin-film r e a c t i o n s
o c c u r a t relatively low t e m p e r a t u r e s . T o p r e v e n t c o m
p o u n d f o r m a t i o n a n i n t e r m e d i a t e layer is d e p o s i t e d a s
a b a r r i e r layer. F o r e x a m p l e , a thin layer of S i 0 2 h a s
been d e p o s i t e d in b e t w e e n N b S i 2 a n d a silicon s u b
s t r a t e ( C h o w et al. 1982). F i g u r e 4 a s h o w s t h e 2 M e V
4
+
H e s p e c t r u m for a n N b S i 2 thin film (406.4 n m ) o n
a n S i 0 2 - S i s u b s t r a t e . T h e silicide films were s p u t t e r e d
from a h o t - p r e s s e d alloy target of stoichiometric
c o m p o s i t i o n S i : N b = 2 o n t o h e a t e d (350 C) s u b
strates. O x i d a t i o n w a s carried o u t in d r y oxygen
Ion Backscattering
Energy (MeV)
0.8
cn
Si0 2
.0 in S i 0 2
X *
\
0 in Nb205 Si
i
~SiO,+
*
Energy (MeV)
S
1.0
1.2
i
-Hr^-NboO.-SiO,
2
2^5
4
uS b s et r a t
140 nm
2 MeV H e ^ .
ft\ 7^ ,
Nb at
i ? ? S i i ^ surface
(C)
-.. 0 at surface
', I Si in NbSi,
I I
Si in Nb205-Si0,
'"""w^
1 Si
surface
"
BF2
(b)
.
5
m
^ channelling
peak corresponds to ionimplanted damage zone
0
i.o
'**V l
^4*^:
S ii
IOO
()
200
Si surface
Channel number
Figure 4
4
+
Backscattered energy spectra for 2 MeV H e ions from
(a) 406.4 nm NbSi 2 polycrystalline film deposited on
Si0 2-Si substrate; (b) thermal oxidation of NbSi 2 layer
carried out in dry oxygen at 600 C for 15 min; (c) thermal
oxidation of NbSi 2 layer carried out in dry oxygen at
650 C for 15 min. NbSi 2 layer is not completely oxidized
(after Chow et al. 1982)
Channelling
Axial o r p l a n a r c h a n n e l l i n g o c c u r s w h e n a c o l l i m a t e d
energetic b e a m o f i o n s (e.g., 2 M e V h e l i u m ions) is
incident o n a single crystal a l o n g a n axial o r p l a n a r
direction. T h e r o w s o r p l a n e s o f a t o m s a c t a s p o t e n t i a l
b a r r i e r s such t h a t t h e i o n s u n d e r g o a series o f c o r r e
lated screened C o u l o m b i c collisions. T h e s e smallangle collisions result in t h e c h a n n e l l e d i o n s b e i n g
steered b y t h e r o w s a n d p l a n e s t o w a r d s t h e c e n t r a l
300
400
500
600
Channel number
Si in NbSi 2
3.
Analysis
Figure 5
Random and (lOO)-aligned backscattering
spectra
for a
l5
2
silicon
crystal implanted with (2 1 0 c m ~ at +25 keV)
+
BF 2 ions. The amorphous zone created by BF 2 implant is
seen in the channelling spectrum
c h a n n e l region b e t w e e n t h e r o w s o r p l a n e s . H e n c e , in
terms of backscattering spectrometry, channelling
effects p r o d u c e strikingly large c h a n g e s in t h e yield o f
b a c k s c a t t e r e d particles a s t h e o r i e n t a t i o n of t h e single
crystal is c h a n g e d w i t h respect t o t h e incident b e a m .
C h a n n e l l i n g of energetic i o n s is well described in t h e
l i t e r a t u r e ( M a y e r et al. 1970, D e a r n a l e y 1973, M o r
g a n 1973, G e m m e l l 1974, P i c r a u x 1975). By c o m b i n
ing c h a n n e l l i n g with b a c k s c a t t e r i n g m e a s u r e m e n t s ,
c r y s t a l l o g r a p h i c i n f o r m a t i o n s u c h a s lattice site loca
t i o n o f i m p u r i t i e s o r lattice d i s o r d e r c a n b e deter
m i n e d ( M o r g a n 1973). F i g u r e 5 s h o w s a c h a n n e l l i n g
+
b a c k s c a t t e r i n g s p e c t r u m from a B F 2 - i m p l a n t e d sili
c o n crystal. F i g u r e 6 s h o w s t h e effect o f t h e r m a l a n d
+
laser a n n e a l i n g o n t h e d a m a g e c r e a t e d b y a B F 2
implant. T h e a m o r p h o u s portion of the as-implanted
layer is a n n e a l e d t h e r m a l l y o r b y laser.
4. Microprobe
Analysis
A recent a p p l i c a t i o n of t h e b a c k s c a t t e r i n g t e c h n i q u e
h a s b e e n in t h e n o n d e s t r u c t i v e analysis o f microelec
t r o n i c circuits. T h e utility of these i o n - b e a m tech
n i q u e s h a s b e e n greatly increased b y t h e i n v e n t i o n o f
lenses c a p a b l e o f focusing h i g h - e n e r g y h e a v y - i o n
beams to micrometer dimensions. The combination of
i o n - b e a m analysis a n d m i c r o m e t e r - d i m e n s i o n i o n
b e a m s yields a powerful, n o n d e s t r u c t i v e m e t h o d for
m a t e r i a l s analysis. F i g u r e 7 s h o w s a line-scan b a c k s c a t t e r i n g s p e c t r u m t a k e n w i t h a recently c o n s t r u c t e d
m i c r o b e a m system a t t h e S a n d i a N a t i o n a l L a b o r a t o r
4
+
ies, N e w M e x i c o ( D o y l e et al. 1981). A 3 M e V H e
203
Ion Backscattering
Analysis
Energy
0 8
nuclear m i c r o p r o b e s in microelectronics a p p e a r s t o be
especially attractive.
(MeV)
i.O
*>'.".
random
Bibliography
>.>....
t h e r m a l l ye annealed
C , 15 min
/ 9 5 0
r^ :*^....
:
^^iSJii*...-laser annealed
300
400
reduction in damage by
t h e r m a l a n d laser
annealing
C h a n n e l number
Figure 6
Random and (lOO)-aligned backscattering
spectra for a
+
silicon crystal implanted with BF 2
64
channels
Figure 7
A line-scan
backscattering
spectra produced by analysis of
4
+
a 3 MeV H e beam of 2-5 from 80 nm thick (30
wide) gold grid on a silicon substrate
204
J
Junction Transient Spectroscopy
T h e necessity of m o n i t o r i n g electrically active defects
in crystalline s e m i c o n d u c t o r m a t e r i a l s h a s led t o t h e
d e v e l o p m e n t of j u n c t i o n t r a n s i e n t m e a s u r e m e n t tech
niques. T h e m o s t i m p o r t a n t of t h e v a r i o u s m e t h o d s is
deep-level t r a n s i e n t s p e c t r o s c o p y ( D L T S ) w h i c h h a s
p r o v e n t o b e a powerful research tool for c h a r a c t e r i z
ing t h e electrical p r o p e r t i e s of p o i n t defects in b o t h
elemental a n d c o m p o u n d s e m i c o n d u c t o r s . T h i s sensi
tive s p e c t r o s c o p y m e a s u r e s deep-level defect c o n c e n
9
3
t r a t i o n s as low as 10 c m " in t h e j u n c t i o n region of a
s e m i c o n d u c t o r device. Since t h e processed device g e o
m e t r y c a n often be used a s a s a m p l e configuration,
D L T S can be a nondestructive measurement. In addi
tion t o the c o n c e n t r a t i o n of deep-level defects in t h e
depletion region, D L T S c a n r o u t i n e l y d e t e r m i n e t h e
spatial profile of t r a p s , t h e energy level for carrier
emission from the defect a n d t h e m a j o r i t y carrier
c a p t u r e cross section. T h e s p e c t r o s c o p i c n a t u r e of
j u n c t i o n t r a n s i e n t m e a s u r e m e n t s h a s b e e n exploited
in e x p e r i m e n t s t h a t h a v e led t o t h e discovery of
r e c o m b i n a t i o n - e n h a n c e d defect diffusion, t h e first
o b s e r v a t i o n of m e t a s t a b l e defect r e a c t i o n s , a n d t h e
c o r r e l a t i o n of energy levels with impurities a n d
r a d i a t i o n - p r o d u c e d p o i n t defects.
1. Junction
Transient
Measurements
J u n c t i o n t r a n s i e n t spectroscopies m o n i t o r t h e electri
cal effects of defects w i t h i n t h e d e p l e t i o n region of a
s e m i c o n d u c t o r j u n c t i o n . A lattice defect (such a s a
vacancy, a n interstitial o r a dislocation), a n i m p u r i t y
(either s u b s t i t u t i o n a l o r interstitial) o r a c o m p l e x of
these simple defects in a crystal c a n i n t r o d u c e electro
nic energy states o r levels i n t o t h e f o r b i d d e n g a p of a
s e m i c o n d u c t o r . I n t e n t i o n a l l y p r o c e s s e d d o p a n t s such
as arsenic o r b o r o n p r o d u c e shallow states in t h e
energy g a p , a p p r o x i m a t e l y 0.03-0.06 eV from their
related b a n d edges. T h e d e e p states, w h i c h a r e
m e a s u r e d b y these spectroscopies, a r e t h o s e w h o s e
energy levels fall d e e p e r in t h e b a n d g a p t h a n
the d o p a n t levels. E v e n small
concentrations
of d e e p levels c a n c o n t r o l t h e carrier lifetime in
semiconductors.
T h e a p p l i c a t i o n of a reverse bias t o a s e m i c o n d u c
t o r j u n c t i o n s t r u c t u r e creates a d e p l e t i o n region free
of m o b i l e carriers. T h e j u n c t i o n c a p a c i t a n c e is a n a l o
g o u s t o t h a t of a parallel-plate c a p a c i t o r w i t h t h e p l a t e
s e p a r a t i o n e q u i v a l e n t t o t h e w i d t h of t h e depleted
region. T h e presence of o c c u p i e d d e e p levels in t h e
m a t e r i a l c h a n g e s this j u n c t i o n c a p a c i t a n c e . All t r a n
sient spectroscopies e m p l o y s o m e m e t h o d t o p e r t u r b
Bias
supply
Capacitance
meter
:4:s
(out)
Pulse
Itransformerl
Pulse
generator
Ref
X-Y
recorder
7"(mV)
Scope
Lock-In output
Lock-in
amplifier
Mixer
Figure 1
Block diagram of a DLTS system employing a capacitance
meter and lock-in amplifier
205
Junction
Transient
Spectroscopy
b a n d edge. A similar expression c a n be w r i t t e n for
hole emission from a defect t o t h e valence b a n d .
E x p e r i m e n t a l l y , the a c t i v a t i o n energy for carrier
emission from a defect t o t h e nearest b a n d edge ET is
o b t a i n e d from t h e slope of a n A r r h e n i u s p l o t of In
2
!
T en~ vs 1 0 0 0 / using E q n . (1). T h e emission r a t e en is
the inverse of t h e time c o n s t a n t of t h e m e a s u r e d
t r a n s i e n t a n d m u s t be d e t e r m i n e d i n d e p e n d e n t l y for
each e x p e r i m e n t a l D L T S system. T h e value of is the
t e m p e r a t u r e of t h e spectral p e a k m a x i m u m .
T h e s e c o n d process i m p o r t a n t in analyzing j u n c t i o n
t r a n s i e n t m e a s u r e m e n t s is the c a p t u r e of carriers at a
- 1
defect. Defect c a p t u r e of majority carriers c ( s ) fol
lows t h e r e l a t i o n s h i p
E,(O.I8eV)
c = <>
(2)
- 3
w h e r e is t h e m a j o r i t y carrier c o n c e n t r a t i o n ( c m ) ,
<v> is t h e t h e r m a l velocity of t h e carriers a n d is the
2
m a j o r i t y carrier c a p t u r e cross section ( c m ) . T h e de
fect c a p t u r e r a t e c is d e t e r m i n e d experimentally a n d
t h e calculated defect c a p t u r e cross section is used with
t h e defect a c t i v a t i o n energy ET t o identify the spectral
feature.
3. Semiconductor
Temperature (K)
Figure 2
DLTS spectra of radiation-induced defects in
phosphorus-doped silicon
2. DLTS
Theory
A n u n d e r s t a n d i n g of carrier emission a n d c a p t u r e a t a
defect in a s e m i c o n d u c t o r j u n c t i o n d e p l e t i o n region is
necessary t o a n a l y z e the o u t p u t of j u n c t i o n spectros
copies.
T h e r m a l carrier emission from a d e e p level follows
- 1
B o l t z m a n n statistics. T h e emission r a t e en ( s ) of a n
electron from a defect of energy ET (eV) is given by
en ~ JJLi-
[ - (Ec - ET)/kT]
e x p
(1)
206
Materials
Characterization
T r a n s i e n t s p e c t r o s c o p y requires t h e filling a n d e m p t y
ing of t r a p s w i t h i n a j u n c t i o n d e p l e t i o n region. T h e r e
fore, devices such a s S c h o t t k y b a r r i e r s , p-n j u n c t i o n s ,
metal-oxide semiconductor structures,
field-effect
t r a n s i s t o r s , light-emitting d i o d e s a n d s e m i c o n d u c t o r
lasers a r e p r o p e r test s t r u c t u r e s . S c h o t t k y barriers
a n d p-n j u n c t i o n s a r e easily fabricated in a l a b o r a
t o r y e n v i r o n m e n t a n d a r e used t o characterize b u l k
materials.
T h e spectroscopic detection limit is a p p r o x i m a t e l y
5
1 0 " times t h e b u l k free carrier c o n c e n t r a t i o n . T h e r e
fore, these m e t h o d s a r e least effective w h e n applied t o
heavily d o p e d s e m i c o n d u c t o r s .
D L T S d o e s n o t p r o v i d e s t r u c t u r a l o r chemical
i n f o r m a t i o n a b o u t a defect. H o w e v e r , extensive
m a t e r i a l s studies o n defects in silicon, in c o n j u n c t i o n
with chemically specific m e a s u r e m e n t s such as p h o t o luminescence, infrared s p e c t r o s c o p y a n d electron
p a r a m a g n e t i c r e s o n a n c e h a v e resulted in t h e identifi
c a t i o n of over 200 D L T S p e a k s . A representative
library is given in T a b l e 1. T h e defect identity (i m e a n s
interstitial, s indicates s u b s t i t u t i o n a l a n d V refers t o
v a c a n c y ) , t h e t e m p e r a t u r e of t h e spectral p e a k m a x i
m u m (at a n i n s t r u m e n t time c o n s t a n t of 1.8 ms) ( ) ,
t h e t h e r m a l a c t i v a t i o n energy for carrier emission t o
the b a n d edge ET (eV) a n d the majority carrier c a p t u r e
2
cross section ( c m ) a r e listed. C o m p a r i s o n s o f
u n k n o w n spectra with this table d o n o t a u t o m a t i c a l l y
g u a r a n t e e firm defect identifications. K n o w l e d g e of
t h e s a m p l e m a t e r i a l a n d c o n s i d e r a t i o n of its p r o c e s s
ing history is crucial. Often, a d d i t i o n a l e x p e r i m e n t s
a r e required for u n a m b i g u o u s defect identification.
Junction
Transient
Spectroscopy
Table 1
DLTS library of defects in silicon
Defect
()
Ag
Ag
Au
Au
Au-Fe
Cr rB c
184
286
288
173
170
123
108
112
243
267
59
C r
CU;BS
Cu
F e
F
ie B
r s
Fe rAl s
Fe rAl s
Fej-Ga,
Fe-In s
Fe rIn s
Mn rB s
Miij
Mn;
Mnj
Mo
N i rB s
Ni
Pds
Pd-V
Pts
Disloc
Disloc
Disloc
oD
oD
4. DLTS
251
207
68
216
191
88
257
174
225
206
288
58
(eV)
18
(10 cm )
H(0.36)
400
E(0.51)
100
E(0.53)
100
H(0.35)
1000
E(0.35)
6000
H(0.28)
>5000
E(0.22)
2000
H(0.22)
>60000
H(0.41)
80000
H(0.45)
>4000
H(0.10)
10000
MH(0.13)
MH(0.20)
MH(0.14)
MH(0.23)
MH(0.15)
MH(0.27)
H(0.55)
H(0.25)
E(0.11)
E(0.42)
H(0.28)
1000
H(0.14)
500
E(0.43)
100
E(0.22)
5000
E(0.18)
5000
H(0.32)
800
E(0.38)
4000
H(0.35)
50
E(0.63)
>1000
E(0.07)
E(0.15)
Applications
D L T S research h a s m a d e a n e x t r a o r d i n a r y c o n t r i b u
tion to the current u n d e r s t a n d i n g of defect reactions in
semiconductors. T h e p h e n o m e n o n of r e c o m b i n a t i o n e n h a n c e d defect reactions w a s first discovered in G a A s
a n d analyzed by j u n c t i o n spectroscopy. T h e localized
energy available at a defect as the result of the re
c o m b i n a t i o n of electrons a n d holes can cause en
hanced defect diffusion a n d h a s p r o v e d t o be t h e
reason for e n h a n c e d d e g r a d a t i o n of injection m o d e
semiconductor devices such as G a A s lasers.
C h a r g e - s t a t e - c o n t r o l l e d defect m e t a s t a b i l i t y w a s
first investigated by D L T S . T h e M - c e n t e r in I n P w a s
the first r e p o r t e d m e t a s t a b l e defect a n d it exhibited
different s t r u c t u r a l c o n f i g u r a t i o n s d e p e n d i n g o n t h e
c h a r g e state of t h e defect. S p e c t r o s c o p i c investiga
tions of silicon, G a A s a n d A l G a A s h a v e u n c o v e r e d
a d d i t i o n a l e x a m p l e s of defect m e t a s t a b i l i t y , a n d these
studies h a v e led t o a n u n d e r s t a n d i n g of configura t i o n a l t r a n s f o r m a t i o n s in t e r m s of b o n d i n g c h a n g e s
at the defect site.
T h e i n t r o d u c t i o n of a t o m i c h y d r o g e n w a s initially
s h o w n by D L T S t o p a s s i v a t e t h e electrical activity
p o i n t defects in silicon resulting from laser a n n e a l i n g .
S u b s e q u e n t t r a n s i e n t s p e c t r o s c o p y h a s revealed
h y d r o g e n p a s s i v a t i o n of d e e p a n d shallow levels in
G a A s , G a P , G a A l A s a n d silicon.
Defect
()
V
V
76
79
131
241
142
98
215
235
224
192
69
282
203
v-v
v-v
v-v
v
~i
P-V
As-V
Sb-V
Sn-V
Sn-V
Al-V
Al,
Al rAl s
Bj
B
i
B-V
B rB s
B.-C.
Bj-O;
Cj
Cj
C sSi-C s
C,-Cs
Ps-Ci
Ps-Ci
87
223
190
64
165
206
(eV)
,8
(10 cm )
E(0.09)
H(0.14)
30
H(0.21)
200
E(0.40)
2000
E(0.23)
400
E(0.17)
1000
E(0.44)
4000
E(0.47)
E(0.44)
40
H(0.32)
9
H(0.07)
20
H(0.52)
> 100
H(0.25)
7
H(0.23)
E(0.13)
>100
E(0.45)
700
H(0.32)
H(0.30)
800 000
H(0.29)
E(0.26)
E(0.12)
H(0.27)
70
H(0.36)
70
ME(0.17)
40
ME(0.10)
MH(0.09)
MH(0.05)
ME(0.30)
10
ME(0.21)
ME(0.23)
ME(0.29)
Recently, engineers h a v e b e g u n t o a p p l y j u n c t i o n
t r a n s i e n t t e c h n i q u e s t o t h e e x a m i n a t i o n of t r a c e c o n
t a m i n a t i o n a n d p r o c e s s - i n d u c e d defects in semicon
d u c t o r device m a n u f a c t u r e . D L T S h a s been e m p l o y e d
t o investigate c o n t a m i n a t i o n i n t r o d u c e d b y process
ing furnaces a n d epitaxial r e a c t o r s . D L T S feasibility
studies h a v e e v a l u a t e d n e w p r o c e s s i n g t e c h n i q u e s
such as l o w - t e m p e r a t u r e , h i g h - p r e s s u r e o x i d a t i o n a n d
rapid thermal annealing. Ion-implantation-induced
t r a p s h a v e also been c h a r a c t e r i z e d b y D L T S .
D L T S is also used t o a n a l y z e t h e effect of d e e p
levels o n device p e r f o r m a n c e . D L T S research h a s
c o r r e l a t e d t h e c o n c e n t r a t i o n of gold levels as well as
v a c a n c y o x y g e n a n d d i v a c a n c y defects with t h e
r e d u c t i o n of majority-carrier lifetime in silicon d e
vices. T h e presence of defects related t o silver a n d
nickel w a s s h o w n t o c a u s e excessive l e a k a g e c u r r e n t in
silicon p l a n a r d i o d e s . Devices t h a t exhibited c h a n g e s
in resistivity a n d m i n o r i t y - c a r r i e r lifetime d u r i n g
p r o c e s s i n g were investigated b y j u n c t i o n t r a n s i e n t
m e t h o d s revealing interstitial i r o n a s t h e c a u s e .
D L T S h a s m a t u r e d as a s e m i c o n d u c t o r c h a r a c t e r
ization t e c h n i q u e a n d c o m m e r c i a l l y m a n u f a c t u r e d
s p e c t r o m e t e r s a r e n o w available. It a p p e a r s , there
fore, t h a t D L T S will s o o n b e utilized regularly in
s e m i c o n d u c t o r device m a n u f a c t u r i n g facilities as a
p r o c e s s m o n i t o r . R e s e a r c h is increasing the n u m b e r of
207
Junction
Transient
Spectroscopy
Bibliography
Benton J L, Kimerling L C 1982 Capacitance transient
spectroscopy of trace contamination in silicon. J. Electrochem. Soc. 129(9): 2098-102
208
L
Laser Microprobe Mass Spectrometry
a r e s h o w n in F i g . 1 a l t h o u g h t h e precise a r r a n g e m e n t
is d e p e n d e n t o n t h e p a r t i c u l a r i n s t r u m e n t used.
G e n e r a l l y , o p e r a t i o n c a n be either in t r a n s m i s s i o n
m o d e , with laser i r r a d i a t i o n of o n e side of a thin
( ~ 1 ) s a m p l e a n d ion e x t r a c t i o n from t h e o p p o s i t e
side, o r in reflection m o d e . T h e reflection m o d e is n o t
only essential for the analysis of b u l k s a m p l e s b u t also
a p p e a r s t o be satisfactory for thin s a m p l e s which are
p e r f o r a t e d by t h e laser pulse.
T h e s a m p l e is viewed t h r o u g h a high-resolution
optical m i c r o s c o p e system w h i c h also serves t o focus
t h e laser pulse o n t o t h e s a m p l e surface. T h e specific
a r e a for analysis is identified a n d defined by the
focused s p o t of a n auxiliary c o n t i n u o u s - w a v e h e l i u m n e o n laser.
In t h e i n s t r u m e n t illustrated in Fig. 1, s a m p l e
viewing, laser i r r a d i a t i o n a n d ion e x t r a c t i o n a r e all
p e r f o r m e d n o r m a l t o the s a m p l e surface by extracting
ions for analysis t h r o u g h a series of axial a p e r t u r e s in
t h e reflecting (Cassegrain) e l e m e n t s of t h e m i c r o s c o p e
objective lens. O t h e r i n s t r u m e n t s use n o n - n o r m a l
incidence of t h e laser b e a m a n d so avoid the Casse
g r a i n lens. A high-stability, precision s a m p l e m a n i p u
l a t o r p r o v i d e s x, y a n d t r a n s l a t i o n s , with o n e axis of
360 r o t a t i o n , a n d p o s i t i o n s t h e s a m p l e with a n accur
acy b e t t e r t h a n 1 . T h e m a x i m u m s a m p l e size is
i n s t r u m e n t d e p e n d e n t b u t specimen c h a m b e r s h a v e
been m a d e t o h a n d l e several s e m i - c o n d u c t o r wafers
200 m m s q u a r e a n d 10 m m in d e p t h , for e x a m p l e .
Although instruments are m a d e to ultrahigh vacuum
s t a n d a r d s , such c o n d i t i o n s generally a r e n o t required
T h e c o m b i n a t i o n of a pulsed, m i c r o f o c u s e d laser
b e a m with a time-of-flight m a s s s p e c t r o m e t e r h a s
allowed t h e d e v e l o p m e n t of c o m m e r c i a l l y available
laser m i c r o p r o b e s ( H i l l e n k a m p et al. 1975, D i n g l e et
al. 1981) w h i c h c a n aid t h e c h a r a c t e r i z a t i o n of m a t e r
ials. In such i n s t r u m e n t s ( k n o w n as L A M M S ) , a s h o r t
pulse of h i g h - e n e r g y laser r a d i a t i o n is focused o n t o
the surface of t h e s a m p l e . T h e very high p o w e r density
in the focused s p o t results in e v a p o r a t i o n a n d p a r t i a l
3
i o n i z a t i o n of a small v o l u m e (a few ) of m a t e r i a l
from t h e s a m p l e surface. A n a l y s i s of t h e resulting i o n s
(either positive o r negative) is effected b y m e a s u r i n g ,
using a time-of-flight m a s s s p e c t r o m e t e r , t h e m a s s - t o c h a r g e r a t i o of either t h e positive o r negative i o n s .
A l t h o u g h a t p r e s e n t t h e t e c h n i q u e is only semi
q u a n t i t a t i v e , it h a s m a n y features w h i c h c a n b e used
with a d v a n t a g e . T h e s e include t h e d e t e c t i o n of i o n s
from all elements (with i s o t o p e d i s c r i m i n a t i o n ) a n d
from m o l e c u l a r species; r e a s o n a b l e trace sensitivity
(to p p m levels); ability t o a n a l y z e a wide r a n g e of
s a m p l e m a t e r i a l s ( c o n d u c t o r s , i n s u l a t o r s a n d organics); m i n i m a l s a m p l e p r e p a r a t i o n ; a n d speed a n d
simplicity of analysis. O f p a r t i c u l a r interest is its role
as a m i c r o p r o b e for d e t e c t i n g o r g a n i c species a n d t h e
light elements, including h y d r o g e n .
1.
Instrumentation
Eyepiece
Pilot
laser
He:Ne
-4s
Pulsed laser
-switched
N d : YAG
Frequency
Transmission
mode optics
converter
Ion
deflector
Specimen
Light
objective
ens
(transmission
Ion
detector
mode)
Ion-extraction
optics
and
objective
light
lens
(reflection
Transient
recorder
Preamplifer
mode)
Figure 1
Schematic diagram of a typical laser microprobe mass spectrometer (Cambridge Mass Spectrometry Ltd. LIMA III)
209
Laser Microprobe
Mass
Spectrometry
(1)
T h e velocity t h a t is r e a c h e d b y a particle of m a s s
m is related t o t h e a b o v e kinetic energy by t h e classical
equation
E = $mv2
(2)
By c o m b i n i n g the a b o v e e q u a t i o n s a n d r e a r r a n g i n g ,
Figure 2
Scanning electron micrograph of laser crater made at
relatively high input laser energy
s p e c t r o m e t e r drift t u b e using either a venetian-blind
electron multiplier o r m i c r o c h a n n e l plates. A fast
(e.g., 60 M H z ) t r a n s i e n t r e c o r d e r a c q u i r e s t h e result
ing amplified signals t o p r o v i d e a s p e c t r u m of ion
a b u n d a n c e versus time. D a t a a r e usually transferred
to a m i c r o c o m p u t e r for c o n v e r s i o n t o ion a b u n d a n c e
versus m a s s - t o - c h a r g e r a t i o , for further d a t a analysis
o r m a n i p u l a t i o n , a n d / o r for o u t p u t as a video display,
h a r d c o p y o r p e r m a n e n t s t o r a g e o n m a g n e t i c disk.
(3)
T h u s , ions of different m a s s - t o - c h a r g e r a t i o s will
a t t a i n different t e r m i n a l velocities a n d , if allowed t o
drift in a field-free region of length / (the drift t u b e ) ,
will be s e p a r a t e d in time t. A c c o r d i n g l y , a n ion
d e t e c t o r a t t h e e n d of t h e drift t u b e s h o u l d receive a
series of precise p a c k e t s of i o n s , e a c h c o r r e s p o n d i n g
t o a specific m a s s - t o - c h a r g e r a t i o .
In fact, the ions f o r m e d b y laser a b l a t i o n d o n o t all
h a v e zero kinetic energy a n d so the time-of-flight m a s s
s p e c t r o m e t e r generally includes s o m e w a y of m a k i n g
a s e c o n d - o r d e r c o r r e c t i o n of t h e relatively large
s p r e a d in initial ion energies. In essence, t h e a i m is t o
give the higher-energy ions a slightly longer flightpath
so t h a t all t h e i o n s of a given m a s s - t o - c h a r g e r a t i o
arrive a t t h e e n d of t h e flight t u b e t o g e t h e r . T h i s is
a c c o m p l i s h e d either b y using a folded drift t u b e (as
s h o w n in F i g . 1) in o r d e r t o i n c o r p o r a t e a n electrosta
tic reflecting element ( M a m y r i n et al. 1973) o r b y a
curved flight t u b e i n c o r p o r a t i n g a t o r o i d a l electrosta
tic field ( P o s c h e n r i e d e r 1972). I n b o t h cases, t h e i o n s
of h i g h e r energy (which a r e travelling faster) p e n
e t r a t e further i n t o t h e electrostatic field before being
repelled b y t h e field t h a n t h o s e of lower energy ( b u t
s a m e m a s s - t o - c h a r g e r a t i o ) ; hence a longer
flightpath
is t a k e n b y t h e higher-energy i o n s .
I o n s a r e detected a t the e n d of the m a s s -
210
2.
Performance
T h e spatial r e s o l u t i o n of t h e t e c h n i q u e is related t o
the d i m e n s i o n s of t h e laser-induced crater, c o m m o n l y
from 3 t o < 1 in d i a m e t e r a n d s o m e t e n t h s of a
m i c r o m e t e r in d e p t h a t a typical p o w e r density of
1 0 14 W m ~ 2 (see Fig. 2). C r a t e r characteristics d e p e n d
strongly o n s a m p l e m a t e r i a l a n d o n laser p o w e r
density. I n p a r t i c u l a r , the d e p t h r e m o v e d p e r pulse
h a s been varied from < 0.1 for a silicon nitride
layer o n a microcircuit t o ~ 30 in polyvinyl
chloride) ( P V C ) . T h e u l t i m a t e limit of lateral resolu
tion is g o v e r n e d by t h e need t o focus the laser b e a m
o n t o t h e surface of t h e s a m p l e a n d so it is unlikely t o
fall m u c h below 1 . H o w e v e r , there is scope for t h e
t e c h n i q u e t o b e c o m e m o r e surface specific by r e m o v
ing a few n a n o m e t e r s in d e p t h , o r even a surface
m o n o l a y e r . A t present, relatively high laser p o w e r s
a r e used in o r d e r n o t only t o r e m o v e m a t e r i a l from
t h e surface of a s a m p l e , b u t also t o c a u s e e n o u g h
i o n i z a t i o n so t h a t a signal c a n be collected. Interest is
g r o w i n g in t h e use of " p o s t - i o n i z a t i o n " which is a
process t h a t uses a second energy source t o ionize
n e u t r a l s (which a r e m o r e a b u n d a n t t h a n ions) f o r m e d
by t h e original laser pulse. If this is successful, for
instance, by m e a n s of a second laser with a n optical
p a t h p e r p e n d i c u l a r t o t h e original laser p a t h a n d
Laser
focused j u s t a b o v e t h e surface of t h e s a m p l e , t h e n it
m i g h t be possible t o r e d u c e t h e p r i m a r y laser p o w e r
sufficiently so t h a t only surface layers a r e r e m o v e d
from the s a m p l e .
M a s s r e s o l u t i o n for L A M M S i n s t r u m e n t s is
generally expressed by t h e r a t i o of p e a k p o s i t i o n m t o
p e a k w i d t h 8m for a single p e a k . O w i n g t o t h e s p r e a d
in ion energies arising from t h e l a s e r - s a m p l e i n t e r a c
tion, t h e ions a r e n o t all accelerated from t h e s a m e
initial energy a n d so m a s s p e a k s h a v e finite w i d t h s .
While the use of either t h e M a m y r i n o r P o s c h e n r i e d e r
s p e c t r o m e t e r design c a n c o m p e n s a t e for s o m e of t h e
energy s p r e a d s , values of m/8m in t h e r a n g e 5 0 0 - 8 0 0
at m a s s 208 (lead) a r e r e p o r t e d ; these values a r e
c o n s i d e r a b l y lower t h a n t h e theoretical figure of 5 0 0 10 000 for such a m a s s s p e c t r o m e t e r . N o n e t h e l e s s , t h e
time-of-flight a p p r o a c h h a s t h e i m p o r t a n t ability of
being able to detect q u a n t i t a t i v e l y all ion species
resulting from a single laser pulse of s h o r t d u r a t i o n
( 4 - 8 ns). Positive o r negative i o n s c a n be selected (by
switching p o l a r i t y of t h e s a m p l e relative t o t h e timeof-flight t u b e ) . T h e s e c a n o r i g i n a t e from all e l e m e n t s
(including h y d r o g e n a n d o t h e r light elements, unlike
x-ray microanalysis) with d i s c r i m i n a t i o n b e t w e n iso
topes as well as from molecules. T h e relative sensi
tivity t o different e l e m e n t s a p p e a r s t o lie w i t h i n a
factor of ten a t m o s t ; it is m o r e u n i f o r m a t a w a v e
length of 266 n m t h a n 532 n m a n d is n e a r u n i t y for
elements of similar i o n i z a t i o n energy. T h e d e t e c t i o n
limit for trace e l e m e n t s is n o r m a l l y ~ 10 p p m for a
single laser pulse a n d ~ 1 p p m h a s been achieved for
b o r o n in silicon. It m a y b e n o t e d t h a t 1 p p m in a n
analyzed d e p t h of ~ 0 . 5 c o r r e s p o n d s t o a few
percent of t h e a t o m s p r e s e n t in a surface m o n o l a y e r .
T h u s , while n o t specifically i n t e n d e d as a surfacesensitive analysis t e c h n i q u e such as s e c o n d a r y - i o n
m a s s s p e c t r o s c o p y ( S I M S ) , A u g e r electron s p e c t r o s
c o p y o r electron s p e c t r o s c o p y for chemical analysis,
L A M M S c a n p r o v i d e surface i n f o r m a t i o n .
U n l i k e m a n y analysis t e c h n i q u e s , L A M M S is a p
plicable t o a wide r a n g e of m a t e r i a l s , including n o t
only c o n d u c t o r s b u t s e m i c o n d u c t o r s , glasses a n d cer
amics, p o l y m e r s a n d c o m p o s i t e s , c o a t i n g s a n d
p o w d e r s , a n d o r g a n i c a n d biological s a m p l e s .
T h e t e c h n i q u e also h a s been r e g a r d e d as t h e first
organic microprobe analyzer although the interpre
t a t i o n of t h e resulting m a s s s p e c t r u m c a n b e m o r e
involved for o r g a n i c s t h a n for m e t a l s since t h e p o s
sible c o m b i n a t i o n s of m o l e c u l a r a n d / o r f r a g m e n t i o n s
b e c o m e s m u c h greater. F o r e x a m p l e , m o l e c u l a r i o n s
m a y form in a n u m b e r of w a y s (Hercules 1983)
including:
(a) i o n - m o l e c u l a r r e a c t i o n s (e.g., molecule p l u s
fragment ion);
Microprobe
Mass
Spectrometry
o r m o l e c u l a r ion t o f r a g m e n t i n t o a n u m b e r of ions of
lower m a s s - t o - c h a r g e r a t i o . N o n e t h e l e s s , the frag
m e n t ion p a t t e r n often c a n be distinctive for a p a r t i c u
lar m o l e c u l e a n d this allows r a p i d identification of
molecules with m i c r o m e t e r - s c a l e spatial resolution.
Very high m a s s (e.g., several t h o u s a n d ) ions c a n also
be detected.
F o r r o u t i n e use, t h e t e c h n i q u e is very quick a n d
simple: s a m p l e p r e p a r a t i o n is s t r a i g h t f o r w a r d ; the
time t a k e n t o l o a d a n e w s a m p l e t h r o u g h t o o b t a i n i n g
a m i c r o a n a l y s i s of a selected region is of t h e o r d e r of
m i n u t e s ; a n d further m i c r o a n a l y s e s m a y t h e n be per
f o r m e d a t intervals of s e c o n d s . S a m p l e s m a y be
p r e c l e a n e d in situ by use of a defocused laser pulse,
a n d r e p e a t e d m i c r o a n a l y s e s a t t h e s a m e p o i n t give the
possbility of c o a r s e depth-profiling, r a p i d l y p e n e t r a t
ing several m i c r o m e t e r s i n t o a s a m p l e .
3.
Applications
T h e r a n g e of m a t e r i a l s a n d analytical p r o b l e m s t o
w h i c h l a s e r - p r o b e m i c r o a n a l y s i s m a y usefully be a p
plied a p p e a r s t o be very wide a n d h a s certainly n o t yet
been fully e x p l o r e d , still less c h a r a c t e r i z e d in a n y
detail. V a r i o u s a p p l i c a t i o n s of t h e L A M M S t e c h n i q u e
t o p r o b l e m s in m a t e r i a l s science h a v e been reviewed
( C o n z e m i u s et al. 1983, Michiels et al. 1984, S o u t h o n
et al. 1985). S o m e a p p l i c a t i o n s of t h e t e c h n i q u e ,
necessarily u n r e p r e s e n t a t i v e of t h e full scope of the
t e c h n i q u e , a r e i n d i c a t e d below.
3.1 Microanalysis
of Borides in a Nickel-Base
Superalloy
N i c k e l - b a s e superalloys a r e h i g h - p e r f o r m a n c e m a t e r
ials used principally for c o m p o n e n t s in t h e h o t z o n e of
g a s - t u r b i n e a e r o e n g i n e s . T h e m i c r o s t r u c t u r e s of these
alloys a r e extremely c o m p l e x . A m o n g their m o r e
interesting features a r e s e c o n d - p h a s e particles c o n
t a i n i n g b o r o n , usually of c o m p o s i t i o n M 3 B 2 w h e r e
is a m e t a l . It is i m p o r t a n t t o identify t h e metallic
c o n s t i t u e n t s a n d t o establish w h e t h e r the particles
c o n t a i n c a r b o n , w h i c h c a n b e difficult t o m e a s u r e
a c c u r a t e l y by c o n v e n t i o n a l e l e c t r o n - m i c r o p r o b e tech
n i q u e s . F i g u r e 3 is a typical m a s s s p e c t r u m , resulting
from a f r e q u e n c y - d o u b l e d (wavelength of 532 n m )
laser pulse a t relatively low intensity, from t h e m a t r i x
p h a s e of t h e alloy. All of t h e expected metallic consti
t u e n t s of t h e alloy a r e clearly seen, w i t h t h e a d d i t i o n
of a trace of ^ C a p r o b a b l y p r e s e n t as a surface
c o n t a m i n a n t . Q u a n t i t a t i v e l y , t h e relative isotopic
a b u n d a n c e s of a given element a r e correctly repre
sented (typically t o b e t t e r t h a n 1 % o f the t o t a l
elemental c o n c e n t r a t i o n ) a n d elements of low o r
c o m p a r a b l e i o n i z a t i o n energy a p p e a r in t h e expected
p r o p o r t i o n s . H o w e v e r , there is s o m e d i s c r i m i n a t i o n
a g a i n s t e l e m e n t s of h i g h e r i o n i z a t i o n energy, the
c o b a l t a n d nickel p e a k s ( , = 7.86, 7.62 eV) being
lower t h a n expected relative t o c h r o m i u m , t i t a n i u m
211
Laser Microprobe
Mass
Spectrometry
Al
Nii
xlO
"Co
6 0
Ni
Cg
20
30
40
Mass
Zrf
M(
'"Ni
62 Ni
fi
*Ni
T T T T W
I
50
number
Figure 3
LAMMS positive-ion mass spectrum from a single laser pulse of relatively low intensity incident on the matrix phase of a
nickel-base superalloy. Note the change of scale at the high-mass end of the spectrum
~ 200 d i a m e t e r w h e n viewed n o r m a l t o t h e p l a n e
of t h e film. P r i o r t o analysis of t h e particle, a series of
spectra were o b t a i n e d from the p o l y m e r a t relatively
high laser p o w e r . All of these s p e c t r a were similar a n d
"B
iob
10
Moss
15
20
25
30
number
Figure 4
Section of the positive-ion spectrum at high laser intensity
from a boride particle in the nickel-base superalloy,
showing the low carbon-to-boron ratio in the boride phase
Laser Microprobe
c 3x
c
I .
!
10
1
20
lul
1
30
c 5x *
C 6X
U
40
Moss
50
60
70
80
number
(a)
Mass
lil
lie:
number
(b)
Figure 5
Positive-ion spectra of poly (vinyl chloride):
(a) characteristic positive-ion LAMMS spectrum of
polyvinyl chloride) at relatively high laser intensity;
(b) positive-ion spectrum obtained during depth profiling
by repeated laser pulsing at the same point on a polyvinyl
chloride) film containing
an inclusion.
The groups
of
+
+
+
+
peaks designated C 3 X , C 4 X , C 5 X and C 6 X in (a) are
greatly diminished,
and groups
of peaks due to the
+
+
isotopes of Ti and to TiO have become prominent
Mass
Spectrometry
213
Laser
Microprobe
Mass
Spectrometry
COOH
molecular weight W 4 4 2 . 5 7
200
100
\U
300
400
500
200
100
Mass number
(a)
300
400
500
Mass number
(b)
M
V
*
molecular
weight
262
-
50
100
150
Mass
200
250
300
number
(c)
100
150
Mass
200
number
(d)
Figure 6
Examples of LAMMS spectra from organic materials: (a) positive-ion spectrum of rhodamine-B at low laser intensity
showing a strong molecular-ion peak and a series of peaks at lower mass due to loss of fragments of the parent molecule;
(b) positive-ion spectrum of rhodamine-B at a higher laser intensity showing a diminished molecular-ion peak and a
prominent series of noncharacteristic fragments at low molecular weights; (c) positive-ion spectrum and
1,4-diphenoxybenzene at low laser intensity, showing a strong molecular-ion peak and very little fragmentation;
(d) spectrum from diphenoxybenzene at a slightly higher laser intensity than (c), showing the development of a
characteristic fragmentation pattern
4.
Quantification
A t present, t h e L A M M S t e c h n i q u e is essentially
s e m i q u a n t i t a t i v e . T h e possibility of o b t a i n i n g fully
q u a n t i t a t i v e L A M M S analyses h a s been discussed for
i n o r g a n i c ( K a u f m a n n 1982, M a u n e y 1985, S o u t h o n et
al. 1985) a n d o r g a n i c ( V e r b u e k e n et al. 1985) m a t e r
ials. O n e p r o b l e m is t h a t t h e t o t a l ion yields in spectra
o b t a i n e d u n d e r n o m i n a l l y identical c o n d i t i o n s s h o w a
significant scatter (e.g., H a r r i s a n d W a l l a c h 1986).
214
Laser
Sampling
5.
Conclusion
It is evident t h a t L A M M S h a s great p o t e n t i a l a s a
versatile, quick a n d relatively simple m i c r o a n a l y t i c a l
m e t h o d applicable t o a very wide r a n g e of s a m p l e
materials a n d analytical s i t u a t i o n s . A special feature
is its p o t e n t i a l a s t h e first o r g a n i c m i c r o p r o b e . E v e n
so, it is unlikely t h a t L A M M S in its p r e s e n t semi
q u a n t i t a t i v e f o r m will replace existing m i c r o a n a l y t i c a l
techniques, m a n y of w h i c h h a v e p e r f o r m a n c e s u p e r i o r
to L A M M S in s o m e respects b u t inferior in o t h e r s .
R a t h e r , it is envisaged t h a t t h e versatility, speed a n d
simplicity of L A M M S t o g e t h e r w i t h t h e c o m b i n a t i o n
of capabilities o u t l i n e d a b o v e i n c l u d i n g m i c r o m e t e r
lateral r e s o l u t i o n , s u b m i c r o m e t e r d e p t h r e s o l u t i o n ,
r o u g h l y u n i f o r m sensitivity t o all elements of t h e
periodic table, p p m d e t e c t i o n sensitivity, d e t e c t i o n of
isotopes a n d m o l e c u l a r i o n s , a n d applicability t o a
wide r a n g e of materialswill e n s u r e L A M M S h a s a
place as a c o m p l e m e n t t o existing t e c h n i q u e s , a n d
m a y well m a k e it in future t h e first m e t h o d w h i c h t h e
m i c r o a n a l y s t will a p p l y t o a n e w p r o b l e m before
t u r n i n g t o o t h e r m o r e specialized, b u t less versatile,
m e t h o d s for m o r e detailed c h a r a c t e r i z a t i o n of p a r
ticular features o r p a r a m e t e r s .
Acknowledgement
T h i s article uses e x a m p l e s w h i c h a p p e a r e d previously
in a p a p e r b y S o u t h o n et al. (1984).
See also: Auger Electron Spectroscopy; Electron Microprobe Analysis; Electron Spectroscopy for Chemical Analy
sis; Laser Sampling Inductively Coupled Plasma Mass Spec
trometry; Organic Mass Spectrometry; Secondary-Ion Mass
Spectrometry; Spark-Source Mass Spectrography
Bibliography
Armstrong J (ed.) 1985 Proc. 20th Int. Conf. Microbeam
Analysis Society. San Francisco Press, San Francisco, CA
Conzemius RJ, Simons D S , Shankai Z, Byrd G D 1983
Inductively
Coupled
Plasma
Mass
Spectrometry
215
Laser Sampling
System
Inductively
Coupled
Plasma
Mass
Spectrometry
computer
Figure 1
Schematic diagram showing the component instruments of an LSICPMS
a n d detection. Laser s a m p l i n g allows a solid specimen
to be s a m p l e d w i t h o u t the need for dissolving t h e
specimen. Because the laser c a n be focused o n a single
spot o r rastered over t h e surface of t h e specimen, the
c o m p o s i t i o n of the b u l k a n d of localized features
(i.e., inclusions, defects) can be studied a n d c o m p a r e d .
In L S I C P M S a h i g h - p o w e r pulsed laser is focused
o n t o a solid specimen held in a n enclosed cell. M a t e r
ial v a p o r i z e d as a result of t h e l a s e r - s o l i d i n t e r a c t i o n
recondenses a n d is swept i n t o the high-energy p l a s m a
of the I C P m a s s s p e c t r o m e t e r . T h e r e it is r e v a p o r i z e d ,
a t o m i z e d a n d ionized a n d is s a m p l e d i n t o a m a s s
spectrometer. T h e ion signal w h i c h is m e a s u r e d is
representative of t h e c o m p o s i t i o n of t h e original
specimen.
W h i l e laser s a m p l i n g is b y n o m e a n s limited t o use
with I C P M S , the c o m b i n a t i o n h a s several a d v a n
tages. T h e I C P M S t e c h n i q u e h a s sufficiently high
sensitivity t o detect trace impurities in m a t e r i a l s s a m
pled by t h e laser, even t h o u g h only 1-10 n g of s a m p l e
a r e t a k e n p e r laser pulse. S p e c t r a r e c o r d e d using
I C P M S a r e less c o m p l e x t h a n t h o s e of emission
spectroscopic techniques. Because spectral interfer
ences a r e fewer, the spectra a r e readily i n t e r p r e t e d a n d
calibrated for either q u a n t i t a t i v e o r s e m i q u a n t i t a t i v e
analysis. T h e ability t o m e a s u r e isotopes m a k e s iso
t o p e r a t i o , dilution a n d t r a c e r studies possible. A
review of I C P M S is given by H o u k (1986).
/.
Instrumentation
F i g u r e 1 is a s c h e m a t i c of the c o m p o n e n t i n s t r u m e n t s
used in L S I C P M S . T h e N d : Y A G laser h a s p r o v e n
216
Laser
Sampling
H a v i n g traversed t h e I C P - M S interface, t h e i o n s
are t h e n directed i n t o t h e m a s s s p e c t r o m e t e r b y m e a n s
of o n e o r m o r e i o n o p t i c elements. T h e q u a d r u p o l e
m a s s s p e c t r o m e t e r is especially suited for L S I C P M S
as it c a n be swept r a p i d l y a c r o s s t h e full m a s s r a n g e of
the p e r i o d i c table. T h i s r a p i d s c a n n i n g allows t r a n
sient signal profiles t o b e a c c u r a t e l y defined for t h e
quantification of m a n y e l e m e n t s , even in a single
signal pulse. I o n s a r e typically detected using a c h a n
8
nel electron multiplier w i t h a gain of u p t o 10 w h i c h is
o p e r a t e d in t h e pulse c o u n t i n g m o d e for m a x i m u m
sensitivity.
2. Laser-Solid
Interaction
T h e m e c h a n i s m s involved in t h e i n t e r a c t i o n of a
focused h i g h - p o w e r laser a n d a solid specimen a r e
c o m p l e x a n d n o t fully u n d e r s t o o d . It is generally
accepted t h a t b o t h a b l a t i o n a n d v a p o r i z a t i o n occur,
b u t the relative i m p o r t a n c e of either m e c h a n i s m
d e p e n d s o n t h e m o d e of laser o p e r a t i o n a n d t h e
c o m p o s i t i o n of t h e s a m p l e itself. H e a t is initially
transferred from t h e laser i n t o t h e solid b y a b s o r p t i o n
of the laser light b y t h e specimen. A t t h e focal p o i n t ,
local t e m p e r a t u r e s rise very r a p i d l y c a u s i n g v a p o r i z a
tion a n d t h e initiation of a t h e r m a l s h o c k front
r a d i a t i n g from t h e s a m p l e surface. A p l a s m a is often
formed in t h e gas j u s t a b o v e t h e s a m p l e surface as a
result of electron emission a n d m u l t i p h o t o n ioniza
tion c a u s e d b y t h e high e n e r g y density at t h e focus of
the laser b e a m . T h i s p l a s m a c a n b e f o r m e d early in t h e
laser pulse a n d c a n a b s o r b a significant p o r t i o n of t h e
r e m a i n i n g laser pulse. T h e energy in t h e p l a s m a c a n
then be transferred b a c k i n t o t h e s a m p l e . T h i s second
ary h e a t i n g c a n result in s a m p l e r e m o v a l b y v a p o r i z a
tion, ion b o m b a r d m e n t a n d physical a b l a t i o n from
the local p r e s s u r e s h o c k .
T w o different m o d e s a r e available for o p e r a t i n g the
N d : Y A G laser. I n t h e free-running m o d e , pulses of
relatively l o n g d u r a t i o n ( 1 5 0 - 2 5 0 \xs) a r e e m i t t e d from
the laser, e a c h actually c o m p r i s i n g a n e n v e l o p e of
m a n y individual s h o r t e r pulse spikes. Because t h e
i n t e r a c t i o n time of t h e pulse e n v e l o p e w i t h t h e solid
specimen is l o n g c o m p a r e d with t h e r a t e of t h e r m a l
transfer within t h e solid, h e a t is c o n d u c t e d relatively
d e e p i n t o t h e specimen u s i n g t h e free-running m o d e .
This establishes a t h e r m a l g r a d i e n t in t h e b u l k of t h e
specimen resulting in t h e fusion a n d v a p o r i z a t i o n of
s a m p l e d m a t e r i a l . R a p i d e x p a n s i o n of t h e h e a t e d
m a t e r i a l causes t h e ejection of m o l t e n particles from
the crater. S o m e of this m a t e r i a l redeposits as a
s h o u l d e r a r o u n d t h e c r a t e r while a q u a n t i t y is ejected
with great force a w a y from t h e s a m p l e d s p o t . V a p o r
ised m a t e r i a l is also released from t h e h e a t e d a r e a a n d
c a n r e c o n d e n s e o n p a r t i c u l a t e nuclei j u s t a b o v e t h e
crater z o n e .
A n alternative m o d e is Q-switched o p e r a t i o n .
U s i n g a n o p t o e l e c t r o n i c gate ( Q switch), t h e efficiency
Inductively
Coupled
Plasma
Mass
Spectrometry
3. Analytical
Considerations
M a n y i n s t r u m e n t a l o p e r a t i n g p a r a m e t e r s a r e avail
able with w h i c h t o c u s t o m i z e t h e analysis t o a specific
a p p l i c a t i o n . T h e N d : Y A G laser is typically fired a t
10-20 H z b u t c a n also b e activated in single o r m u l t i
ple pulses. C o n t i n u o u s p u l s i n g (typically > 200 pulses
p e r s a m p l i n g ) results in a steady r e m o v a l of s a m p l e
from t h e specimen a n d a s t e a d y - s t a t e signal, while a
single pulse results in discrete s a m p l i n g a n d a t r a n
sient signal. A single laser pulse minimizes t h e i m p a c t
of t h e laser o n t h e s a m p l e p r o v i d i n g the best spatial
r e s o l u t i o n , b u t it also results in t h e smallest analytical
signal (see Fig. 2). S t e a d y - s t a t e pulsing results in the
p o o r e s t spatial r e s o l u t i o n b u t p r o v i d e s t h e best a n a l y
tical sensitivity, a l t h o u g h t h e s p e c t r o m e t e r interface
c a n b e c o m e o v e r l o a d e d b y t h e large a m o u n t of s a m
ple r e m o v e d . Discrete s a m p l i n g b y pulsing the laser
5 0 - 2 0 0 times is a g o o d a l t e r n a t i v e b e c a u s e it p r o v i d e s
relatively high spatial r e s o l u t i o n a n d high sensitivity
b u t only m o d e s t s a m p l e l o a d i n g o n t h e interface.
M o n i t o r i n g a c o n t i n u o u s signal c a n p r o v i d e infor
m a t i o n a b o u t c o m p o s i t i o n a l g r a d i e n t s in t h e s a m p l e .
If a single p o i n t is i r r a d i a t e d , a d e p t h profile m a y be
i n d i c a t e d b y v a r i a t i o n in t h e signal with time. If the
b e a m is swept a c r o s s t h e specimen surface, lateral
c o m p o s i t i o n a l g r a d i e n t s c a n be reflected by v a r i a t i o n s
in signal as a function of t r a n s l a t i o n . If t h e c o m p o s i
tion of t h e b u l k of t h e specimen is t o be d e t e r m i n e d ,
t h e b e a m is usually s c a n n e d a c r o s s t h e s a m p l e . O t h e r
wise, several individual p o i n t analyses c a n be inte
g r a t e d . T h e degree t o w h i c h t h e a n a l y t e s of interest
a r e d i s t r i b u t e d h e t e r o g e n e o u s l y in t h e s a m p l e c a n
limit t h e precision of t h e m e a s u r e m e n t . F o r b u l k
analysis, a larger laser b e a m s p o t size is generally
desirable for a m o r e representative s a m p l i n g of the
specimen. Q-switched o p e r a t i o n usually results in a
larger surface c r a t e r as a result of t h e p l a s m a induced
a b o v e t h e specimen surface. F r e e - r u n n i n g o p e r a t i o n
n o r m a l l y results in s a m p l i n g s p o t s with a m u c h
smaller d i a m e t e r , a l t h o u g h m u c h d e e p e r t h a n those
217
Laser Sampling
Inductively
Coupled
Plasma
Mass
I0
/
4
--/-
V
/
/
i<-
10
Number
10*
of
laser
I0
pulses
Figure 2
LSICPMS signal generated as a function of the number of
discrete laser pulses (strontium analyte in glass specimen;
Q-switched Nd: YAG laser operation)
218
Spectrometry
4.
Applications
Laser s a m p l i n g c a n be used t o s a m p l e a l m o s t a n y
solid m a t e r i a l , w h e t h e r r o u g h o r s m o o t h , c o m p o s i t e
o r h o m o g e n e o u s , reflective o r a b s o r p t i v e . Because t h e
q u a d r u p o l e c a n be s c a n n e d rapidly, a c o m p l e t e m a s s
s p e c t r u m of a m a t e r i a l of u n k n o w n c o m p o s i t i o n c a n
be r e c o r d e d in milliseconds. T h e L S I C P M S s p e c t r u m
of a glass m a t e r i a l in Fig. 4 illustrates t h e a m o u n t of
i n f o r m a t i o n c o n t a i n e d in a single L S I C P M S spec
t r u m . T h o u g h relatively new, t h e t e c h n i q u e h a s
a l r e a d y f o u n d a p p l i c a t i o n in t h e analysis of alloys,
glasses, ceramics, m i n e r a l s , plastics, s e m i c o n d u c t o r s
and environmental materials.
A r r o w s m i t h (1987) r e p o r t e d t h e analysis of lowalloy steels, c o p p e r alloys, A l 2 0 3 - T i C - Z r 0 2 ceramics
a n d c o b a l t - p l a t i n u m thin films o n a l u m i n a . H a g e r
(1990) analyzed zircon, d e m o n s t r a t i n g q u a n t i t a t i v e
analysis of impurities r a n g i n g in c o n c e n t r a t i o n from
1
2 4 g g ~ to 10.5 w t % . D e p t h - c o n c e n t r a t i o n profiles
in a n a n c i e n t C h i n e s e m i r r o r were also m e a s u r e d t o
s t u d y the surface finishes of H a n d y n a s t y m i r r o r s . In
a d d i t i o n , the ability of L S I C P M S t o p r o v i d e isotopic
a b u n d a n c e i n f o r m a t i o n w a s illustrated for lead in
zircon. T y e et al. (1989) also used L S I C P M S t o
identify r a d i o g e n i c lead in g y p s u m .
Abell et al. (1990) a n d M o c h i z u k i et al. (1991)
r e p o r t e d t h e analysis of impurities in silicon nitride
a n d o t h e r ceramics. T h e possibility of analyzing trace
impurities w i t h o u t dissolving c e r a m i c m a t e r i a l s is a n
especially a t t r a c t i v e feature of t h e t e c h n i q u e a n d
reduces t h e c h a n c e of c o n t a m i n a t i o n associated with
the lengthy dissolution p r o c e d u r e s c o m m o n l y used in
t h e analysis of refractory m a t e r i a l s . D e n o y e r a n d
Laser
-0.5
0.5
Relative focal
1.5
position
Sampling
Inductively
Plasma
200
(mm)
(c)
Coupled
400
Laser energy
Mass
Spectrometry
600
(mj)
"(d)
.7
150
250
Laser energy
350
(mj)
50
Crater
100
diameter
150
(//m)
Figure 3
(a-d) The interrelationships of laser beam focus, laser energy, sample crater size and signal intensity in LSICPMS (cobalt
analyte in steel specimen; free-running Nd: YAG laser operation)
Transition metals
100
Mass
Rare e a r t h s
150
(amu)
Figure 4
LSICPMS spectrum of trace elements present at 50 gg~
(nominal) in glass showing the high information content
of a single spectrum; isotopes of gadolinium are
highlighted (Q-switched Nd: YAG laser operation)
W a l l a c e (1989) e x a m i n e d h i g h - p u r i t y q u a r t z used in
silicon wafer m a n u f a c t u r e . T h e p r o b i n g capabilities of
L S I C P M S were used t o establish c o m p o s i t i o n a l dif
ferences b e t w e e n b u l k q u a r t z a n d localized i m p u r i t y
inclusions. M a r s h a l l et al. (1991) a n a l y z e d plastics
directly, e m p l o y i n g b o t h q u a n t i t a t i v e a n d s e m i q u a n t i
tative c a l i b r a t i o n . T h e results of t h e s e m i q u a n t i t a t i v e
analysis agreed t o within a factor of t w o o r better with
results from x-ray fluorescence ( X R F ) analysis a n d
a d d i t i o n a l e l e m e n t s w h i c h c o u l d n o t be detected by
X R F were readily identified.
Because of t h e sensitivity of t h e t e c h n i q u e a n d the
fact t h a t t h e q u a d r u p o l e c a n scan t h e full periodic
t a b l e rapidly, a c o m p l e t e s e m i q u a n t i t a t i v e analysis of
h i g h - p u r i t y m a t e r i a l s c a n be carried o u t within 1-2
m i n a n d t h e presence of u n s u s p e c t e d trace i m p u r i
ties revealed. C a l i b r a t i o n s t a n d a r d s a p p r o p r i a t e
for t h e q u a n t i t a t i v e analysis of m a n y n e w hight e c h n o l o g y a n d u l t r a p u r e m a t e r i a l s a r e n o t avail
able. T h e r e f o r e , t h e possibility of s e m i q u a n t i t a t i v e
219
Laser Sampling
Inductively
Coupled
Plasma
Mass
c a l i b r a t i o n with L S I C P M S b e c o m e s m o r e a n d m o r e
attractive as new exotic m a t e r i a l s a r e discovered.
See also: Chemical Analysis of Solid Surfaces; Laser Microprobe Mass Spectrometry
Bibliography
Abell I D, Gregson D, Shuttleworth S 1990 Laser ablation
ICP-MS analysis of ceramic materials. In: Freer R (ed.)
1990 The Physics and Chemistry of Carbides, Nitrides and
Borides. Kluwer, Dordrecht, The Netherlands, pp. 12130
Arrowsmith A 1987 Laser alblation of solids for elemental
analysis by inductively coupled plasma mass spectrom
etry. Anal Chem. 59: 1437-44
Arrowsmith A 1990 Applications of laser ablation: ele
mental analysis of solids by secondary plasma source
mass spectrometry. In: Lubman D (ed.) 1990 Lasers
and Mass Spectrometry. Oxford University Press, New
York
Denoyer R, Wallace G 1989 The analysis of high purity
quartz by laser sampling ICP-MS. 16th Annual Meeting
Federation of Analytical Chemistry and Spectroscopy
Societies., Chicago, IL, Paper 742, Meeting Abstract
Hager J W 1989 Relative elemental responses for laser
ablation inductively coupled plasma mass spectrometry.
Anal. Chem. 61: 1243-8
Hager J W 1990 Elemental analysis of solids using laser
sampling inductively coupled plasma mass spectrometry.
In: Lerner J M, McNamara J (eds.) 1990 SPIE Optical
Spectroscopic Instrumentation and Techniques for the
1990s, Vol. 1318. Society of Photo-Optical Instrumen
tation Engineers, Bellingham, WA, pp. 166-77
Houk R S 1986 Mass spectrometry of inductively coupled
plasmas. Anal. Chem. 58: 97A
Marshall J, Franks J, Abell I, Tye C 1991 Determination of
trace-elements in solid plastic materials by laser ablation
inductively coupled plasma mass-spectrometry. J. Anal.
At. Spectrom. 6: 145-50
Mochizuki T, Sakashita A, Iwata H, Ishibashi Y, Gunji
1991 Direct analysis of silicon nitride powders by induc
tively coupled plasma mass spectrometry with a laser
ablation technique. Anal. Sci. 7: 151-3
Moenke-Blankenburg L 1989 Laser Microanalysis. Wiley,
New York
Tye C T, Henry R, Abell I D, Gregson D 1989 Analyze the
elements without dissolving the solid. Res. Dev. 31: 76-9
E. R. D e n o y e r
[The P e r k i n - E l m e r C o r p o r a t i o n , N o r w a l k ,
Connecticut, USA]
220
Spectrometry
i . Direct Liquid
Injection
T h e earliest a t t e m p t s a t liquid c h r o m a t o g r a p h y m a s s
s p e c t r o m e t r y involved either the use of micro-liquidc h r o m a t o g r a p h y c o l u m n s with very low flows o r
s t a n d a r d c o l u m n s with splitting of the effluent so t h a t
only very small q u a n t i t i e s r e a c h t h e m a s s spec
t r o m e t e r . T h i s m e t h o d of interfacing is by far t h e
simplest since it involves only the use of a t u b e t o
c o n d u c t the flowing solvent from the liquid c h r o m a t o
g r a p h t o t h e m a s s s p e c t r o m e t e r . H o w e v e r , this
m e t h o d h a s m a n y limitations. First, t h e q u a n t i t i e s of
a n a l y t e which reach t h e m a s s s p e c t r o m e t e r a r e very
small. M i c r o - l i q u i d - c h r o m a t o g r a p h y c o l u m n s h a v e
small capacities for s a m p l e a n d splitting of effluent
reduces t h e s a m p l e r e a c h i n g t h e m a s s s p e c t r o m e t e r in
direct p r o p o r t i o n t o t h e split. T h i s m e a n s t h a t t h e
sensitivities of detection for this a p p r o a c h a r e p o o r .
F u r t h e r , it is still necessary t o i n t r o d u c e a t least
several t e n t h s of a milliliter of solvent p e r m i n u t e i n t o
the m a s s s p e c t r o m e t e r . Even this a m o u n t of solvent
p r o d u c e s so m u c h pressure t h a t c o n v e n t i o n a l electron
i o n i z a t i o n is n o t possible a n d instead only c h e m i c a l
i o n i z a t i o n m a s s spectra m a y be o b t a i n e d . I n this
Liquid
Chromatography
Liquid
Mass
Spectrometry
chromatograph
effluent
Infrared reflector
Split
Flash
vaporizer
option
Vacuum
locks
JTl_Am_\^_iTL
Scrubber
solvent
Ion
source-*
-Spring-loaded
idler w h e e l
Kb)fja1
(C)
Pump
Pump
Drive wheels
Waste
Figure 1
Moving belt interface: scrubbing solution enters at (a), salt deposits are extracted at (b) and waste leaves at (c) (after
Kelley 1981 Proc. 29th ASMS Conf. Mass Spectrometry and Allied Topics. American Society of Mass Spectrometry,
East Lansing, MI. Reproduced with permission)
2. Moving
Belt
Interface
s p e c t r o m e t r y t e c h n i q u e s . N e x t , t h e belt exits t h e m a s s
s p e c t r o m e t e r i n t o a final p u m p i n g c h a m b e r w h e r e it is
very strongly h e a t e d t o r e m o v e a n y r e m a i n i n g traces
of s a m p l e . I n s o m e designs t h e belt m a y also b e rinsed
with solvent. T h e n in a c o n t i n u o u s l o o p process, t h e
belt r e t u r n s t o t h e b e g i n n i n g w h e r e it picks u p a d d i
t i o n a l effluent from t h e liquid c h r o m a t o g r a p h a n d
repeats the process.
A l t h o u g h this m e t h o d represents a m a j o r i m p r o v e
m e n t with respect t o direct injection, there a r e a
n u m b e r of serious p r o b l e m s . First, consider, for ex
a m p l e , t h a t t h e degree of h e a t i n g r e q u i r e d t o e v a p o r
a t e solvent d e p e n d s o n t h e n a t u r e of t h e solvent. If t h e
liquid c h r o m a t o g r a p h y m e t h o d utilizes g r a d i e n t elu
tion t e c h n i q u e s , t h e n t h e n a t u r e of t h e solvent is
c o n t i n u o u s l y c h a n g i n g a n d t h e a m o u n t of h e a t a p
plied m u s t b e c o n t i n u o u s l y adjusted. Second, consider
t h a t d e p o s i t i o n o n t h e belt w i t h o u t b a n d s p r e a d i n g is
very difficult. T h e w e t t i n g characteristics of v a r i o u s
solvents o n a given belt c o m p o s i t i o n varies a n d there
fore, in a g r a d i e n t e l u t i o n , t h e w e t t i n g b e h a v i o r c a n
v a r y as t h e c h r o m a t o g r a p h y progresses. A l s o , c o n
sider t h a t m a n y a n a l y t e s m a y b e difficult t o r e m o v e
from t h e belt a n d m a y slowly build u p as a partially
volatile residue. Finally, a n d p e r h a p s m o s t f u n d a m e n
tally, c o n s i d e r t h a t m o s t often liquid c h r o m a t o g r a p h y
m e t h o d s a r e selected for t h o s e m a t e r i a l s which h a v e
limited volatility. Volatile m a t e r i a l s a r e usually r u n b y
gas c h r o m a t o g r a p h y b e c a u s e of t h e vastly i m p r o v e d
r e s o l u t i o n afforded b y this t e c h n i q u e . H o w e v e r , using
t h e m o v i n g belt t e c h n i q u e , a n a l y t e s w h i c h m a y b e
only slightly volatile a r e r e q u i r e d t o e v a p o r a t e i n t o
t h e m a s s s p e c t r o m e t e r . T h i s aspect a l o n e d r a m a t i c a l l y
limits t h e r a n g e o f m a t e r i a l s which c a n b e e x a m i n e d .
F i g u r e 1 s h o w s a n e x a m p l e of a typical m o v i n g belt
interface.
221
Liquid
Chromatography
3. Thermospray
Spectrometry
Liquid
Mass
Spectrometry
Chromatography-Mass
222
Electron filament
Thermospray ion
source body
Discharge electrode
" Adjustable fragmentor electrode
Figure 2
Thermospray liquid chromatography-mass spectrometry
interface (after Goodley 1990 Proc. 38th ASMS Conf.
Mass Spectrometry and Allied Topics. American Society of
Mass Spectrometry, East Lansing, MI. Reproduced with
permission)
Chromatography-Mass
Liquid
Chromatography
Mass
Spectrometry
Figure 3
Particle beam liquid chromatography-mass spectrometry interface
5. Electrospray
Spectrometry
Liquid
Interface
Chromatography-Mass
E l e c t r o s p r a y c o n s t i t u t e s yet a n o t h e r a p p r o a c h t o
liquid c h r o m a t o g r a p h y - m a s s s p e c t r o m e t r y interfac
ing. I n this case, a very small flow of liquid c h r o m a t o g r a p h effluent is m a d e t o p a s s t h r o u g h a h o l l o w
c o n d u c t i v e needle held a t a b o u t 10 000 V relative t o a
c o u n t e r electrode a s h o r t d i s t a n c e a w a y . D e p e n d i n g
o n t h e c o m p o s i t i o n of t h e effluent from t h e liquid
c h r o m a t o g r a p h , such a n a r r a n g e m e n t c a n cause a
stable p h e n o m e n o n in which t h e effluent is ejected as a
s t r e a m i n g s p r a y from t h e tip of t h e needle. S k i m m i n g
c o n e s facing t h e needle collect t h e ionic c o m p o n e n t of
t h e ejected m a t e r i a l a n d i n t r o d u c e it i n t o a m a s s
s p e c t r o m e t e r . T h e i o n s p r o d u c e d in this w a y a r e often
very highly c h a r g e d . T h e e l e c t r o s p r a y liquid c h r o m a
t o g r a p h y - m a s s s p e c t r o m e t r y interface h a s been f o u n d
m o s t useful for biological species such as p e p t i d e s .
F o r this class of m a t e r i a l s , m a s s spectra h a v e been
o b t a i n e d in t h e lOOOOOdalton r a n g e .
Because t h e p e p t i d e s m a y b e very highly c h a r g e d ,
their m a s s - t o - c h a r g e r a t i o c a n fall within the r a n g e of
c o n v e n t i o n a l m a s s s p e c t r o m e t e r s . Often a series of
c h a r g e d states is o b s e r v e d . T h e o b s e r v e d m a s s of e a c h
of t h e c o m p o n e n t s of such a series in c o m b i n a t i o n
with t h e s e p a r a t i o n b e t w e e n c o m p o n e n t s differing by
o n e positive c h a r g e m a y be used t o calculate t h e true
m a s s . T h e sensitivity of this t e c h n i q u e for m a t e r i a l s
like p e p t i d e s c a n be exceptionally g o o d . M a n y ex
a m p l e s of picomole-level analyses h a v e been r e p o r t e d .
223
Liquid
Chromatography
Mass
Spectrometry
Figure 4
Electrospray liquid chromatography-mass spectrometry
interface (after Lee 1990 Proc. 38th ASMS Conf. Mass
Spectrometry and Allied Topics. American Society of Mass
Spectrometry, East Lansing, ML Reproduced with
permission)
b a r d m e n t ( F A B ) m e t h o d of i o n i z a t i o n . I n this case,
t h e c o n v e n t i o n a l F A B target is replaced with a m o d i
fied target w h e r e t h e effluent from t h e liquid c h r o m a
t o g r a p h c a n be c o n t i n u o u s l y p u m p e d o n t o t h e surface
of the target. A s in e l e c t r o s p r a y i o n i z a t i o n , very low
liquid c h r o m a t o g r a p h y flows a r e used. I n a typical
e x p e r i m e n t , a second s t r e a m of solvent c o n t a i n i n g a n
a p p r o p r i a t e F A B m a t r i x such as glycerol is m i x e d
with t h e effluent from t h e liquid c h r o m a t o g r a p h a n d
t h e c o m b i n e d s t r e a m is p u m p e d o n t o t h e t a r g e t of the
mass spectrometer. The mass spectrometer vacuum
r e m o v e s t h e solvent leaving t h e a n a l y t e dissolved in
the F A B m a t r i x . T h e r e m o v a l of s a m p l e a n d m a t r i x
by t h e s p u t t e r i n g of t h e p r i m a r y ion b e a m , p r o v i d e s
a c o n t i n u o u s l y refreshed target which preserves
c h r o m a t o g r a p h i c resolution.
T h e classes of s a m p l e a p p r o p r i a t e for liquid c h r o m a t o g r a p h y - F A B analyses a r e very similar t o t h o s e
w h i c h w o r k well with t h e r m o s p r a y a n d with electro
spray. T h i s is t h e highly p o l a r , water-soluble class
of m a t e r i a l s often associated with d r u g s a n d n a t u r a l
p r o d u c t s . F r e e fatty acids a n d q u a t e r n a r y a m m o n i u m
salts also w o r k well. F o r m a t e r i a l s which ionize well
by F A B , t h e sensitivity of this a p p r o a c h t o liquid
c h r o m a t o g r a p h y - m a s s s p e c t r o m e t r y c a n be quite
good.
See also: Gas and Liquid Chromatography
Bibliography
6. Fast-Atom-Bombardment-Based
Chromatography-Mass
Spectrometry
Liquid
Interfaces
pl
2000
'
2200
2400
2600
2800
3000
11
3200
3400
3600
3800
4000
Figure 5
Mass spectrum of human transferrin (molecular weight
79 754) obtained by electrospray (after JEOL Sales
Brochure 1990 JEOL, Tokyo. Reproduced with
permission)
224
Magnetic Materials: Measurements
T h e investigation, u n d e r s t a n d i n g a n d use of m a g n e t i c
m a t e r i a l s requires t h e m e a s u r e m e n t of m a g n e t i c
p r o p e r t i e s . S u p e r c o n d u c t o r s also possess i m p o r t a n t
m a g n e t i c p r o p e r t i e s , as a c o n s e q u e n c e of t h e exclu
sion of m a g n e t i c flux from fully s u p e r c o n d u c t i n g
m a t e r i a l s (the M e i s s n e r effect). T h i s article describes
the m e a s u r e m e n t of basic m a g n e t i c p r o p e r t i e s a n d of
i m p o r t a n t engineering m a g n e t i c p r o p e r t i e s , e m p h a
sizing m a i n l y t e c h n i q u e s used a t very low frequency
(dc), p o w e r frequencies a n d a u d i o frequencies ( u p t o
a b o u t 20 k H z ) .
7.
Magnetization
T h e f u n d a m e n t a l e x p e r i m e n t a l q u a n t i t y in m a g n e t i c
m a t e r i a l s is t h e m a g n e t i z a t i o n , defined as the m a g
netic m o m e n t p e r u n i t v o l u m e . I n SI u n i t s , m a g n e t i z a
2
3
_ 1
tion is m e a s u r e d in A m m " = A m . Alternatively,
2
m a g n e t i z a t i o n c a n b e m e a s u r e d in tesla ( W b m ~ ) , in
which case it is called m a g n e t i c p o l a r i z a t i o n . In cgs
(electromagnetic) u n i t s , using t h e c o n v e n t i o n t h a t
m a g n e t i c m o m e n t is m e a s u r e d in e m u ( e l e c t r o m a g n e
1
3
tic units, erg O e " ) , m a g n e t i z a t i o n is in e m u c m .
W h e n the v o l u m e of t h e s a m p l e m a y c h a n g e , as with
t e m p e r a t u r e , it is c o n v e n i e n t t o m e a s u r e t h e m o m e n t
p e r u n i t m a s s r a t h e r t h a n p e r u n i t v o l u m e ; this
q u a n t i t y is usually given t h e s y m b o l a n d is e q u a l t o
the m a g n e t i z a t i o n p e r u n i t v o l u m e multiplied b y t h e
density, in a p p r o p r i a t e u n i t s . Values of a r e n u m e r i
cally e q u a l in SI a n d cgs u n i t s .
M a g n e t i z a t i o n is in general a strongly n o n l i n e a r
function of t h e a p p l i e d field a n d , in sufficiently high
field, reaches a limiting value called t h e s a t u r a t i o n
m a g n e t i z a t i o n , Ms. T h e s a t u r a t i o n m a g n e t i z a t i o n is
t e m p e r a t u r e d e p e n d e n t , in general decreasing from a
m a x i m u m value a t 0 t o a z e r o value a t t h e C u r i e
t e m p e r a t u r e . A t fixed t e m p e r a t u r e , m a g n e t i z a t i o n vs
field is b o t h n o n l i n e a r a n d hysteretic; a p l o t of vs
for a cycle of field from + H->0-+
H-+0-*
+ is
called a m a g n e t i c hysteresis l o o p a n d c o n t a i n s m u c h
of the i n f o r m a t i o n n e e d e d t o c h a r a c t e r i z e a m a g n e t i c
material.
1.1 Force
Methods
A m a g n e t i c m o m e n t m in a g r a d i e n t field VH experi
ences a force F = mVH. A g r a d i e n t field c a n be
p r o d u c e d b y t a p e r i n g t h e p o l e pieces of a n electro
m a g n e t ; a s a m p l e is s u s p e n d e d in t h e g a p of the
m a g n e t , w h e r e it is subject t o a n a v e r a g e field a n d
a field g r a d i e n t VH. T h e s a m p l e is s u s p e n d e d from
a force-measuring device, c o m m o n l y a chemical
b a l a n c e o r a n e l e c t r o b a l a n c e , a n d t h e m e a s u r e d force
Figure 1
Magnetic balance: P, electromagnet pole piece with
tapered gap; S, sample and B, balance or other
force-measuring device
225
Magnetic
Materials:
Measurements
Figure 2
Alternating-gradient magnetometer: P, electromagnet pole
piece; C, drive coil to create alternating-field gradient in
horizontal direction; S, sample; R, support rod;
Pz, piezoelectric crystal motion detector;
V, vibration-damping support table; and M, meter
(usually lock-in amplifier)
226
= 0( + )
a coil of t u r n s
dB, a voltage is
E = kNA(dB/
Magnetic
Materials:
Measurements
>)
()
Figure 3
(a) VSM and (b) alternate version in which the signal from sample S is balanced against a signal from a reference sample
(Ref) of fixed magnetic moment: P, electromagnet pole piece; R, sample support rod; C, sensing or pickup coils
(orientation and location may vary); D, sample motion (mechanism not shown); and M, meter (usually lock-in amplifier)
m a g n e t i z a t i o n of t h e s a m p l e . V a r i o u s m e t h o d s h a v e
been used t o m e a s u r e this field; t h e principal difficulty
is to s e p a r a t e the field p r o d u c e d b y t h e s a m p l e from
the applied field c a u s i n g t h e m a g n e t i z a t i o n of t h e
sample. O n e m e t h o d is t o c h o o s e a m e a s u r i n g p o i n t
w h e r e the field from t h e s a m p l e h a s a large c o m
p o n e n t p e r p e n d i c u l a r t o t h e a p p l i e d field a n d m e a s u r e
the p e r p e n d i c u l a r field, usually with a Hall-effect
sensor. Since t h e applied field is usually large c o m
p a r e d with t h e s a m p l e field, careful o r i e n t a t i o n of t h e
field sensor is r e q u i r e d .
T h e m o s t c o m m o n s o l u t i o n is t o oscillate o r v i b r a t e
the s a m p l e a t a fixed frequency. T h e s a m p l e field is
then ac, n o t d c , a n d c a n b e easily s e p a r a t e d from t h e
dc applied field. T h e i n s t r u m e n t b a s e d o n this p r i n
ciple is the v i b r a t i n g - s a m p l e m a g n e t o m e t e r , o r V S M
(also s o m e t i m e s called a F o n e r m a g n e t o m e t e r after its
inventor). It is widely used for m e a s u r e m e n t s o n small
samples a t high fields. T h e s a m p l e is usually oscillated
p e r p e n d i c u l a r t o t h e applied field, either b y a l o u d
speaker c o n e o r b y a m e c h a n i c a l c a m (see F i g . 3). I n
the former case t h e frequency is a b o u t 100 H z a n d t h e
a m p l i t u d e is a b o u t 0.1 m m ; in t h e latter case t h e
frequency is a b o u t 20 H z a n d t h e a m p l i t u d e a b o u t
2 m m . T h e l o u d s p e a k e r system needs s o m e k i n d of
feedback c o n t r o l t o m a i n t a i n t h e v i b r a t i o n a m p l i t u d e
c o n s t a n t a n d , generally, is limited t o s a m p l e s of less
Measurements
227
Magnetic
Materials:
Measurements
2. Measurement
of Magnetic
Field
T h e s t a n d a r d g e n e r a l - p u r p o s e field-measuring instru
m e n t uses the H a l l effect in a small p l a t e of a
s e m i c o n d u c t i n g m a t e r i a l . U s u a l l y k n o w n as a g a u s s meter, this i n s t r u m e n t c a n m e a s u r e fields from levels
1
c o m p a r a b l e with t h e e a r t h ' s field ( ~ 10 A m " ) u p t o
_1
1
at least 5 M A m
a n d often 15 M A m
with a c c u r a
cies of a b o u t 1 % . T h e sensing element c a n b e as small
2
as 1 m m a n d b o t h d c a n d a c fields c a n be m e a s u r e d .
Special H a l l elements a r e m a d e for use a t cryogenic
t e m p e r a t u r e s a n d c a n be repeatedly cycled t o low
temperatures without damage (Rubin and Sample
1980).
A simple c o p p e r coil c o n n e c t e d t o a fluxmeter c a n
be used t o m e a s u r e c h a n g e s in t h e flux t h r o u g h t h e
coil, which is equivalent t o t h e a v e r a g e field in t h e coil.
Because of drift in t h e i n t e g r a t o r o u t p u t , this system is
useful primarily w h e n t h e field is cycled fairly rapidly,
as in the m e a s u r e m e n t of hysteresis l o o p s . H o w e v e r , if
the signal is large (a big coil with m a n y t u r n s in a
s t r o n g field), drift m a y n o t be a p r o b l e m . Coils of
special geometries c a n be used t o m i n i m i z e t h e e r r o r s
d u e t o fields t h a t a r e n o n u n i f o r m over d i m e n s i o n s
c o m p a r a b l e with t h e size of the coil (Zijlstra 1967 P t .
2, p p . 3-7). If the coil is oscillated o r r o t a t e d in t h e
field, a n ac voltage is g e n e r a t e d w h o s e m a g n i t u d e is
p r o p o r t i o n a l t o the field. C o m m e r c i a l i n s t r u m e n t s
called rotating-coil g a u s s m e t e r s h a v e been built using
this principle, b u t a r e less c o n v e n i e n t t o use t h a n H a l l effect i n s t r u m e n t s .
T h e r e s o n a n c e frequency of v a r i o u s a t o m i c nuclei
d e p e n d s linearly o n the applied m a g n e t i c field, w i t h a
p r o p o r t i o n a l i t y c o n s t a n t k n o w n t o high a c c u r a c y .
T h e m e a s u r e d r e s o n a n c e frequency t h e n establishes
the value of t h e applied field. F o r successful n u c l e a r
m a g n e t i c r e s o n a n c e ( N M R ) m e a s u r e m e n t s , t h e field
m u s t be highly u n i f o r m b o t h in s p a c e a n d time
( a l t h o u g h in m o d e r n i n s t r u m e n t s t h e size of t h e p r o b e
h a s been m u c h r e d u c e d ) ; c o n s e q u e n t l y this m e t h o d is
used m a i n l y t o calibrate o t h e r sensors.
F o r fields lower t h a n the e a r t h ' s field, the m o s t
c o m m o n field-measuring i n s t r u m e n t is t h e fluxgate
m a g n e t o m e t e r , which m e a s u r e s the applied d c field
required t o m a k e t h e ac hysteresis l o o p of a high-
228
3. Demagnetizing
Fields
A s n o t e d , a n y m a g n e t i z e d s a m p l e n o t in a closed
m a g n e t i c circuit creates a field in t h e s u r r o u n d i n g
space. T h i s field exists within t h e s a m p l e itself, as well
as in t h e s u r r o u n d i n g space, a n d inside t h e s a m p l e is
a l w a y s o p p o s i t e in d i r e c t i o n t o t h e s a m p l e m a g n e t i z a
tion. It is therefore called t h e d e m a g n e t i z i n g field.
T h i s is a perfectly real field, n o t a m a t h e m a t i c a l
a b s t r a c t i o n , a n d is often far from negligible. P r o p e r
a n d a c c u r a t e c o r r e c t i o n for t h e d e m a g n e t i z i n g field is
a persistent p r o b l e m in m a n y m a g n e t i c m e a s u r e
ments.
If t h e s a m p l e is a n ellipsoid a n d is u n i f o r m l y
m a g n e t i z e d , t h e d e m a g n e t i z i n g field is u n i f o r m
t h r o u g h o u t t h e s a m p l e a n d is linearly related t o t h e
m a g n e t i z a t i o n of t h e s a m p l e b y a p r o p o r t i o n a l i t y
c o n s t a n t k n o w n as t h e d e m a g n e t i z i n g factor (D in SI,
in cgs), w h i c h d e p e n d s o n t h e s a m p l e s h a p e . T h e
d e m a g n e t i z i n g factor c a n be calculated from f o r m u l a e
given in t e x t b o o k s , a n d t a b u l a t e d values a n d g r a p h s
a r e also widely available. T h e m a x i m u m v a l u e of t h e
d e m a g n e t i z i n g field, for a n infinite p l a t e m a g n e t i z e d
p e r p e n d i c u l a r t o its surface, is u n i t y in SI o r 4 in cgs.
T h e m a x i m u m possible d e m a g n e t i z i n g field is t h e r e
fore numerically e q u a l t o M s (SI) o r 4nMs (cgs); this
1
c o r r e s p o n d s t o over 1.6 M A m
( 2 0 k O e ) for iron
samples.
Ellipsoidal s a m p l e s a r e difficult t o m a k e a n d t o
m o u n t in e x p e r i m e n t a l e q u i p m e n t a n d a r e n o t used as
often as they s h o u l d be. T h e d e m a g n e t i z i n g factor
parallel t o t h e axis of a r o d decreases w i t h increasing
l e n g t h / d i a m e t e r a n d , for a disk s a m p l e a l o n g a dia
m e t e r , decreases with increasing d i a m e t e r / t h i c k n e s s ,
so l o n g thin r o d s o r thin disks a r e often used as
s a m p l e s with t h e d e m a g n e t i z i n g factor a s s u m e d e q u a l
t o t h a t of t h e e q u i v a l e n t ellipsoid. T h e " e q u i v a l e n t "
ellipsoid is usually t a k e n t o be t h e ellipsoid of t h e
s a m e aspect r a t i o as t h e s a m p l e , a l t h o u g h this is n o t
strictly correct.
If t h e d e m a g n e t i z i n g c o r r e c t i o n needs t o be m a d e
with high a c c u r a c y , t w o general m e t h o d s a r e avail
able. Since t h e t a n g e n t i a l fields j u s t o u t s i d e a n d j u s t
inside t h e surface of a s a m p l e a r e e q u a l , a direct
m e a s u r e m e n t of t h e parallel field at t h e surface of t h e
s a m p l e gives t h e t r u e field acting inside t h e s a m p l e :
t h a t is, t h e a p p l i e d field m i n u s t h e d e m a g n e t i z i n g
field. T h i s field c a n b e m e a s u r e d w i t h a H a l l p r o b e , o r
with a coil a n d fluxmeter. Since t h e field c a n n o t b e
m e a s u r e d exactly a t t h e s a m p l e surface, a n d is usually
c h a n g i n g r a p i d l y with d i s t a n c e from the surface, it
m a y b e necessary t o m e a s u r e a t several p o i n t s , e a c h a
Magnetic
Effect
W h e n m e a s u r e m e n t s a r e m a d e in t h e g a p of a n
e l e c t r o m a g n e t , t h e presence of large v o l u m e s of highpermeability m a g n e t i c m a t e r i a l in t h e p o l e pieces acts
to d i s t o r t t h e field s u r r o u n d i n g t h e s a m p l e . I n t h e
limiting case of semi-infinite slabs of u n i f o r m l y per
m e a b l e m a t e r i a l , t h e effect c a n b e described m a t h e m a
tically b y m a g n e t i c " i m a g e s " of t h e s a m p l e existing in
the pole pieces a t t h e m i r r o r i m a g e p o s i t i o n s . A t high
fields, the m a t e r i a l of t h e p o l e pieces a p p r o a c h e s
m a g n e t i c s a t u r a t i o n , t h e p e r m e a b i l i t y decreases t o
wards unity and the images tend to disappear. The
c a l i b r a t i o n c o n s t a n t relating t h e m a g n e t i z a t i o n of t h e
sample t o t h e o u t p u t signal of t h e m a g n e t o m e t e r t h e n
changes with field. T h i s usually results in a n a p p a r e n t
decrease in m a g n e t i z a t i o n with increasing field a t high
fields; this p h e n o m e n o n is w h a t is usually m e a n t b y
the image effect. T h e i m a g e effect m a y be m i n i m i z e d
by increasing t h e m a g n e t g a p , a t t h e cost of lower
Measurements
5. Curie
Temperature
T h e C u r i e t e m p e r a t u r e is t h e t e m p e r a t u r e a t which
a f e r r o m a g n e t i c o r ferrimagnetic m a t e r i a l loses its
m a g n e t i z a t i o n a n d b e c o m e s p a r a m a g n e t i c . T h e equiv
alent t e m p e r a t u r e in a n a n t i f e r r o m a g n e t is called the
Neel t e m p e r a t u r e . A n a p p r o x i m a t e value for the
C u r i e t e m p e r a t u r e c a n be o b t a i n e d b y m e a s u r i n g t h e
m a g n e t i z a t i o n (by a n y m e t h o d ) as a function of
t e m p e r a t u r e . H o w e v e r , in high fields t h e t r a n s i t i o n
from f e r r o m a g n e t i c t o p a r a m a g n e t i c b e h a v i o u r is
often n o t s h a r p l y defined, so t h a t either a low-field
m e a s u r e m e n t o r a n e x t r a p o l a t i o n t o low field is
- 1
necessary. T h e low-field susceptibility ( 0 . 1 - 1 0 A m )
often s h o w s a m a x i m u m a t o r n e a r t h e C u r i e t e m
p e r a t u r e ; this is k n o w n as t h e H o p k i n s o n effect
( H o p k i n s o n 1889) a n d is strongly d e p e n d e n t o n t h e
sample microstructure.
6. Magnetocrystalline
4. Image
Materials:
Anisotropy
M a g n e t o c r y s t a l l i n e a n i s o t r o p y describes t h e fact t h a t
t h e energy of a m a g n e t i c crystal d e p e n d s o n the
direction of t h e s a t u r a t i o n m a g n e t i z a t i o n relative t o
t h e c r y s t a l l o g r a p h i c axes. O t h e r m a g n e t i c a n i s o t r o
pics, d u e t o s h a p e , stress a n d so o n , c a n also exist.
A c c u r a t e m e a s u r e m e n t of t h e crystal a n i s o t r o p y re
quires a single-crystal s a m p l e , a l t h o u g h s o m e infor
m a t i o n c a n be e x t r a c t e d from m e a s u r e m e n t s o n a n
aligned p o w d e r s a m p l e o r a t e x t u r e d polycrystal.
A n i s o t r o p y is expressed as a series of t r i g o n o m e t r i c
t e r m s , e a c h multiplied b y a c o n s t a n t called a n a n i s o
tropy constant.
T h e m o s t satisfactory e x p e r i m e n t a l m e t h o d for t h e
d e t e r m i n a t i o n of a n i s o t r o p y is t h e m e a s u r e m e n t of
t h e t o r q u e a c t i n g o n a n ellipsoidal (or d i s k - s h a p e d )
s a m p l e as t h e s a m p l e is r o t a t e d a b o u t its axis of
s y m m e t r y in a s a t u r a t i n g a p p l i e d field p e r p e n d i c u l a r
t o this axis. A n i n s t r u m e n t m a d e for this p u r p o s e is
called a t o r q u e m a g n e t o m e t e r o r simply a t o r q u e m e t e r . T h e s h a p e of t h e t o r q u e c u r v e reflects t h e
229
Magnetic
Materials:
Measurements
crystallographic s y m m e t r y of t h e s a m p l e a n d t h e
m a g n i t u d e of t h e t o r q u e is related t o t h e m a g n i t u d e of
the a n i s o t r o p y . A difficulty is t h a t t h e direction of t h e
m a g n e t i z a t i o n relative t o the field a n d t h e crystal axes
is n o t k n o w n directly, b u t m u s t b e d e d u c e d from t h e
value of t h e s a t u r a t i o n m a g n e t i z a t i o n ( a s s u m e d c o n
s t a n t a t high fields) a n d t h e m e a s u r e d t o r q u e .
Generally, t h e a p p a r e n t a n i s o t r o p y increases slightly
with field a n d s o m e k i n d of e x t r a p o l a t i o n is r e q u i r e d .
Details of t h e m e t h o d a n d the m a t h e m a t i c s t h a t a p p l y
to v a r i o u s crystal s t r u c t u r e s a n d t o different crystallo
g r a p h i c p l a n e s in the p l a n e of t h e disk s a m p l e a r e
given by C h i k a z u m i (1964), Cullity (1972) a n d
P e a r s o n (1979).
A variety of t o r q u e - m e a s u r i n g m e t h o d s c a n be used
( P e a r s o n 1979). If the samples a n d t o r q u e s a r e large,
rigid systems with deflections m e a s u r e d b y strain
gauges c a n be used. Small t o r q u e s associated with
small samples o r small values of t h e a n i s o t r o p y re
quire sensitive t o r q u e - m e a s u r i n g systems using fine
filaments. T h e wide r a n g e of t o r q u e values t h a t m a y
be e n c o u n t e r e d m a k e s t h e d e v e l o p m e n t of c o m m e r
cial i n s t r u m e n t s difficult a n d m o s t i n s t r u m e n t s a r e
p u r p o s e built.
If a m a g n e t i c field p r o d u c e s a t o r q u e o n a disks h a p e d s a m p l e , there m u s t be a c o m p o n e n t of m a g n e
tization p e r p e n d i c u l a r t o the applied field a n d a
m e a s u r e m e n t of this p e r p e n d i c u l a r m a g n e t i z a t i o n is
equivalent t o t h e m e a s u r e m e n t of t h e t o r q u e . V a r i o u s
schemes for the m e a s u r e m e n t of p e r p e n d i c u l a r m a g
netization h a v e been used ( P e a r s o n 1979); they c a n
h a v e the a d v a n t a g e of being able t o be c o n t i n u o u s l y
read, which is c o n v e n i e n t for following t h e c h a n g e s in
a n i s o t r o p y with t e m p e r a t u r e o r field. T h e y h a v e t h e
d i s a d v a n t a g e t h a t the m e a s u r e d signal decreases with
increasing field, so t h a t e x t r a p o l a t i o n t o high fields is
somewhat uncertain.
Values of the a n i s o t r o p y c o n s t a n t s c a n also be
o b t a i n e d by m e a s u r i n g t h e m a g n e t i z a t i o n curves (M
vs H) in v a r i o u s c r y s t a l l o g r a p h i c directions, a n d c o m
p a r i n g the energy r e q u i r e d t o reach m a g n e t i c s a t u
r a t i o n . Physically, this is n o t strictly e q u i v a l e n t t o
r o t a t i n g the s a t u r a t i o n m a g n e t i z a t i o n from o n e crys
t a l l o g r a p h i c direction t o a n o t h e r b u t , in practice, t h e
difference is n o t usually significant.
T h e d e p e n d e n c e of t h e f e r r o m a g n e t i c r e s o n a n c e
frequency o r field o n c r y s t a l l o g r a p h i c direction c a n
also be i n t e r p r e t e d t o give a n i s o t r o p y c o n s t a n t s .
S o m e r a r e - e a r t h elements a n d c o m p o u n d s h a v e
very s t r o n g a n i s o t r o p y , so t h a t fields higher t h a n
t h o s e available from l a b o r a t o r y e l e c t r o m a g n e t s
1
o r 2 0 k O e ) a r e necessary for their
( ~ 1.6 A m
m e a s u r e m e n t . S u p e r c o n d u c t i n g m a g n e t s o r Bitter
m a g n e t s (see Sect. 8) m a y be used, except their u s u a l
configuration m a k e s t o r q u e m e a s u r e m e n t s difficult.
Very high pulsed fields with pulse w i d t h s of m a n y
milliseconds c a n be p r o d u c e d b y d i s c h a r g i n g a large
c a p a c i t o r b a n k t h r o u g h a reinforced coil; e q u i p m e n t
of this k i n d is m a d e c o m m e r c i a l l y for m a g n e t i z i n g
230
7.
Magnetostriction
M a g n e t o s t r i c t i o n describes t h e c h a n g e in d i m e n s i o n s
of a m a g n e t i c s a m p l e with c h a n g e s in t h e state o r
direction of m a g n e t i z a t i o n . F r o m a n engineering
p o i n t of view, t h e q u a n t i t y of interest is the c h a n g e in
length of a s a m p l e w h e n its m a g n e t i z a t i o n is c h a n g e d ,
typically from p l u s t o m i n u s s a t u r a t i o n o r n e a r satu
r a t i o n . Scientifically, t h e m e a s u r e d values a r e the
c h a n g e s in d i m e n s i o n of a single crystal as the satu
r a t i o n m a g n e t i z a t i o n is r o t a t e d t o v a r i o u s crystallo
g r a p h i c directions. T h e e x p e r i m e n t a l c o n s i d e r a t i o n s
a r e similar in b o t h cases (Lee 1979).
M a g n e t o s t r i c t i v e strains a r e generally small, of the
5
o r d e r of 1 0 " . If the available s a m p l e s a r e large
e n o u g h , electric resistance strain gauges p r o v i d e t h e
simplest m e a s u r e m e n t t e c h n i q u e . T h e y c a n be driven
with either ac o r d c c u r r e n t s , a n d the m a n u f a c t u r e r ' s
c a l i b r a t i o n c o n s t a n t s a r e sufficient for a c c u r a c y of
a b o u t 1 % . M o s t strain g a u g e alloys s h o w significant
m a g n e t o r e s i s t a n c e , w h i c h m u s t b e b a l a n c e d with a
d u m m y g a u g e n o t a t t a c h e d t o t h e s a m p l e b u t in the
s a m e field, o r o t h e r w i s e c o r r e c t e d for.
L i n e a r variable differential t r a n s f o r m e r s ( L V D T s )
a r e p o s i t i o n sensors with sufficient sensitivity for
m a g n e t o s t r i c t i o n m e a s u r e m e n t s a n d a r e useful for
r i b b o n o r wire s a m p l e s t h a t a r e t o o thin o r t o o n a r r o w
for strain gauges. L V D T s h a v e t h e a d v a n t a g e t h a t the
m e a s u r i n g i n s t r u m e n t c a n b e held a t r o o m t e m p e r a
t u r e w h e n t h e s a m p l e is h e a t e d o r cooled. Very small
s a m p l e s m a y be m e a s u r e d using c a p a c i t a n c e m e t h o d s ,
w h e r e c h a n g e s in t h e length of t h e s a m p l e v a r y t h e
spacing of a p a i r of c a p a c i t o r plates.
If l o n g s a m p l e s (1 m ) a r e t o be m e a s u r e d , as o n steel
t r a n s f o r m e r sheets, c o m m e r c i a l p h o n o g r a p h p i c k u p s
h a v e sufficient sensitivity a n d a r e easy a n d c o n v e n i e n t
to use.
8. Use of Superconducting
Magnets
Solenoids
or
Bitter
Magnetic
currently r e q u i r e o p e r a t i o n in liquid h e l i u m a l t h o u g h
the a p p l i c a t i o n of h i g h - t e m p e r a t u r e s u p e r c o n d u c t o r s
in small coils h a s a l r e a d y b e e n d e m o n s t r a t e d . ) T h e r e
are n o f u n d a m e n t a l differences b e t w e e n m a g n e t i c
m e a s u r e m e n t s in e l e c t r o m a g n e t s a n d in solenoids o r
coils, b e y o n d t h e o b v i o u s fact t h a t access t o t h e
s a m p l e a n d a n y s a m p l e m o t i o n a r e generally parallel
t o the applied field in a solenoid a n d p e r p e n d i c u l a r t o
the field in a n e l e c t r o m a g n e t . T h i s g e o m e t r y m a k e s
t o r q u e m e a s u r e m e n t s difficult, b u t n o t impossible.
(Both s u p e r c o n d u c t i n g a n d w a t e r - c o o l e d solenoids
c a n be built a s split coils t o p e r m i t r a d i a l o r t r a n s v e r s e
access t o t h e highest-field region, a t t h e cost of lower
m a x i m u m field.) Pulsed fields m a y r e q u i r e special
m e a s u r e m e n t t e c h n i q u e s , especially if t h e pulse time is
very s h o r t .
T h e fact t h a t s u p e r c o n d u c t o r s exclude m a g n e t i c
flux a t low fields b u t n o t c o m p l e t e l y a t high fields
gives rise t o a n i m a g e effect in s u p e r c o n d u c t i n g m a g
nets a n a l o g o u s t o t h a t in e l e c t r o m a g n e t s .
9. Magnetic
Measurements
on
Superconductors
Materials:
Measurements
a s q u a r e frame w h i c h is t h e n o p e r a t e d as a t r a n s
f o r m e r u n d e r n o - l o a d c o n d i t i o n s . T h e p o w e r loss in
t h e t r a n s f o r m e r is m e a s u r e d , usually with a sensitive
a n d a c c u r a t e w a t t m e t e r , with a c o r r e c t i o n applied (if
necessary) for t h e J o u l e h e a t i n g in t h e w i n d i n g s . T h i s
is k n o w n as t h e E p s t e i n test; t h e results a r e q u o t e d in
w a t t s p e r k i l o g r a m (or w a t t s p e r p o u n d ) at a specified
m a x i m u m flux density, usually I T , 1.5 o r 1.8
(10 k G , 1 5 k G o r 18 k G ) , a n d a specified frequency,
n o r m a l l y 50 H z o r 60 H z . T h e o u t p u t voltage w a v e
f o r m of t h e E p s t e i n frame s h o u l d be sinusoidal, which
m e a n s t h a t the flux c h a n g e with t i m e in t h e m a t e r i a l is
sinusoidal; this c o n d i t i o n requires a very n o n s i n u s o i d a l i n p u t c u r r e n t , a c o n d i t i o n t h a t is increasingly
difficult t o m e e t as the m a x i m u m flux density is
increased.
Because the E p s t e i n test uses a relatively large
a m o u n t of m a t e r i a l , a n d a s s e m b l i n g t h e test frame is a
slow m a n u a l o p e r a t i o n , there is a s t r o n g t e n d e n c y t o
s u p p l e m e n t o r replace t h e E p s t e i n test with s o m e form
of single-strip test, using a single strip of test m a t e r i a l
a n d a h i g h - p e r m e a b i l i t y y o k e . H o w e v e r , n o generally
a c c e p t e d single-strip test h a s been d e v e l o p e d .
S o m e t i m e s , t h e i r o n loss ( o r c o r e loss) is " s e p a r
a t e d " i n t o hysteresis loss, m e a s u r e d a t very low fre
q u e n c y o r " d c , " a n d a s s u m e d t o be i n d e p e n d e n t of
frequency; a n d e d d y c u r r e n t loss, a s s u m e d t o vary as
t h e s q u a r e of t h e frequency a n d inversely as the
electrical resistivity. If t h e m e a s u r e d hysteresis loss
p l u s t h e c a l c u l a t e d e d d y c u r r e n t loss is less t h a n the
m e a s u r e d t o t a l a c loss (as is a l w a y s t h e case), t h e
difference is called t h e a n o m a l o u s loss. T h i s simple
linear s e p a r a t i o n of losses is a l m o s t entirely w i t h o u t
physical m e a n i n g .
A n o t h e r c o m m o n specification for high-quality
t r a n s f o r m e r m a t e r i a l is t h e p e a k flux density at a n
1
a p p l i e d field of 800 A m " ( 1 0 O e ) . T h i s is n o r m a l l y
m e a s u r e d a t 50 H z o r 60 H z a n d is a m e a s u r e of the
c r y s t a l l o g r a p h i c o r i e n t a t i o n of t h e steel; h i g h e r values
a r e better.
F o r m a n y a p p l i c a t i o n s , either t h e initial p e r m e a b i
lity o r t h e m a x i m u m p e r m e a b i l i t y / / m ax is i m p o r t a n t ;
p e r m e a b i l i t y is defined as B/H. O t h e r tests a r e used o n
h i g h - p e r m e a b i l i t y m a t e r i a l s t h a t a r e m o r e o r less
directly related t o their i n t e n d e d a p p l i c a t i o n as relays,
high-frequency t r a n s f o r m e r s , shielding m a t e r i a l s , a n d
so o n .
Materials
11.
Permanent
Magnet
Materials
P e r m a n e n t m a g n e t s a r e always used t o c r e a t e a m a g
netic field in space a n d so a l w a y s o p e r a t e in their o w n
d e m a g n e t i z i n g field. T h e i r b e h a v i o r in t h e second
q u a d r a n t of t h e hysteresis l o o p (H < 0, > 0) is
therefore of p r i m a r y interest. Since high fields a r e
r e q u i r e d for m e a s u r e m e n t s , ring s a m p l e s c a n n o t be
used; s a m p l e s a r e either c l a m p e d in t h e g a p of a n
e l e c t r o m a g n e t , w h i c h o p e r a t e s as a y o k e , o r a r e
231
Magnetic
Materials:
Measurements
Bibliography
American Society for Testing and Materials 1964 Magnetic
TestingTheory and Nomenclature. ASTM Technical
Publication 371. ASTM, Philadelphia. PA
American Society for Testing and Materials 1970 Direct
Current Measurements of Soft Magnetic
Materials.
ASTM Technical Publication 371 SI. ASTM, Philadel
phia, PA
American Society for Testing and Materials 1991 Annual
Book of ASTM Standards, Pt. 44. ASTM, Philadelphia,
PA
Chikazumi S 1964 Physics of Magnetism. Wiley, New York,
pp. 15-37; 128^7
Cullity D 1972 Introduction to Magnetic
Materials.
Addison-Wesley, Reading, MA, Chaps. 1,2; pp. 215-33
Flanders J 1988 An alternating gradient magnetometer.
J. Appl. Phys. 63: 3940-6
Foner S 1967 Special magnetic measurement techniques.
J. Appl. Phys. 38: 1510-19
Frey Th, Jantz W, Stibal R 1988 Compensated vibrating
reed magnetometer. / . Appl. Phys. 64: 6002-8
Goldfarb R, Spomer R L 1990 Magnetic characteristics and
measurements of filamentary Nb-Ti wire for the super
conducting supercollider. Adv. Cryog. Eng. (Mater.) 36:
215-22
232
1. Physical
Capabilities
A n M P M is a n exciting c o n c e p t . A system w i t h t h e
ability t o s a m p l e t h e m e c h a n i c a l r e s p o n s e of a speci
m e n w i t h s u b m i c r o m e t e r spatial r e s o l u t i o n h a s a n
extremely wide r a n g e of a p p l i c a t i o n s . R e c e n t d e v e l o p
m e n t s in h a r d w a r e a n d u n d e r s t a n d i n g h a v e m a d e this
goal a reality.
T h e m e c h a n i c a l p r o p e r t i e s m i c r o p r o b e will a d v a n c e
o u r u n d e r s t a n d i n g of m a c r o s c o p i c p r o p e r t i e s in t h e
Mechanical
s a m e w a y t h a t t h e chemical m i c r o p r o b e h a s i m p r o v e d
o u r u n d e r s t a n d i n g of t h e c h e m i s t r y of t h e m a t e r i a l s
a n d t h e t r a n s m i s s i o n electron m i c r o s c o p e ( T E M ) h a s
i m p r o v e d o u r u n d e r s t a n d i n g of s t r u c t u r e s .
O n l y o n e t y p e of m e c h a n i c a l test c a n b e used a s a n
M P M . G i l m a n (1973) s h o w e d t h a t a m i c r o i n d e n t a t i o n test, if p r o p e r l y i n s t r u m e n t e d a n d c o n t r o l l e d ,
c a n p e r f o r m as a n M P M . D u r i n g a n i n d e n t a t i o n test
b o t h elastic a n d plastic s t r a i n s a r e g e n e r a t e d . F o r
m a n y m a t e r i a l s t h e s t r a i n s from b o t h fields a r e of
sufficient m a g n i t u d e t o b e m e a s u r e d . T h e test c a n b e
scaled d o w n so t h a t s u b m i c r o m e t e r v o l u m e s of m a t e r
ial a r e s a m p l e d .
M i c r o i n d e n t a t i o n tests h a v e b e e n used t o m e a s u r e
a n extremely w i d e variety of m a t e r i a l p r o p e r t i e s .
Yield s t r e n g t h ( T a b o r 1951), c r e e p resistance (Westb r o o k 1957, C h u a n d Li 1977), stress r e l a x a t i o n ( C h u
a n d Li 1980), m o d u l u s (Bulychev et al. 1975), fracture
t o u g h n e s s ( L a w n a n d W i l s h a w 1975, L a w n a n d E v a n s
1977) a n d even fatigue tests (Li a n d C h u 1979) h a v e
been p e r f o r m e d u s i n g v a r i o u s types of i n d e n t a t i o n
tests. In a d d i t i o n , b e c a u s e t h e m a t e r i a l being tested is
close t o a surface, e n v i r o n m e n t a l effects c a n b e
m e a s u r e d ( W e s t w o o d a n d M a c m i l l a n 1973). W i t h t h e
p r o p e r c o m b i n a t i o n of m i c r o i n d e n t a t i o n tests a
nearly c o m p l e t e c o n s t i t u t i v e e q u a t i o n of t h e m e c h a n i
cal r e s p o n s e of t h e s a m p l e c a n b e m a p p e d o u t .
Strength (Pethica et al. 1983, Oliver et al. 1984) a n d
m o d u l u s ( D o e r n e r a n d N i x 1986) a r e t w o p r o p e r t i e s
t h a t a r e n o w r o u t i n e l y d e t e r m i n e d from s u b m i c r o
meter volumes.
T h e e x p e r i m e n t a l p a r a m e t e r s a s s o c i a t e d with a n
i n d e n t a t i o n test t h a t relate t o t h e m e c h a n i c a l p r o p e r
ties j u s t m e n t i o n e d include t h e force o n t h e i n d e n t e r ,
the g e o m e t r y of t h e i n d e n t e r , t h e t e m p e r a t u r e ( a n d
other important environmental parameters), the
m e c h a n i c a l p r o p e r t i e s of t h e i n d e n t e r a n d t h e t i m e
d e p e n d e n c e of all t h e p a r a m e t e r s . I n a d d i t i o n , for
special a p p l i c a t i o n s , o t h e r p a r a m e t e r s m u s t b e a d d e d
to this list (e.g., t h e stiffness o r electrical p r o p e r t i e s of
the c o n t a c t ) .
O n e of t h e m o r e difficult p a r a m e t e r s t o m e a s u r e is
the g e o m e t r y of t h e i n d e n t . T h e c o n t a c t a r e a b e t w e e n
the s a m p l e a n d i n d e n t e r u n d e r l o a d is t h e m o s t
i m p o r t a n t g e o m e t r i c aspect of a n i n d e n t a t i o n test.
T h e final a r e a of a s t a n d a r d m i c r o h a r d n e s s test is
m e a s u r e d optically after t h e i n d e n t e r is r e m o v e d , a n d
the a s s u m p t i o n is m a d e t h a t t h e a r e a d o e s n o t c h a n g e
o n u n l o a d i n g . A l t h o u g h i m a g i n g i n d e n t s d o e s give a
direct m e a s u r e of t h e m o s t i m p o r t a n t aspect of t h e
g e o m e t r y , it b e c o m e s m o r e difficult as t h e size of t h e
indent is r e d u c e d . S u b m i c r o m e t e r - s i z e d i n d e n t s c a n
only be i m a g e d u s i n g electron m i c r o s c o p y . T h e tech
niques used a r e t i m e c o n s u m i n g a n d o n l y yield t h e
final size of t h e i n d e n t .
O n e geometric characteristic of t h e i n d e n t t h a t is
m o r e easily m e a s u r e d a n d c a n b e m e a s u r e d c o n t i
n u o u s l y d u r i n g t h e entire i n d e n t a t i o n p r o c e s s is t h e
displacement of t h e i n d e n t e r after c o n t a c t . T h i s
Properties
Microprobe
Current
Digitize
source
Coil
Displacement
detecting
electronics
Table c o n t r o l
V
x-y
table
lOOnm/step
Micro
computer
Figure 1
Schematic diagram of the Nanoindenter
m e a s u r e m e n t p r o v i d e s several o t h e r distinct a d v a n
tages o v e r direct a r e a m e a s u r e m e n t . T h e s e include t h e
ability t o s a m p l e b o t h elastic a n d plastic strains, t h e
ability t o c o n t r o l a n d m o n i t o r stress a n d strain rates
a n d , finally, t h e e l i m i n a t i o n of t h e n e e d for c o m p l i
c a t e d , t i m e - c o n s u m i n g i m a g i n g t e c h n i q u e s . T h e dis
p l a c e m e n t c a n b e m e a s u r e d w i t h sufficient r e s o l u t i o n
t o c h a r a c t e r i z e extremely small i n d e n t s ; h o w e v e r ,
m o d e l s of t h e i n d e n t a t i o n p r o c e s s m u s t b e e m p l o y e d
t o allow t h e c o n t a c t a r e a t o b e calculated. T h e s e
m o d e l s h a v e b e e n d e v e l o p e d a n d used successfully
(Bulychev et al. 1975, Oliver et al. 1984).
2.
Mechanics
A s c h e m a t i c of a n M P M is s h o w n in F i g . 1. T h e force
is a p p l i e d t o t h e i n d e n t e r electromagnetically. T h e
d i s p l a c e m e n t - s e n s i n g system consists of a capacitive
d i s p l a c e m e n t g a u g e . I n this case, t h e m o v a b l e p o r t i o n
of t h e g a u g e is fixed t o t h e shaft c o n n e c t i n g t h e forcea p p l i c a t i o n system t o t h e i n d e n t e r . T h e w h o l e as
sembly is s u p p o r t e d b y leaf springs ( n o t s h o w n ) . T h e
s a m p l e is m o v e d b y a m o t o r i z e d x-y table. All aspects
of t h e system a r e c o n t r o l l e d b y a m i c r o c o m p u t e r . T h e
entire p r o c e s s is a u t o m a t e d so t h a t a set of i n d e n
t a t i o n e x p e r i m e n t s is p e r f o r m e d from initiation t o
c o m p l e t i o n w i t h o u t o p e r a t o r supervision.
T h e r e s o l u t i o n s of t h e v a r i o u s c o m p o n e n t s of the
system d e p i c t e d a r e carefully m a t c h e d t o p e r f o r m as
a n M P M . T h e force a p p l i c a t i o n of this p a r t i c u l a r
233
Mechanical
Properties
Microprobe
Figure 2
TEM image of a replica of a 200 nm deep indent in nickel
system h a s t w o r a n g e s , 0 - 2 0 m N a n d 0 - 1 2 0 m N , with
resolutions of 300 n N a n d 1.5 , respectively. T h e
d i s p l a c e m e n t sensing system h a s a r e s o l u t i o n of
0.2 n m . T h e x-y t a b l e h a s a precision of 0.1 .
F i g u r e s 2 a n d 3 s h o w t h e scale of m i c r o i n d e n t a t i o n s
m a d e w i t h s u c h a system. T h e i m a g e in F i g . 2 is
200 n m d e e p in nickel. T h i s i n d e n t is a factor of ten
larger t h a n t h e smallest i n d e n t s from which r e a s o n
ably precise d a t a c a n b e o b t a i n e d . T h e scale of the
e x p e r i m e n t relative t o t h e scale of a microcircuit is
s h o w n in Fig. 3. T h e i n d e n t s a r e clearly visible a t the
highest magnification.
A l t h o u g h a variety of i n d e n t a t i o n tests a r e useful,
there a r e s o m e e x p e r i m e n t a l similarities c o m m o n t o
all tests p e r f o r m e d with such a system. First, the
p o s i t i o n of e a c h i n d e n t o n t h e surface of t h e specimen
m u s t be established. A c o m b i n a t i o n of a n optical
m i c r o s c o p e a n d t h e high a c c u r a c y x-y table allows
Figure 3
Two indents in a microcircuit demonstrating the fine scale of the experiment
234
Mechanical
Properties
Microprobe
Q_
20
3.
Applications
S o m e e x a m p l e s of h o w t h e M P M h a s been a p p l i e d t o
material research p r o b l e m s a r e s h o w n in Figs. 5 - 1 1 .
F i g u r e 5 s h o w s t h e c h a n g e in h a r d n e s s a s a function of
d e p t h associated with a n a m o r p h o u s surface layer o n
s a p p h i r e caused b y ion b o m b a r d m e n t . Surface t r e a t
m e n t s such as ion b o m b a r d m e n t a r e being c o n s i d e r e d
for high-wear a p p l i c a t i o n s . F r a c t u r e a n d w e a r rates
associated with p i n - o n - d i s k w e a r tests a r e r e d u c e d
b y t h e presence o f these layers ( M c H a r g u e 1987).
T h e s e t r e a t m e n t s e x t e n d in d e p t h only a few h u n d r e d
n a n o m e t e r s ; h e n c e , it is very difficult t o s a m p l e t h e
m e c h a n i c a l p r o p e r t i e s of t h e t r e a t e d layer. B o t h t h e
h a r d n e s s a n d m o d u l u s c a n b e d e t e r m i n e d in such t h i n
layers as s h o w n in F i g . 6 (Oliver et al. 1987a). T h e
decreased m o d u l u s s h o w n in F i g . 6 a n d t h e decreased
h a r d n e s s s h o w n in F i g . 5 h e l p t o explain t h e w e a r
p r o p e r t i e s of this m a t e r i a l . T h e s e d a t a s h o w h o w
m i c r o i n d e n t a t i o n tests c a n b e used t o c h a r a c t e r i z e
thin films.
A n o t h e r a r e a w h e r e t h e M P M will h a v e a n i m p a c t
is rapidly solidified m a t e r i a l s . T h e p r o d u c t of r a p i d solidification processing (i.e., p o w d e r , ribbon o r
splats) h a s a t least o n e small d i m e n s i o n . N o r m a l l y , t o
test t h e p r o p e r t i e s o f these m a t e r i a l s t h e y m u s t first b e
c o n s o l i d a t e d i n t o large e n o u g h p r o d u c t s t o allow
m a c r o s c o p i c tests t o b e a c c o m p l i s h e d . T h e c o n s o l i d a
tion step often involves s o m e h e a t i n g ; h e n c e , t h e a s solidified m i c r o s t r u c t u r e c a n b e d i s t u r b e d . F i g u r e 7
shows a series of i n d e n t a t i o n s m a d e in t h e edge of a
ribbon of rapidly solidified A l - L i - B e alloy (Oliver et
al. 1987b). T h e r i b b o n w a s a p p r o x i m a t e l y 50
thick. A s t u d y of t h e p r o p e r t i e s of this alloy after
v a r i o u s a n n e a l i n g t r e a t m e n t s indicates a 3 0 % d r o p in
strength after a 1 h a n n e a l a t 200 C. T h e ability t o
characterize t h e m e c h a n i c a l p r o p e r t i e s of this alloy in
the as-solidified s t a t e h a s g e n e r a t e d further interest in
processing t e c h n i q u e s a n d alloy d e v e l o p m e n t .
I n t h e a r e a of welding, t h e M P M is being used t o
a d d r e s s t h e p r o b l e m o f weld e m b r i t t l e m e n t in d u p l e x
stainless steels. F i g u r e 8 ( D a v i d et al. 1987) s h o w s
s o m e relatively large i n d e n t s m a d e in a specimen from
I2H
*>
200
400
Depth (nm)
Figure 4
Typical load vs displacement and hardness vs
displacement curves for electropolished nickel
5Qr-
40
Q2 30
unimplanted
implanted
150
200
250
350
Figure 5
The change in hardness of a sapphire surface associated
with an amorphous surface layer caused by ion
implantation
235
Mechanical
Properties
Microprobe
a 308 austenitic stainless steel weld. T h e m i c r o s t r u c t u r e consists of a n austenite m a t r i x with ferrite islands
a few m i c r o m e t e r s in d i m e n s i o n . By s t u d y i n g the
c h a n g e s in t h e p r o p e r t i e s of b o t h t h e a u s t e n i t e a n d
ferrite as a function of aging t r e a t m e n t , t h e causes of
the e m b r i t t l i n g processes will be b e t t e r u n d e r s t o o d .
A n o t h e r e x a m p l e of h o w t h e M P M is applied t o
m a t e r i a l s d e v e l o p m e n t p r o b l e m s involves r a d i a t i o n d a m a g e d m a t e r i a l s . H e a v y ion b o m b a r d m e n t h a s
long been used t o simulate d a m a g e s t r u c t u r e s associ
a t e d with n e u t r o n i r r a d i a t i o n . S u c h t r e a t m e n t s only
affect m a t e r i a l within a few m i c r o m e t e r s of t h e surface
a n d h a v e been extremely useful for s t r u c t u r a l studies.
H o w e v e r , for m e c h a n i c a l - p r o p e r t i e s studies, m a c r o
scopic n e u t r o n - d a m a g e d specimens a r e typically
required a n d a r e extremely expensive. F i g u r e s 9-11
(Zinkle a n d Oliver 1986) s h o w h o w t h e M P M c a n b e
used t o c h a r a c t e r i z e t h e less expensive i o n b o m b a r d e d
m a t e r i a l . F i g u r e 9 s h o w s the result of i n d e n t i n g the
d a m a g e d surface directly a n d c o m p a r i n g t h e resulting
l o a d - d i s p l a c e m e n t curve with t h a t s a m e d a t a o b t a i n e d
from a n u n d a m a g e d section of t h e specimen. Clearly,
the effects of t h e d a m a g e a r e evident as a h a r d n e s s
increase n e a r the surface. C u r v e s of t h e t y p e s h o w n in
Fig. 9 a r e very sensitive t o surface p r o p e r t i e s ; h o w
ever, their i n t e r p r e t a t i o n is challenging o w i n g t o t h e
u n c e r t a i n t y as t o which region of m a t e r i a l below t h e
i n d e n t e r is c o n t r i b u t i n g m o s t t o t h e h a r d n e s s a t a n y
given d e p t h of p e n e t r a t i o n . F i g u r e s 10 a n d 11 a r e t h e
result of using cross-sectional t e c h n i q u e s t o s a m p l e
the surface layer of interest. T h e s a m p l e is p r e p a r e d
by p l a t i n g t h e surface s u b s e q u e n t t o the i r r a d i a t i o n
a n d then cross sectioning t h e resulting s a n d w i c h . A
series of m i c r o i n d e n t a t i o n tests t h a t a r e spatially
progressed across t h e original interface a r e used t o
sample t h e m a t e r i a l of interest in cross section. F i g u r e
10 shows such a series, a n d Fig. 11 s h o w s t h e resulting
d a t a . T h e e x p e r i m e n t resulting in F i g . 9 is m u c h
simpler t o p e r f o r m h o w e v e r , t h e results of t h e crosssectional t e c h n i q u e a r e m o r e easily i n t e r p r e t e d .
M o d e l s a n d n u m e r i c a l c a l c u l a t i o n s t o relate t h e t w o
are being p u r s u e d . If such s a m p l e s a n d tests c a n b e
used as a n initial sorting tool for c h a r a c t e r i z i n g
resistance t o r a d i a t i o n d a m a g e , t h e cost of such
research could be r e d u c e d by a t least a n o r d e r of
magnitude.
4. Descriptive
4 0 0 '
unimplanted
implanted
100
150
200
J250
3 0I0
Figure 6
The change in modulus of the same ion-implanted
sapphire surface shown in Fig. 5
a function of d e p t h from l o a d - d i s p l a c e m e n t d a t a
r e q u i r e careful c o n s i d e r a t i o n . T h e d a t a r e q u i r e d a r e
o b t a i n e d from a n i n d e n t a t i o n test consisting of a
series of l o a d i n g a n d u n l o a d i n g sequences going t o
progressively higher m a x i m u m l o a d s . T h e displace
m e n t m e a s u r e m e n t s m a d e d u r i n g l o a d i n g sequences,
in w h i c h the size of t h e i n d e n t is increased plastically,
c o n t a i n i n f o r m a t i o n a b o u t b o t h t h e elastic a n d plastic
strain fields. T h e u n l o a d i n g d a t a represents t h e re
s p o n s e of t h e elastic field only. U s i n g i n f o r m a t i o n
from b o t h sequences of d a t a the plastic a n d elastic
c o m p o n e n t s c a n be s e p a r a t e d ; hence, the h a r d n e s s
a n d m o d u l u s c a n be calculated for each p o i n t a t
w h i c h a n u n l o a d i n g sequence begins ( D o e r n e r a n d
N i x 1986).
Models
A p p l i c a t i o n s like t h e o n e s j u s t discussed p r o v i d e t h e
driving force for t h e second a r e a of research related t o
M P M s . T h i s is t h e d e v e l o p m e n t of m o d e l s t o allow
researchers t o d e c o n v o l u t e t h e c o m p l i c a t e d g e o m e t r y
of i n d e n t a t i o n tests a n d extract useful m e c h a n i c a l
properties.
O n e e x a m p l e of such a n effort is d e m o n s t r a t e d b y
Figs. 5 a n d 6 w h i c h h a v e a l r e a d y been discussed. T h e
m o d e l s necessary t o retrieve m o d u l u s a n d s t r e n g t h as
236
500
Figure 7
Indents in the edge of a rapidly solidified Al-Li-Be alloy
ribbon
Mechanical
Properties
Microprobe
Figure 8
SEM image of indents traversing a ferrite island in a weld
in a duplex stainless steel
Figure 10
Series of indents approaching the original surface of a
heavy ion damaged specimen that has been cross sectioned
5. The
0
200
400
600
Indent
800
1000
1200
1400
depth (nm)
Figure 9
Hardness changes in copper due to radiation damage
associated with heavy ion bombardment sampled by direct
indentation of the treated surface
(4 MeV F e + + + 50 at.ppm, peak.damage = 15 dpa,
r i rr = 220C)
Future
I n t e r e s t in t h e M P M is high. T h e d u r a t i o n of t h a t
interest will d e p e n d o n t h e success such systems h a v e
in c o n t r i b u t i n g t o t h e s o l u t i o n of i m p o r t a n t t e c h n o l o
gical q u e s t i o n s . T h e e x a m p l e s o u t l i n e d h e r e s h o w t h e
diversity of industries t h a t c a n m a k e use of the
i n f o r m a t i o n t h e M P M g e n e r a t e s . If a fraction of such
cases result in real p r o g r e s s , t h e future of M P M s is
a s s u r e d . S u c h systems will b e c o m e a n o t h e r i m p o r t a n t
t o o l available t o all m a t e r i a l scientists.
237
Mechanical
Properties
Microprobe
mechanical
u sn
P
\i /
..
electropolish
2
3
4
Depth from interface (/zm)
Figure 11
Results of the series of indents shown in Fig. 10:
cross-section hardness of copper following 14 MeV
copper-ion irradiation (indent depth = 150 nm, peak
damage = 40 dpa, TiTI = 100 C)
Acknowledgements
T h e a u t h o r w o u l d like t o a c k n o w l e d g e t h e s p o n s o r i n g
of this w o r k by t h e Division of M a t e r i a l s Sciences, U S
D e p a r t m e n t of E n e r g y , u n d e r c o n t r a c t D E - A C 0 5 840R21400 with M a r t i n M a r i e t t a E n e r g y Systems,
Inc.
Oliver W C, Hutchings R, Pethica J 1984 Microindentation techniques in materials science. In: Blau J, Lawn
R (eds.) 1984 American Society for Testing and Mater
ials Special Technical Publication 889. ASTM Philadel
phia, PA, p. 303
Oliver W C, McHargue C J, Zinkle S J 1987a Thin film
characterization using a mechanical properties micro
probe. Thin Solid Films 153: 185-6
Oliver W C, Wadsworth J, Nieh G 1987b Characteriza
tion of rapidly solidified Al-Be-Li and Al-Be ribbons.
Scr. Metall. 21: 1429-33
Pethica J B, Hutchings R, Oliver W C 1983 Hardness
measurement at penetration depths as small as 20 nm.
Philos. Mag. A 48(A): 593-606
Tabor D 1951 The Hardness of Metals. Clarendon Press,
Oxford
Westbrook J 1957 Microhardness testing at high tempera
tures. Proc. Am. Soc. Test. Mater. 57: 873-95
Westwood A R C , Macmillan 1973 Environmentsensitive hardness of nonmetals. In: Conrad H, West
brook J (eds.) 1973 American Society for Metals. ASM,
Materials Park, OH, pp. 377-417
Zinkle S J, Oliver W C 1986 Mechanical property measure
ments on ion-irradiated copper and Cu-Zr. J. Nucl.
Mater. 143 (Nov): 548-52
W . C. Oliver
[Oak R i d g e N a t i o n a l L a b o r a t o r y ,
O a k R i d g e , Tennessee, U S A ]
Microengineering of Materials:
Characterization
Bibliography
238
Microengineering
m e t h o d s for t r a n s p a r e n t m a t e r i a l s , a n d electron
b e a m c h a r a c t e r i z a t i o n a n d x-ray t e c h n i q u e s for b o t h
opaque and transparent materials.
1. Optical
Methods
1.1
Microscopes
T h e w o r k h o r s e of t h e I C F target i n d u s t r y is t h e
optical m i c r o s c o p e used for a s s e m b l y of I C F t a r g e t s .
T a r g e t builders use stereo m i c r o s c o p e s with a w o r k i n g
distance of a t least 0.1 m t o allow for free m a n i p u l a
tion of t h e t a r g e t w i t h o u t t h e risk of d a m a g e . A
c o n t i n u o u s z o o m from a p p r o x i m a t e l y x 3 t o x 60
allows t h e f a b r i c a t o r t o k e e p all t h e aspects of t h e
assembly in view a n d t o focus closely o n details w h e n
necessary.
P r e l i m i n a r y selection of t a r g e t m a t e r i a l s is generally
accomplished o n a b i n o c u l a r m i c r o s c o p e , usually a
higher q u a l i t y i n s t r u m e n t t h a n a n assembly m i c r o
scope. A m o v a b l e cross-hair o r filar eyepiece is useful
in sizing the target c o m p o n e n t s . Alternatively a s t a n
d a r d eyepiece c a n m e a s u r e t h e shell d i a m e t e r t o a b o u t
0.5 . T h e target surface c a n b e inspected with t h e
s a m e i n s t r u m e n t b y r o t a t i n g it u n d e r t h e objective.
Dark-field i l l u m i n a t i o n using stain-free optics will
detect surface defects a n d r o u g h s p o t s . F i n e focus a n d
a shallow d e p t h of field allow inspection of t h e
interior surfaces of t r a n s p a r e n t shells.
1.2
Interferometry
of Materials:
Characterization
239
Microengineering
of Materials:
Characterization
240
Microsphere
target
motion
motion
Figure 1
Schematic showing detail of An manipulator design:
(a) magnetic loading, (b) driven plate and (c) captive
master spheres
2. Electron
Beam
Characterization
of ICF
Targets
Highly d e m a n d i n g r e q u i r e m e n t s for c o m p o s i t i o n ,
g e o m e t r y a n d surface finish a r e c o m m o n t o t h e crea
tion of t a r g e t s for I C F . T h e s e r e q u i r e m e n t s generally
stem from t h e need t o m a i n t a i n s y m m e t r y a n d stabi
lity d u r i n g t h e i m p l o s i o n - c o m p r e s s i o n p h a s e of e a c h
test. T a r g e t s for these e x p e r i m e n t s typically h a v e
overall d i m e n s i o n s less t h a n 1 m m , i n t e n t i o n a l struc
tures in t h e m i c r o m e t e r r a n g e a n d u n w e l c o m e features
in t h e n a n o m e t e r r a n g e . S u c h small scales r e q u i r e d t h e
use early o n of t h e s c a n n i n g electron m i c r o s c o p e
( S E M ) a n d related electron b e a m t e c h n i q u e s t o c h a r
acterize I C F t a r g e t s .
2.1 Signals and Detector
Types
T h e i m p a c t of accelerated electrons with m a t t e r re
sults in a variety of e m i t t e d signals as e n u m e r a t e d in
T a b l e 1. M a n y S E M s h a v e d e t e c t o r s c a p a b l e of
m e a s u r i n g these signals a n d r e a c h i n g a c o m p l e t e
a n s w e r t o a n analytical q u e s t i o n usually involves
m a k i n g full use of these signals a n d d e t e c t o r s . T h e
Microengineering
Table 1
Types of signals available in SEM and methods of detection
Emitted signal
Detector
Secondary
electrons
Backscattered
electrons
Scintillator/
photomultiplier
Silicon diode
Absorbed current
electrons
Auger electrons
Current amplifier
Characteristic and
bremsstrahlung
rays
Solid state
detector or
curved crystal
spectrometer
Film
Kossel diffraction
rays
Cathodoluminescence
Heat
Electron energy
Monochromator/
photomultiplier
Piezoelectric
transducer
Information
conveyed
Topography,
dimensions
Topography,
dimensions,
atomic number
Dimensions,
atomic number
Elemental
analysis
Elemental
analysis
Crystallography
Chemistry, carrier
lifetimes
Subsurface
mechanical
defects
m o s t c o m m o n use of t h e S E M is t o p r o d u c e i m a g e s
using t h e first three signals listed in T a b l e 1. S e c o n d
ary electrons a r e c o n v e n t i o n a l l y defined as t h o s e
electrons e m i t t e d from t h e s a m p l e surface t h a t h a v e
energies less t h a n 50 eV. S u c h low energies i m p l y t h a t
these electrons o r i g i n a t e w i t h i n a few n a n o m e t e r s of
t h e surface. A s a c o n s e q u e n c e , this signal h a s t h e
highest spatial r e s o l u t i o n of all t h e e m i t t e d signals.
B a c k s c a t t e r e d electrons a r e t h o s e incident e l e c t r o n s
t h a t u n d e r g o elastic collisions in t h e s a m p l e a n d t h u s
retain energy n e a r t h a t of t h e original b e a m . T h e
b a c k s c a t t e r e d electron intensity d e p e n d s o n t h e aver
age a t o m i c n u m b e r of t h e s a m p l e . T h i s signal t h u s
m a p s t h e c o m p o s i t i o n of t h e surface. R e s o l u t i o n for
elements from r o w f o u r o f t h e p e r i o d i c table is
a p p r o x i m a t e l y o n e - t h i r d of a n a t o m i c n u m b e r .
A b s o r b e d c u r r e n t consists of t h o s e e l e c t r o n s t h a t
a r e n o t e m i t t e d from t h e s a m p l e a n d a r e n o r m a l l y
c o n d u c t e d t o g r o u n d . T h e c o n t r a s t in t h e a b s o r b e d
c u r r e n t i m a g e is similar t o t h e b a c k s c a t t e r e d signal
except inverted; b r i g h t a r e a s in the b a c k s c a t t e r e d
i m a g e a p p e a r d a r k in a b s o r b e d c u r r e n t i m a g e s .
T h e p o p u l a r i t y of S E M i m a g e s c a n b e a t t r i b u t e d t o
three basic characteristics. First, t h e i m a g e s possess
e x t r a o r d i n a r y d e p t h of field. T h i s is t h e result of t h e
very small divergence of t h e electron b e a m in t h e
S E M , typically less t h a n 50 m r a d . S e c o n d , high reso
lution results from t h e s h o r t w a v e l e n g t h of t h e
e l e c t r o n s r o u g h l y 100 000 times less t h a n t h a t of
of Materials:
Characterization
Figure 2
Magnified fracture cross section of a glass microballoon
coated with gold; "cone defect" originated from
contamination on glass microballoon
241
Microengineering
of Materials:
Characterization
h a s resulted in the d e v e l o p m e n t of c o m m e r c i a l
m a c h i n e s designed specifically for this use, b a s e d o n
electron c o l u m n s from S E M s (see Sect. 3.1).
Figure 3
Measurement of coating thickness; glass microballoon
coated with plastic and gold
m e t h o d s cover t h e r a n g e from a p p r o x i m a t e l y
00 n m .
242
2.5 Quantitative
Analysis
T h e a d v e n t of low-cost lithium-drifted silicon x-ray
d e t e c t o r s h a s afforded a l m o s t all electron m i c r o s c o p e s
s o m e c a p a b i l i t y in m e a s u r i n g e l e m e n t a l c o m p o s i t i o n .
T h e real utility of these d e t e c t o r s lies in c o n v e r t i n g
m e a s u r e d x-ray intensity t o elemental c o n c e n t r a t i o n .
T h r e e factors m u s t be c o n s i d e r e d in this p r o c e d u r e
( B e a m a n a n d Isasi 1972). T h e a t o m i c n u m b e r effect
describes t h e g e n e r a t i o n of rays in t h e s a m p l e b y
i n t e g r a t i n g t h e d e p t h d i s t r i b u t i o n function from the
surface t o t h e m e a n d e p t h a t which t h e a v e r a g e
electron energy e q u a l s t h e excitation energy of the
element being m e a s u r e d . T h e a b s o r p t i o n factor A
c o r r e c t s t h e g e n e r a t e d intensity for t h e a b s o r p t i o n
p a t h length b e t w e e n t h e specimen a n d the d e t e c t o r .
Finally, t h e fluorescence c o r r e c t i o n F a c c o u n t s for
s e c o n d a r y rays g e n e r a t e d from t h e c o n t i n u u m
a n d characteristic r a y s from o t h e r elements in t h e
sample.
T h e p r o d u c t ZAF of these c o r r e c t i o n s gives t h e
t e c h n i q u e its a c r o n y m as well as a n u m e r i c a l value
used t o c o n v e r t m e a s u r e d intensities t o c o n c e n t r a
tions. M a n y c o m p u t e r c o d e s use empirical a n d / o r
a n a l y t i c m o d e l s t o i m p l e m e n t this p r o c e d u r e . T h i s
m e t h o d c a n p r o v i d e a c c u r a c y within 1-2% relative
for m a j o r c o n s t i t u e n t s in a v o l u m e of a b o u t 10 3.
T h e ZAF m e t h o d m a k e s several a s s u m p t i o n s a b o u t
s a m p l e g e o m e t r y t h a t I C F t a r g e t s d o n o t meet. I n
p a r t i c u l a r , t h e small spherical g e o m e t r y of m a n y
t a r g e t s c a n grossly affect t h e a b s o r p t i o n p a t h length
of e m i t t e d r a y s . U n f o r t u n a t e l y , m o s t ZAF r o u t i n e s
p r o v i d e d b y e q u i p m e n t m a n u f a c t u r e r s a r e n o t flexible
e n o u g h t o allow c o r r e c t i o n for g e o m e t r y , so c o d e s
w r i t t e n i n - h o u s e a r e generally preferred. T h i s aspect
Film
Figure 4
Schematic showing technique for producing magnified
radiograph in the SEM
Microengineering
3. X-Ray
Inspection
Techniques
X - r a y t e c h n i q u e s a r e used o n I C F t a r g e t s t o m e a s u r e
(a) c o a t i n g a n d wall thicknesses, (b) v a r i a t i o n s in
of Materials:
Characterization
Using
243
Microengineering
of Materials:
Characterization
Void
(a)
(b)
Dimple
(C)
Figure 6
Three types of defects found in coatings on ICF targets:
(a) concentric, (b) elliptical and (c) warts and dimples
Transmitted
rays
(In s c a l e )
0 %
Figure 5
X-ray transmission along a diameter of a uniform
spherical coating
244
t h a n , for e x a m p l e , S E M c h a r a c t e r i z a t i o n b e c a u s e it
n o n d e s t r u c t i v e l y detects w a r t s a n d d i m p l e s o n b o t h
surfaces of t h e c o a t i n g s a n d d o e s n o t require t h e
s a m p l e s t o be c o n d u c t i n g . I m a g e analysis systems t h a t
a r e sensitive t o thickness v a r i a t i o n s of 5 - 1 0 % a r e u s e d
t o p r e s o r t i m a g e s for gross c o n c e n t r i c a n d elliptical
defects a n d r e d u c e c o m p u t e r processing times.
R a d i o g r a p h i c g a u g i n g relies o n a step w e d g e (penet r a m e t e r ) t o m e a s u r e t h e a b s o l u t e c o a t i n g thickness
b y c o m p a r i n g t h e optical density in t h e center of the
target i m a g e with t h a t of k n o w n thicknesses of the
c o a t i n g m a t e r i a l in t h e step w e d g e . T h e i m a g e of t h e
p e n e t r a m e t e r m u s t a p p e a r o n t h e s a m e r a d i o g r a p h as
t h e targets. I n this w a y a b s o l u t e thicknesses a r e
d e t e r m i n e d w i t h a b o u t 1 0 % a c c u r a c y , a l t h o u g h with
e x t r e m e c a r e m e a s u r e m e n t s c a n be as a c c u r a t e as 1 % .
H o w e v e r , in either case, v a r i a t i o n s as small as 1 % a r e
detected.
X - r a y sources with energies b e t w e e n 1 k V a n d
50 k V a r e used t o r a d i o g r a p h the thinnest free
s t a n d i n g shells. W h e n possible, these sources use the
characteristic o r L x-ray r a d i a t i o n of the a n o d e s t o
p r o d u c e nearly m o n o e n e r g e t i c x-ray fluxes t o i m p r o v e
c o n t r a s t . H i g h - e n e r g y b r e m s s t r a h l u n g sources a r e
used for thicker shells. X rays from l a s e r - p r o d u c e d
p l a s m a s give extremely fine r e s o l u t i o n using p h o t o
resists r a t h e r t h a n film ( K i m a n d W h i t m a n 1987).
Advanced techniques: microfocus digital
radiography
and microtomography.
Microfocal radiography and
m i c r o t o m o g r a p h y a r e a d v a n c e d t e c h n i q u e s t h a t will
i m p r o v e o u r ability t o m e a s u r e wall thickness a n d
v a r i a t i o n s in wall thickness. M i c r o f o c u s x-ray sources
with energies of 10-30 k V a n d focal s p o t s of
detect thickness v a r i a t i o n s a s small as 0 . 1 % ( S t u p i n
1987b, 1988, S t u p i n et al. 1989), a n d i m p r o v e m e n t s in
this t e c h n i q u e a r e p r e d i c t e d t o detect v a r i a t i o n s as
small as 0 . 0 1 % . M i c r o t o m o g r a p h y using s y n c h r o t r o n
x-ray light sources images s t r u c t u r e s only 1 across
( F l a n n e r y et al. 1987, K i n n e y et al. 1988). B o t h
m e t h o d s use digital i m a g i n g ; t h a t is, images stored in
c o m p u t e r m e m o r y , r a t h e r t h a n p h o t o g r a p h i c films.
3.2 Gas Fill Pressures
T a r g e t s a r e filled with gas either b y diffusion o r b y
c o n s t r u c t i n g t h e shells in a c h a m b e r c o n t a i n i n g t h e fill
Microengineering
Bibliography
Beaman D R, Isasi J A 1972 Electron Beam Microanalysis.
American Society for Testing and Materials, Philadel
phia, PA
Bernat , Darling D H, Sanchez J J 1982 Applications of
holographic interferometry to cryogenic ICF target char
acterization. / . Vac. Sci. Technol. 20: 1362-5
Clement X, Coudeville A, Eyharts P, Perrine J P, Rouillard
R 1983 X-ray absorption in characterization of laser
fusion targets. / . Vac. Sci. Technol. A 1(2): 949-51
Cooper D 1982 A phase modulation interferometer for
ICF target characterization. J. Vac. Sci. Technol. 20:
1075-8
Elliott , Anderson W E, Archuleta A, Stupin D
1982 Thin film thickness measurement using x-ray peak
ratioing in the scanning electron microscope. J. Vac. Sci.
Technol. 20(4): 1372-3
Feldkamp L A, Kubinski D J, Jesion G 1988 Application of
high magnification to 3D x-ray computed tomography.
In: Thomson D O, Chimenti D (eds.) 1988 Review of
Progress in Quantitative Nondestructive Evaluation, Vol.
7. Plenum, New York, pp. 381-8
Flannery B P , Deckman W, Roberge W, Roberge W G,
D'Amico A 1987 Three-dimensional x-ray microtomography. Science 237: 1439-44
Goldstein J I, Newbury D E, Echlin P, Joy D C, Fiori G,
Lipshin 1981 Scanning Electron Microscopy and X-Ray
Microanalysis: A Text for Biologists, Materials Scientists,
& Geologists. Plenum, New York
Heinrich F 1981 Electron Beam X-Ray Microanalysis.
Van Nostrand Reinhold, New York
Henderson , Cielaszyk D E, Simms R J 1977 Microra
diography characterization of laser fusion pellets. Rev.
Sci. Instrum. 48: 835-40
Johns W D 1967 Measurement of film thickness. In: Kaeble
F (ed.) 1967 Handbook of X-Rays. McGraw-Hill, New
York, pp. 44-4 to 44^12
Jorgensen S 1982 A technique for calculating DT content
of Materials:
Characterization
245
Microengineering
of Materials:
Characterization
246
Microstructural
1. The Monte
1.1 General
Carlo
Method
Features
- e x p ( - AH/kT)
if
AH>0
(<^>) =
(1)
otherwise
and
1 + exp( -
AH/kT)
^{exp( -
Evolution:
Q/kT)
Computer
exp[ -
(AH
w h e r e A is a positive c o n s t a n t ,
frequency a n d Q is t h e a c t i v a t i o n
t h e b a c k j u m p r a t e (i.e., from
subtracted out. Normalizing Eqn.
tion p r o b a b i l i t y
W(oc--
'
+ Q)/kT\}
(3)
l / is t h e a t t e m p t
energy. I n E q n . (3)
t o a ) h a s been
(3) yields t h e transi
e x p ( - AH/kT)
Simulation
L l +cxp(-AH/kT)J
(4)
(2)
w h e r e is a positive c o n s t a n t w i t h d i m e n s i o n s of t i m e ,
AH = Ha is t h e difference in energy b e t w e e n
configurations a n d a , a n d kT is t h e t h e r m a l energy.
E q u a t i o n (2) is generally e m p l o y e d with c o n s e r v e d
( K a w a s a k i ) d y n a m i c s a n d is used in cases s u c h a s
diffusion, w h e r e t h e t o t a l n u m b e r o f e a c h species is
conserved. E q u a t i o n (1) is used with n o n c o n s e r v e d
( G l a u b e r ) d y n a m i c s a n d is e m p l o y e d in cases such a s
grain g r o w t h , w h e r e t h e c r y s t a l l o g r a p h i c o r i e n t a t i o n
of a p a r t o f t h e solid m a y c h a n g e . T h e c o n f i g u r a t i o n
of t h e system a p p r o a c h e s e q u i l i b r i u m a s t h e n u m b e r
of t r a n s i t i o n a t t e m p t s (using E q n . (1) o r (2)) b e c o m e s
large.
The connection between the M o n t e Carlo m e t h o d
a n d real kinetic processes c a n b e d e m o n s t r a t e d b y
simple r a t e t h e o r y . F o r e x a m p l e , in t h e case o f
vacancy diffusion, t h e n e t flux o f vacancies J from site
t o site is given b y
1.2 Grain
Growth
In o r d e r t o s i m u l a t e m i c r o s t r u c t u r a l e v o l u t i o n , a
m o d e l m u s t b e identified t h a t describes the a p p r o p r i
a t e m i c r o s t r u c t u r a l features. A s a simple e x a m p l e ,
c o n s i d e r t h e case o f n o r m a l g r a i n g r o w t h (i.e., grainsize e v o l u t i o n driven b y g r a i n - b o u n d a r y c u r v a t u r e )
( A n d e r s o n e t al. 1984). T o i n c o r p o r a t e t h e complexity
of g r a i n - b o u n d a r y t o p o l o g y , t h e m i c r o s t r u c t u r e is
m a p p e d o n t o a discrete lattice (see F i g . 1). E a c h
lattice site is assigned a n u m b e r b e t w e e n 1 a n d Q
c o r r e s p o n d i n g t o t h e o r i e n t a t i o n o f t h e grain in which
it is e m b e d d e d . T h e value o f Q m u s t b e c h o s e n t o b e
sufficiently large t h a t i m p i n g e m e n t o f grains with like
o r i e n t a t i o n is infrequent. A g r a i n - b o u n d a r y segment
is defined t o lie b e t w e e n t w o sites o f unlike orien
t a t i o n . A site w h i c h is s u r r o u n d e d b y o t h e r s o f like
o r i e n t a t i o n is in t h e i n t e r i o r o f a grain. T h e H a m i l t o n i a n describing t h e i n t e r a c t i o n b e t w e e n t h e lattice
sites is
247
Microstructural
Evolution:
Computer
2/ 4
14
8
8
8
8
4
4
4
8
8
8
4 /
4 / 9
4
4
4
4
4
8
4
4
4 4
5X4^
4
4
5/8
2 74
Simulation
4
8
19
4\
4
4 / 6
6
6
6
9-9
9
9
9 9
/6
&X4/
/9
6
6
9
9
9^
3 3
61 3 3
3 3 3 3
\ 3
6
6
6 \ 3
6
6\3
3 3 3
3
3
3
8 8 8 8 8 8 8\ 6 6 6 6 6 6/7 7
8 8 8 8 8 8 8
\ 6 6 6 6 6 / 7
7 7
8 8 8 8 8 8 8
\ 6 6 6 6 / 7
7 7
8 8 8 8 8 8 8 8
\ 6 6 6 / 7 7 7 7
8 8 8 8 8 8 8 8/ l \ 7 7 7
Figure 1
Sample microstructure on a triangular lattice where the integers denote local crystallographic orientation and the lines
represent grain boundaries
H=
-/Z(<W,-0
(5)
w h e r e St is o n e of t h e Q possible g r a i n o r i e n t a t i o n s
associated with site i a n d Sab is t h e K r o n e c k e r delta.
T h e s u m is t a k e n over all n e a r e s t - n e i g h b o r ( n n ) p a i r s
of sites. T h u s , n e a r e s t - n e i g h b o r p a i r s c o n t r i b u t e J t o
the system energy w h e n they a r e of unlike o r i e n t a t i o n ,
a n d zero otherwise. Therefore, t h e grain b o u n d a r y
energy is p r o p o r t i o n a l t o J. T h i s m o d e l is k n o w n a s
the g - s t a t e P o t t s m o d e l in statistical-mechanics litera
ture.
T h e kinetics of b o u n d a r y m o t i o n a r e s i m u l a t e d b y
e m p l o y i n g t h e M o n t e C a r l o m e t h o d described a b o v e .
Since grain o r i e n t a t i o n s a r e n o t c o n s e r v e d d u r i n g t h e
process of grain g r o w t h , n o n c o n s e r v e d d y n a m i c s a r e
employed. In the standard M o n t e Carlo method, a
lattice site a n d a n e w trial o r i e n t a t i o n a r e c h o s e n a t
r a n d o m , t h e latter from o n e of t h e o t h e r Q 1
possible o r i e n t a t i o n s . T h e c h a n g e in t h e energy of t h e
system d u e t o t h e r e o r i e n t a t i o n of t h e site is calculated
via E q n . (5). T h e p r o b a b i l i t y t h a t t h e n e w trial
o r i e n t a t i o n is accepted is xW, w h e r e W i s defined a s in
E q n . (1). Successful t r a n s i t i o n s of sites a t grain
b o u n d a r i e s t o o r i e n t a t i o n s of n e a r e s t - n e i g h b o r grains
c o r r e s p o n d t o grain b o u n d a r y m i g r a t i o n . T h i s leads
to a description of b o u n d a r y m o t i o n which is e q u i v a
lent t o t h a t derived from classical r e a c t i o n - r a t e
theory.
248
I n t h e s i m u l a t i o n s described in t h e following, t h e
system is s t a r t e d a t a t e m p e r a t u r e well in excess of t h e
melting o r critical t e m p e r a t u r e Tc a n d rapidly
q u e n c h e d t o < Tc. T o r e d u c e finite size effects, very
large systems with p e r i o d i c b o u n d a r y c o n d i t i o n s a r e
usually e m p l o y e d : 40 000 sites o n t r i a n g u l a r lattices o r
6
10 sites o n a cubic lattice a r e typical. T h e u n i t of time
is defined as 1 M o n t e C a r l o step ( M C S ) which c o r r e s
p o n d s to microtrials or reorientation attempts,
w h e r e TV is t h e t o t a l n u m b e r of sites in t h e system.
V a r i a t i o n s of t h e p r o c e d u r e a r e often e m p l o y e d t o
increase t h e efficiency of t h e s i m u l a t i o n m e t h o d .
T h e m a i n result of a n y s t u d y of m i c r o s t r u c t u r a l
e v o l u t i o n is t h e a c t u a l m i c r o s t r u c t u r e : all o t h e r infor
m a t i o n m a y b e e x t r a c t e d from this a n d its d e v e l o p
m e n t over time. F i g u r e 2 s h o w s a representative series
of m i c r o g r a p h s r e p r e s e n t i n g different times in a t w o dimensional normal grain-growth simulation. T h e
general a p p e a r a n c e of t h e m i c r o s t r u c t u r e s h o w s g o o d
c o r r e s p o n d e n c e with t h o s e in polished sections of
samples h a v i n g u n d e r g o n e n o r m a l grain g r o w t h .
M o r e detailed e x a m i n a t i o n s h o w s t h a t
grain
b o u n d a r i e s t e n d t o m e e t a t 120; small grains t e n d t o
h a v e fewer t h a n six sides a n d u n d e r g o s h r i n k a g e ; large
grains t e n d t o h a v e m o r e t h a n six sides a n d u n d e r g o
g r o w t h . All of these results a r e in a g r e e m e n t with
experimental observations.
O n e of t h e p o t e n t i a l p r o b l e m s of c o m p a r i n g t h e
s i m u l a t i o n results with e x p e r i m e n t a l o b s e r v a t i o n s is
t h a t t h e s i m u l a t i o n s a r e p e r f o r m e d in t w o d i m e n s i o n s
Microstructural
= 1000
=5000
Evolution:
Computer
Simulation
=3000
=7000
Figure 2
The temporal evolution of a typical microstructure undergoing normal grain growth
while the e x p e r i m e n t a l o b s e r v a t i o n s a r e m a d e o n
cross sections of t h r e e - d i m e n s i o n a l s a m p l e s . I n o r d e r
to test t h e validity of r e p r e s e n t i n g cross sections of
real m a t e r i a l s b y t w o - d i m e n s i o n a l s i m u l a t i o n s , a d d i
tional s i m u l a t i o n s of n o r m a l g r a i n g r o w t h were per
formed in three spatial d i m e n s i o n s ( A n d e r s o n et al.
1989). C o m p a r i s o n of t h e g r a i n size (RA) d i s t r i b u t i o n
d e t e r m i n e d from cross sections of t h e t h r e e d i m e n s i o n a l s i m u l a t i o n w i t h t h a t for p u r e i r o n a n d
the t w o - d i m e n s i o n a l s i m u l a t i o n s s h o w excellent
a g r e e m e n t . A similar c o m p a r i s o n of t h e n o r m a l i z e d
grain size versus t h e n u m b e r of edges p e r g r a i n (Fig.
3) for M g O a n d tin, d e t e r m i n e d e x p e r i m e n t a l l y in
two-dimensional and three-dimensional simulations,
also shows a n excellent c o r r e s p o n d e n c e . R e c e n t s i m u
lation results s h o w t h a t for later times t h e m e a n g r a i n
112
size g r o w s as R = At
in t w o - a n d t h r e e - d i m e n s i o n a l
simulations, a n d with a slightly smaller e x p o n e n t a t
earlier times. T h e o r e t i c a l analyses of g r a i n - g r o w t h
m
kinetics typically s h o w t g r o w t h laws, b u t experi
m e n t a l w o r k usually yields a smaller e x p o n e n t ( p r e
l/2
s u m a b l y d u e t o i m p u r i t y effects) a l t h o u g h t g r o w t h
has been observed.
O n e of t h e m a j o r benefits of this class of s i m u l a t i o n
studies is t h e ability t o test theoretical ideas. Simula
tion often p r o v i d e s a b e t t e r test t h a n e x p e r i m e n t since
s i m u l a t i o n s c a n b e p e r f o r m e d t o e x a m i n e t h e effects
of different a s s u m p t i o n s directly w i t h o u t t h e inevi
t a b l e c o m p l i c a t i o n s associated with impurities, m i c
r o s t r u c t u r a l features o t h e r t h a n t h o s e being studied
a n d destructive e v a l u a t i o n t e c h n i q u e s . A n e x a m p l e of
w h e r e s i m u l a t i o n h a s d e m o n s t r a t e d t h e p o o r state of
theoretical u n d e r s t a n d i n g is in t h e a r e a of a b n o r m a l
g r a i n g r o w t h (also k n o w n as s e c o n d a r y recrystallization a n d e x a g g e r a t e d g r a i n g r o w t h ) . It is generally
believed t h a t a b n o r m a l g r o w t h is associated with the
presence a n d t h e n d i s s o l u t i o n of s e c o n d - p h a s e p a r t i
cles. S i m u l a t i o n s h a v e s h o w n , h o w e v e r , t h a t texture
effects a n d t h e related g r a i n - b o u n d a r y mobility a n i s o
t r o p y c a n lead t o a b n o r m a l g r o w t h (Rollett et al.
1989). A relatively s t r o n g t e x t u r e is a c o m m o n by
p r o d u c t of processing m a t e r i a l c o n t a i n i n g particles.
249
Microstructural
Evolution:
Computer
Simulation
MgO
OSn
2 - d simulation
3 - d simulation
Y
V
A
Number of sides
Figure 3
Relationship between the number of sides exhibited by
grains when viewed in cross section and the average grain
radius determined from the cross-sectional area for the
given number of sides
250
Figure 4
A late stage sintering microstructure: the black regions are
voids, the white ones are grains and the lines represent
grain boundaries
Microstructural
Evolution:
Computer
Simulation
MCS
5 0 MCS
b
C
2 0 0 MCS
Figure 5
The temporal evolution of a two-phase (misfitting, coherent) microstructure under the influence of a tensile stress applied
vertically
Microstructural
Evolution:
Computer
Simulation
of t h e s a m p l e t o t h a t of t h e interface. A p p l i c a t i o n of
this m o d e l t o d e n d r i t i c g r o w t h in t w o d i m e n s i o n s
yields
. dx
(
2. Equation
of Motion
Methods
Tracking
F r o n t t r a c k i n g m e t h o d s h a v e f o u n d wide a p p l i c a t i o n
in the physical sciences, including studies of flame
fronts, chemical reaction fronts, c l o u d s , fluid flow,
shocks, solidification fronts a n d p l a s m a s (see B i s h o p
et al. 1984). T h e s e m e t h o d s r e d u c e t h e physical p r o b
lem to o n e which m a y be solved strictly o n a front o r
interface. T h e t r u e ^/-dimensional (where d is t h e
d i m e n s i o n of the b o d y ) d y n a m i c a l p r o b l e m is
generally t r a n s f o r m e d i n t o a set of p a r t i a l differential
or integrodifferential e q u a t i o n s which a r e numerically
solved at a finite set of p o i n t s o n the front o r interface.
A s the interface d e f o r m s , e x p a n d s o r c o n t r a c t s , the
n u m b e r of p o i n t s describing the interface is often
c h a n g e d in o r d e r t o g u a r a n t e e n u m e r i c a l a c c u r a c y .
T h e a c t u a l i m p l e m e n t a t i o n of this m e t h o d varies
widely: the c o m p u t a t i o n a l t e c h n i q u e s involved a r e
described by Wilson et al. (1978). T h i s section de
scribes the a p p l i c a t i o n of such m e t h o d s t o t w o p r o b
lems in m i c r o s t r u c t u r a l e v o l u t i o n , n a m e l y t o the
f o r m a t i o n of d e n d r i t e s d u r i n g solidification, a n d t o
grain g r o w t h .
(a) Dendritic growth. This h a s received a great deal of
a t t e n t i o n in recent years, d u e , in p a r t , to the rich
p a t t e r n s formed d u r i n g t h e g r o w t h process a n d o u r
inability t o describe theoretically t h e c o m p l e t e d y n a
mic evolution of these structures. W h e n t h e melt is
u n d e r c o o l e d (i.e., below the melting p o i n t Tm), the
solid-liquid interface is u n s t a b l e a n d d e n d r i t e s form.
T h e rate-limiting step in such a process is t h e diffusion
of the (latent) h e a t a w a y from the solidification front.
Such a process m a y be m o d e l l e d by t h e ( t h e r m a l )
diffusion e q u a t i o n in the entire b o d y plus a n equi
librium c o n d i t i o n for the interface. T h i s c o n d i t i o n
a c c o u n t s for the melting t e m p e r a t u r e a n d its varia
tions with c u r v a t u r e (i.e., the G i b b s - T h o m p s o n
effect).
Recent p h e n o m e n o l o g i c a l w o r k o n d e n d r i t i c
g r o w t h (see B r o w e r et al. 1984) b a s e d o n a set of
simplistic a s s u m p t i o n s k n o w n as the " g e o m e t r i c a l
m o d e l , " reduces the p r o b l e m from the d i m e n s i o n a l i t y
252
ds
) [1 + cos(m0)]
(6)
(7)
) J W ) ]
ds'
Jo
doc
* ( "()
doc' - a^KF(e)
dot' ) /
(8)
dsT
f
- = s T \ <xF(6) doc
ot
JQ
1
w h e r e = (\/sT)d6/doi.
D i s c r e t i z a t i o n of E q n s . (8)
yields a c o u p l e d set of o r d i n a r y differential e q u a t i o n s
which c a n t h e n be i n t e g r a t e d using a p r e d i c t o r c o r r e c t o r o r d i n a r y differential e q u a t i o n
solver.
Finally, t h e physical interface is r e c o n s t r u c t e d b y
integrating
x(oc)=
I c o s [ 0 ( a ' ) ] doc'
J 0
(9)
y(*) = y
- i s i n [ 0 ( a ' ) ] doc'
Jo
Microstructural
Evolution:
Computer
Simulation
Figure 6
A two-dimensional dendrite simulated within the
framework of the geometrical model
F i g u r e 6 s h o w s a typical d e n d r i t e s i m u l a t e d using this
m e t h o d with 300 p o i n t s a n d t h e p a r a m e t e r s m = 4,
A = 4, B = 2 a n d = 0.15. T h e r e s u l t a n t d e n d r i t i c
s t r u c t u r e exhibits a fourfold s y m m e t r y , s i d e - b r a n c h e s
a n d overall s h o w s a n excellent c o r r e s p o n d e n c e w i t h
experimentally o b s e r v e d d e n d r i t i c m o r p h o l o g i e s .
F u r t h e r m o r e , this class of s i m u l a t i o n s h a s led t o a
theoretical u n d e r s t a n d i n g of o p e n q u e s t i o n s such a s
w h a t d e t e r m i n e s t h e g r o w t h velocity.
(b) Grain growth.
F r o n t tracking methods have
recently been a p p l i e d t o t h e s t u d y of g r a i n g r o w t h (see
C e p p i a n d N a s e l l o 1984, F r o s t et al. 1988). I n this case
the p a r t i a l differential e q u a t i o n describing t h e t e m
p o r a l e v o l u t i o n of t h e g r a i n b o u n d a r i e s is q u i t e sim
ple. G r a i n b o u n d a r i e s a r e a s s u m e d t o m o v e a c c o r d i n g
to v n = , w h e r e v n is t h e velocity of a b o u n d a r y
segment n o r m a l t o itself, is t h e local b o u n d a r y
c u r v a t u r e a n d is a c o n s t a n t " m o b i l i t y . " A n initial
t w o - d i m e n s i o n a l s t r u c t u r e is c o n s t r u c t e d , i n t e g r a t i o n
points are distributed along the grain boundaries and
each p o i n t is m o v e d a l o n g t h e local b o u n d a r y n o r m a l
by d u r i n g e a c h i n t e g r a t i o n t i m e step /. Since
three b o u n d a r i e s t e n d t o m e e t a t 120 triple p o i n t s , t h e
positions of t h e triple p o i n t s m u s t also b e u p d a t e d .
T h i s is a c c o m p l i s h e d b y m o v i n g t h e m t o s u c h a
position, w i t h respect t o t h e t h r e e b o u n d a r i e s , t h a t t h e
120 c o n d i t i o n is satisfied. T h e b o u n d a r y - m i g r a t i o n
a n d triple-point u p d a t e steps a r e i t e r a t e d alternately.
T o p o l o g i c a l c h a n g e s , such as t h e s h r i n k i n g a w a y of a
small grain o r c h a n g e s in t h e n u m b e r of edges of a
grain by vertex i m p i n g e m e n t , a r e a c c o u n t e d for b y
reconnecting t h e local n e t w o r k in t h e vicinity of t h e
a p p r o p r i a t e vertex.
This method has been applied to b o t h n o r m a l a n d
a b n o r m a l g r a i n g r o w t h . I n b o t h cases c a l c u l a t i o n s
yield r e a s o n a b l e m i c r o s t r u c t u r e s a n d kinetics a r e in
253
Microstructural
Evolution:
Computer
Simulation
Figure 7
3
The evolution of a microstructure containing 10 dislocations distributed on parallel slip planes: the _L and symbols
indicate edge dislocations with Burgers vectors of opposite signs
- r i , +
e x t
(10)
w h e r e x, is the c o o r d i n a t e of dislocation /, d o t s
indicate differentiation with respect t o time, w * is t h e
effective dislocation m a s s , F e xt is t h e force o n disloca
tion i in t h e direction d u e t o a n external stress, is
the d a m p i n g factor a n d t h e last t e r m a c c o u n t s for t h e
i n t e r a c t i o n of dislocation / with all o t h e r dislocations.
S e p a r a t e e q u a t i o n s m u s t b e w r i t t e n for glide a n d
climb, a n d a p p r o p r i a t e d a m p i n g factors m u s t b e
d e t e r m i n e d for each. All of t h e t e r m s in E q n . (10) c a n
be calculated directly from t h e elastic t h e o r y of dislo
cations.
E q u a t i o n (1) c a n be i n t e g r a t e d for e a c h dislocation
by t a k i n g small finite time-steps. If dislocations of
o p p o s i t e sign b e c o m e closer t h a n a cutoff d i s t a n c e
(defined in t e r m s of the size of the time-step At), they
are annihilated. T h e i n t e g r a t i o n of E q n . (10) is carried
o u t in the s a m e w a y as the i n t e g r a t i o n of N e w t o n ' s
e q u a t i o n of m o t i o n in n o r m a l m o l e c u l a r d y n a m i c s
calculations. H o w e v e r , unlike m o l e c u l a r d y n a m i c s ,
the particles a r e n o t a t o m s b u t d i s l o c a t i o n s . F i g u r e 7
3
shows the t e m p o r a l e v o l u t i o n of 10 dislocations o n
t h e s a m e slip system w i t h either positively o r negati
vely signed B u r g e r s vectors. T h e initial s t r u c t u r e is
r a n d o m , b u t after a s h o r t time it f o r m s oppositely
signed dislocation walls. T h e dislocation density, t h e
s t r e n g t h a n d density of s e c o n d - p h a s e particles, the
applied stress, the t e m p e r a t u r e ( t h r o u g h t h e relative
values of the glide a n d climb d a m p i n g ) a n d t h e
available slip systems c a n be varied i n d e p e n d e n t l y in
these s i m u l a t i o n s . V a r i a t i o n s of this type of m o d e l
b a s e d o n different e q u a t i o n s of m o t i o n a n d m e t h o d s
254
(11)
w h e r e v, is t h e velocity of vertex , is a c o n s t a n t
" m o b i l i t y , " etj is t h e line tension of t h e grain b o u n d a r y
c o n n e c t i n g sites / a n d j , a n d t h e s u m is t a k e n over t h e
three g r a i n b o u n d a r i e s m e e t i n g a t vertex i. E q u a t i o n
(11) is t h e n i n t e g r a t e d with a small time-step At. A s in
t h e front t r a c k i n g m e t h o d , special h a n d l i n g is
r e q u i r e d t o deal with t h e t o p o l o g i c a l c h a n g e s t h a t
o c c u r w h e n vertices meet.
T h i s m o d e l yields m i c r o s t r u c t u r e s a n d g r o w t h kin
etics w h i c h a r e in a g r e e m e n t with t h o s e f o u n d b y t h e
front t r a c k i n g a n d M o n t e C a r l o m e t h o d s a n d in cross
sections of e x p e r i m e n t a l g r a i n - g r o w t h s a m p l e s . Since
this m e t h o d focuses o n vertices r a t h e r t h a n g r a i n
b o u n d a r i e s (as is d o n e in t h e front t r a c k i n g m e t h o d s )
o r g r a i n s (as is d o n e in t h e M o n t e C a r l o m o d e l ) it is in
principle m o r e efficient.
3.
Conclusions
W h i l e grain g r o w t h is n o t necessarily t h e m o s t im
p o r t a n t a r e a of m i c r o s t r u c t u r a l e v o l u t i o n , it h a s b e e n
e m p h a s i z e d b e c a u s e of t h e wide variety of t e c h n i q u e s
Microtextural
t h a t h a v e b e e n a p p l i e d in its s i m u l a t i o n s t u d y . A s t h e
s i m u l a t i o n m e t h o d s b e c o m e increasingly efficient b y
c o n c e n t r a t i n g o n smaller a n d smaller c o m p o n e n t s of
the microstructure, m o r e assumptions are required
a n d a certain degree of simplicity is lost. T h i s is clearly
evident as t h e s i m u l a t i o n of g r a i n g r o w t h h a s evolved
from (least t o m o s t efficient) M o n t e C a r l o m e t h o d s
(which focus o n t h e g r a i n ) via front t r a c k i n g m e t h o d s
(which focus o n t h e g r a i n b o u n d a r i e s ) t o t h e particle
m e t h o d s (which focus o n t h e g r a i n b o u n d a r y ver
tices). I n cases w h e r e t h e identical s i m u l a t i o n is t o b e
r u n m a n y times (with different p a r a m e t e r s ) , as in a
p r o d u c t i o n e n v i r o n m e n t , t h e m o s t efficient m e t h o d s
should b e used even t h o u g h they e m p l o y t h e m o s t
a s s u m p t i o n s a n d a r e n o t easily generalizable. I n a
research e n v i r o n m e n t , h o w e v e r , generalizability, sim
plicity a n d t h e m i n i m u m n u m b e r of a s s u m p t i o n s a r e
necessities a n d clearly favor t h e m o r e
basic
approaches.
The computer simulation methods and applications
described represent o n l y a s a m p l i n g of t h e s i m u l a t i o n
methods currently applied to microstructure-related
p r o b l e m s in m a t e r i a l s science. O t h e r a r e a s t o w h i c h
m i c r o s t r u c t u r a l s i m u l a t i o n s h a v e been a p p l i e d in
clude directional solidification, film g r o w t h , particle
coarsening and texture development during deforma
tion. T o d a t e , m o s t of t h e interest in t h e s i m u l a t i o n of
m i c r o s t r u c t u r a l e v o l u t i o n h a s c o m e f r o m t h e basic
research a r e a of m a t e r i a l s science a n d engineering.
H o w e v e r , as t h e p o w e r a n d availability of c o m p u t e r s
continues to grow a n d new simulation m e t h o d s are
developed, c o m p u t e r s i m u l a t i o n of m i c r o s t r u c t u r a l
e v o l u t i o n will m o v e increasingly from t h e h a n d s of
researchers t o t h o s e of engineers.
Analysis
Bibliography
Anderson , Grest G S, Srolovitz D J 1989 Computer
simulation of normal grain growth in 3 dimensions.
Philos. Mag. 59 (3): 293-329
Anderson , Srolovitz D J, Grest G S, Sahni P S 1984
Computer simulation of grain growth. 1. Kinetics. Acta
Metall 32: 783-91
Binder 1979 Monte Carlo Methods in Statistical Physics.
Springer, Berlin
Bishop A R, Campbell L J, Channell J 1984 Fronts,
Interfaces and Patterns. North-Holland, Amsterdam
Brower R C, Kessler D A, Koplik J, Levine 1984
Geometrical models of interface evolution. Phys. Rev. A
29: 1335-42
Ceppi A, Nasello 1984 Computer simulation of
bidimensional grain growth. Scr. Metall. 18: 1221-5
Frost J, Thompson C V, Howe C L, Whang J 1988 A twodimensional computer simulation of capillarity-driven
grain growth: preliminary results. Scr. Metall. 22: 65-70
Gayda J, Srolovitz D J 1989 A Monte-Carlo finite element
model for strain-energy controlled microstructural evolu
tionrafting in superalloys. Acta Metall. 37 (2): 641-50
Ghoniem , Amodeo R 1988 Computer simulation of
Microtextural Analysis
A polycrystalline m a t e r i a l is said t o be t e x t u r e d if its
c o n s t i t u e n t g r a i n s h a v e a preferred o r i e n t a t i o n : t h a t is
t o say, t h e crystal axes a r e statistically oriented in a
n o n r a n d o m w a y . U n t i l recently, a t e x t u r e h a s always
been d e t e r m i n e d a n d d e p i c t e d m a c r o s c o p i c a l l y , in the
sense t h a t t h e o r i e n t a t i o n s of millions of grains a r e
collectively s h o w n in a p o l e figure ( t w o d i m e n s i o n a l )
o r a n o r i e n t a t i o n d i s t r i b u t i o n function (three d i m e n
sional) (see Texture:
Nondestructive
Characteriza
tion). A n y s u c h d e p i c t i o n leaves o u t o n e i m p o r t a n t
piece of i n f o r m a t i o n , t h a t is, t h e d i s t r i b u t i o n of m i s o r i e n t a t i o n s b e t w e e n all p a i r s of adjacent grains in
t h e polycrystal. S u c h a d i s t r i b u t i o n is called a microtexture o r a mesotexture;
o t h e r t e r m s which h a v e
b e e n used include grain misorientation
texture, grainboundary
character
distribution
and
misorientation
distribution', t h e t e r m " m i c r o t e x t u r e " will be used
255
Microtextural
Analysis
Figure 1
Stereographic unit triangle for a statistically random
assemblage of cubic grains, showing the percentages of
axes of misorientation lying within the various regions
bounded by solid curves. The regions are bounded, in
part, by small circles at 5, 10, 15, 30 and 45 from [100]
and by small circles at 5 and 9.7 from [111] (after
Mackenzie 1964)
1. Representation
of
Microtextures
256
this t r e a t m e n t . R a n d l e a n d B r o w n w e n t o n t o e s t i m a t e
t h e p r o p o r t i o n of c o n t i g u o u s grain p a i r s t h a t a r e in a
C S L r e l a t i o n s h i p t o each other; t h e a b b r e v i a t i o n
refers t o coincidence lattice site t h e o r y a n d d e n o t e s a
family of " s p e c i a l " o r i e n t a t i o n relationships, of which
the m o s t familiar is t h e simple twin pair. T h e b e t t e r
t h e "fit" of t h e c o n t i g u o u s lattices at t h e b o u n d a r y
p l a n e , t h e lower t h e integer w h i c h defines t h e C S L
r e l a t i o n s h i p a n d (generally) t h e lower t h e specific
b o u n d a r y energy; is t h e reciprocal of t h e fraction of
lattice n o d e s of o n e grain t h a t coincide with lattice
n o d e s of t h e n e i g h b o r i n g grain. R a n d l e a n d B r o w n
f o u n d t h a t t h e p r o p o r t i o n of C S L p a i r s increased
steadily d u r i n g grain g r o w t h .
F r a n k (1988) h a s resurrected a n i n e t e e n t h c e n t u r y
g r a p h i c a l m e t h o d d u e t o O . R o d r i g u e s of r e p r e s e n t i n g
grain r o t a t i o n s , n o w t e r m e d the
Rodrigues-Frank
method: t h e o r i e n t a t i o n of t h e r o t a t i o n axis relative t o
t h e crystal axes of o n e of t h e grains is d e n o t e d b y a
line from t h e origin, while the length of t h a t line is
p r o p o r t i o n a l t o t h e r o t a t i o n angle. T h e loci of t h e
e n d s of such lines for t h e m a x i m u m feasible r o t a t i o n
angles for e a c h o r i e n t a t i o n of r o t a t i o n axis m a p s o u t a
p o l y g o n o r z o n e , l o o k i n g r a t h e r like a Brillouin z o n e .
T h e details of t h e m e t h o d , a n d its utility for a n a l y z i n g
t h e m i c r o t e x t u r a l c h a n g e s t h a t a c c o m p a n y recrystalli
z a t i o n of stainless steel with a n initial rolling t e x t u r e ,
h a v e been set o u t b y R a n d l e (1990a, b) I n t h e second
of t h e cited p a p e r s , R a n d l e g e n e r a t e d m e s o t e x t u r e s b y
c o m p u t e r o n the h y p o t h e s i s t h a t m u l t i p l e g e n e r a t i o n s
of t w i n n i n g d e t e r m i n e recrystallized o r i e n t a t i o n s , dis
p l a y e d these b y t h e R o d r i g u e s - F r a n k m e t h o d a n d
c o m p a r e d t h e m with o b s e r v e d m i c r o t e x t u r e s as a
m e a n s of v a l i d a t i n g t h e initial h y p o t h e s i s as t o t h e
origin of a n n e a l i n g textures.
Figure 2
Microtexture figure for the axes of (minimum)
misorientation corresponding to pairs of contiguous grains
in a recrystallized stainless steel specimen annealed for
11 h at 950 C, which has undergone extensive grain
growth (after Randle and Brown 1989)
Microtextural
Analysis
Table 1
Microtextural examination: pros and cons of available methods
Pattern
Transmission (electrons)
SAD (selected-area diffraction)
SAD
microdiffraction
microdiffraction
Kikuchi (electrons)
SAD
microdiffraction
SACP
EBSP
Kossel (x rays)
Laue (x rays)
2. Determination
of
Instrument
Highest
spatial
resolution
Angular
resolution
()
Usable for
very
imperfect
grains?
HVEM
TEM
TEM/STEM
FEG/STEM
0.4
1.5
10 nm
1 nm
2
2
2
5
yes
yes
yes
yes
TEM
TEM/STEM
SEM
SEM/STEM
SEM
SEM
synchrotron
source
1.5
20 nm
10
1-2
0.5
10
5
0.2
0.2
>0.5
0.5
<0.5
0.5
<0.5
no
no
no
no
no
yes
yes
Microtextures
A r a n g e of e x p e r i m e n t a l m e t h o d s h a s b e e n used t o
d e t e r m i n e m i c r o t e x t u r e s . W h i c h e v e r is used, t h e
o r i e n t a t i o n s of i n d i v i d u a l g r a i n s h a v e t o be s e p a r a t e l y
d e t e r m i n e d , so there is a g r e a t p r e m i u m o n r a p i d
m e t h o d s . T a b l e 1, slightly modified from o n e p u b
lished b y H u m p h r e y s (1988), sets o u t t h e available
m e t h o d s a n d their p r o s a n d c o n s . M o s t of t h e m e t h
o d s d e p e n d o n diffraction. T h e o r d i n a r y Laue method
h a s h i t h e r t o been t o o slow w h e n a n x-ray m i c r o b e a m
is used, b u t t h e availability of s y n c h r o t r o n sources h a s
n o w r e d u c e d t h e n e e d e d e x p o s u r e time from h o u r s t o
seconds. T h e Kossel method, in w h i c h a n electron
b e a m is focused o n a m e t a l grain t o g e n e r a t e a p o i n t
source of characteristic rays w h i c h s p r e a d o u t a n d
p r o d u c e diffraction p a t t e r n s in t h e f o r m of c o n i c
sections ( F e r r a n et al. 1971), h a s been extensively
used a n d requires e x p o s u r e s of a few m i n u t e s . Inter
p r e t a t i o n of K o s s e l p a t t e r n s h a s b e e n c o m p u t e r i z e d .
Diffraction of electrons is widely used (the first six
entries in T a b l e 1), b u t t h e a n g u l a r r e s o l u t i o n for m o s t
such m e t h o d s is n o t impressive. T w o o t h e r m e t h o d s ,
electron back scattering patterns ( E B S P ) a n d selectedarea channelling patterns ( S A C P ) , b o t h r e q u i r i n g t h e
use of a s c a n n i n g electron m i c r o s c o p e a n d o p e r a t i n g
with s h o r t e x p o s u r e s , h a v e n o w largely replaced t h e
Kossel m e t h o d .
I n o k u t i a n d his c o - w o r k e r s ( I n o k u t i et al. 1987a, b)
h a v e long used t h e K o s s e l m e t h o d intensively t o s t u d y
m i c r o t e x t u r e s in silicon steel used for t r a n s f o r m e r
l a m i n a t i o n s ; such studies h a v e p r o v e d essential for t h e
u n d e r s t a n d i n g a n d c o n t r o l of t e x t u r e f o r m a t i o n in
these sheets. T h e y d e v e l o p e d a m e t h o d of d i s p l a y i n g
t h e results of a large n u m b e r of such o r i e n t a t i o n
d e t e r m i n a t i o n s , in which e a c h g r a i n is s h o w n o n a
c o m p u t e r screen in its c o r r e c t m i c r o s t r u c t u r a l loca
tion, with a c o l o r t h a t directly defines its o r i e n t a t i o n ,
as s t a n d a r d i z e d o n a r a i n b o w - c o l o r e d u n i t stereog r a p h i c triangle. T h e thickness of a g r a i n b o u n d a r y in
such a display is g r a d e d a c c o r d i n g t o the m a g n i t u d e of
t h e m i s o r i e n t a t i o n b e t w e e n t h e adjacent grains. A n
e x a m p l e of o n e of I n o k u t i ' s displays in color is
r e p r i n t e d in a recent overview of textures by C a h n
(1991).
3. Microtextures
and
Properties
A polycrystal with a l a r g e r - t h a n - r a n d o m p o p u l a t i o n
of special ( C S L ) b o u n d a r i e s is expected t o h a v e
u n u s u a l m e c h a n i c a l p r o p e r t i e s ; o t h e r p r o p e r t i e s , such
as resistance t o g r a i n - b o u n d a r y c o r r o s i o n a n d grainb o u n d a r y mobility, a r e t h e n also likely t o be a b n o r
mal. Where mechanical properties are concerned, a
J a p a n e s e investigator, W a t a n a b e , h a s been a s t r o n g
p r o p o n e n t of t h e c o n c e p t of grain-boundary design, by
w h i c h h e m e a n s t h e processing of a polycrystal with
t h e objective of g e n e r a t i n g a desirable d i s t r i b u t i o n of
special b o u n d a r i e s , so as t o achieve g r e a t e r - t h a n n o r m a l s t r e n g t h o r ductility.
A g o o d e x a m p l e of this a p p r o a c h is p r o v i d e d b y a
recent s t u d y by W a t a n a b e et al. (1989) of a specially
t r e a t e d f o r m of c o n c e n t r a t e d ( 6 . 5 w t % S i ) silicon
steel w h i c h h a s t u r n e d o u t t o be a serious c o m p e t i
t o r in t r a n s f o r m e r l a m i n a t i o n s b o t h for s t a n d a r d
(3.5 w t % S i ) silicon steel a n d for metallic glasses. T h e y
d e t e r m i n e d g r a i n o r i e n t a t i o n s b y electron channelling
( S A C P ) a n d identified special b o u n d a r i e s , classified
257
Microtextural
Analysis
29 13
81 27
9
3
^42.5%
4 1 %
304
30 h
steel
Fe-6.5
0 nickel
wt%Si
rapidly solidified
and
annealed
I363K
I h
Bibliography
20
Fe-3wt%Si
7 4 % rolled and
annealed, 1333
10
p u r e Fe
rolled annealed
9 7 3 K, 100 h
random orientn
distribution
Q5
1.0
1.5
Figure 3
The frequency of special boundaries, as a function of , in
a rapidly solidified and annealed ribbon of Fe-6.5 wt%Si
transformer steel, heat-treated for optimum ductility. Data
for other alloys also shown (after Watanabe et al. 1989)
by their characteristic n u m b e r s . F i g u r e 3 s h o w s
their results ( o p e n circles), c o m p a r e d with d a t a for a
differently t r e a t e d silicon steel as well as o t h e r alloys,
a n d also with a line c o r r e s p o n d i n g t o a texture-free
m a t e r i a l . T h e t o p abscissa o n this g r a p h m a r k s
n u m b e r s , t h e b o t t o m abscissa is c a l i b r a t e d in t e r m s of
1/3
~ , because t h e a u t h o r s f o u n d empirically t h a t t h e
frequencies of special b o u n d a r i e s varied linearly w i t h
this function of . T h e r a p i d l y solidified a n d a n n e a l e d
6.5 w t % silicon steel ( t h a t is, t h e f o r m of this alloy
with exceptional p r o p e r t i e s ) h a s a high p r o p o r t i o n
( a b o u t 5 0 % ) of low- grain b o u n d a r i e s .
T h e high ductility of t h e specially t r e a t e d silicon
steel w a s a t t r i b u t e d b y W a t a n a b e t o t h e high resis
t a n c e of special b o u n d a r i e s t o i n t e r g r a n u l a r fracture.
In a recent s t u d y , L i m a n d W a t a n a b e (1990) h a v e
d e m o n s t r a t e d a m e c h a n i s m b y w h i c h a high fraction
of fracture-resistant special (low-energy) b o u n d a r i e s
c a n e n h a n c e t h e overall fracture t o u g h n e s s of a polycrystal.
O r t n e r a n d R a n d l e (1989) h a v e d e m o n s t r a t e d t h a t
individual g r a i n b o u n d a r i e s in a stainless steel p a r
tially sensitized t o c o r r o s i o n b e h a v e differently
a c c o r d i n g t o their c r y s t a l l o g r a p h y . L o w - a n g l e b o u n d
258
Mossbauer
Mossbauer Spectroscopy
T h e history of t h e M o s s b a u e r effect is u n i q u e in t h e
field of s p e c t r o s c o p y a n d in writing a general i n t r o
d u c t i o n , it is necessary t o c o n s i d e r a few facts a b o u t
such a significant discovery. M o s s b a u e r w a s a s t u d e n t
w h e n he m a d e a n u n e x p e c t e d o b s e r v a t i o n . W o r k i n g
conscientiously a n d skilfully he f o u n d t h e origin of
the s t r a n g e effect ( M o s s b a u e r 1958a, b ) , b u t w h e n h e
published his findings in 1958, surprisingly n o o n e
seemed t o notice, c a r e a b o u t o r believe t h e m . W h e n
the greatness of t h e discovery w a s finally a p p r e c i a t e d ,
fascination g r i p p e d t h e scientific c o m m u n i t y , a n d
m a n y scientists i m m e d i a t e l y s t a r t e d researching t h e
p h e n o m e n o n . I m p o r t a n t e x p e r i m e n t s were initiated
a n d significant discoveries were m a d e s u c h as t h e
g r a v i t a t i o n a l red shift a n d hyperfine i n t e r a c t i o n s with
v a r i o u s i s o t o p e s a n d m a n y a p p l i c a t i o n s in physics,
chemistry, biology a n d m a t e r i a l s science were f o u n d .
Suddenly t h e n u m b e r of p a p e r s dealing with the n e w
m e t h o d b e c a m e so large t h a t the e d i t o r of Physical
Review Letters h a d t o b r i n g it t o a s t o p (April 1960).
T h e N o b e l Prize w a s a w a r d e d t o M o s s b a u e r in 1961,
de facto for his first p u b l i c a t i o n a u n i q u e achieve
m e n t in t h e h i s t o r y of this distinction ( M o s s b a u e r
1962).
I n the following years, m o r e a n d m o r e i s o t o p e s
( a b o u t 100) were f o u n d t o be useful for t h e n e w
m e t h o d ( M u i r et al. 1966, Stevens a n d Stevens 1966
5 7
76, 1977-87), with F e (the m o s t i m p o r t a n t e l e m e n t
in physical m e t a l l u r g y ) p r o v i d i n g the m o s t f a v o u r a b l e
nuclear p a r a m e t e r s for M o s s b a u e r studies ( G o n s e r
1975, 1981, 1986).
7.
Principles
T h e p h e n o m e n o n of r e s o n a n c e m a y o c c u r b e t w e e n
t w o bodies. In t h e case of t h e M o s s b a u e r effect, these
t w o bodies a r e nuclei of t h e s a m e i s o t o p e . R e s o n a n c e
is a c c o m p l i s h e d b y e l e c t r o m a g n e t i c r a d i a t i o n : y r a y s
emitted a n d a b s o r b e d b e t w e e n t h e excited a n d g r o u n d
state. H o w e v e r , y-ray r e s o n a n c e fluorescence h a d
already been realized a n d p e r f o r m e d earlier. T h e n e w
i m p o r t a n t o b s e r v a t i o n t h a t M o s s b a u e r m a d e in
cluded t h e p r o p e r t y of "recoil-free" y-ray r e s o n a n c e
fluorescence. I n o r d e r t o explain t h e n e w effect, t h e
q u a n t u m m e c h a n i c s of t h e system m u s t b e c o n s i d e r e d .
In a c o n d e n s e d system (a solid) t h e t h e r m a l p r o p e r t i e s
of a lattice a r e described b y v i b r a t i o n a l oscillations of
the a t o m s with frequencies v. T h e energy of t h e
oscillations is q u a n t i z e d in discrete u n i t s of hv
(h = 2nh = P l a n c k ' s c o n s t a n t ) . T h e v i b r a t i o n a l m o d e s
constitute the p h o n o n s . The Debye model represents
v i b r a t i o n a l states with a certain d i s t r i b u t i o n of fre
quencies a n d a characteristic m a x i m u m v i b r a t i o n a l
1 2
1 3
frequency v D typically in t h e r a n g e of 1 0 - 1 0 H z .
W i t h B o l t z m a n n ' s c o n s t a n t KB t h e D e b y e t e m p e r a
ture is defined:
Spectroscopy
hvO = kB0O
(1)
2
ER = E /2Mc
(2)
/=exp(-A: <x
(3)
w h e r e k is t h e m a g n i t u d e of t h e w a v e vector of the y
2
r a y a n d <x > is t h e m e a n - s q u a r e v i b r a t i o n a l a m p l i
t u d e of t h e r e s o n a t i n g a t o m in t h e direction of obser
v a t i o n . T w o i m p o r t a n t results a r e o b t a i n e d from this
e q u a t i o n . T h e recoil-free fraction / increases with
d e c r e a s i n g y-ray energy k a n d increasing D e b y e t e m
p e r a t u r e .
In the recoil-free t r a n s i t i o n b e t w e e n the excited a n d
t h e g r o u n d state n o energy is e x c h a n g e d with the
s u r r o u n d i n g s , t h a t is, t h e y r a y carries the t o t a l
energy. W i t h t h e m e a n lifetime of t h e excited state
(the g r o u n d state is stable o r h a s a l o n g lifetime),
H e i s e n b e r g ' s u n c e r t a i n t y principle applies:
= /
(4)
259
Mossbauer
Spectroscopy
-excited
state -
^ j O y s ^
-ground
state-
fa)
drive
3. Hyperfine
Absorber
Source
counter
system
(b)
multichannel
analyzer
Figure 1
(a) Relevant transitions between the nuclear excited and
the ground state; (b) combined experimental setup of y-ray
absorption and conversion electron emission geometry
2. Experimental
Details
260
Interactions
T h e b r e a k t h r o u g h for M o s s b a u e r s p e c t r o s c o p y oc
c u r r e d w h e n it w a s realized t h a t for t h e first time t h e
hyperfine i n t e r a c t i o n c o u l d be resolved b e c a u s e of t h e
high r e s o l u t i o n of t h e r e s o n a n c e lines ( H a n n a et al.
1960, K i s t n e r a n d S u n y a r 1960). T h e hyperfine inter
a c t i o n consists of t h e i n t e r a c t i o n b e t w e e n t h e n u c l e u s
a n d its associated electric a n d m a g n e t i c m o m e n t s , a n d
t h o s e of t h e electrons in t h e i m m e d i a t e s u r r o u n d i n g s .
T h e hyperfine c o u p l i n g m e c h a n i s m s a r e of great signi
ficance, yielding electron a n d spin density distribu
tions. T h e r e a r e three m a i n hyperfine i n t e r a c t i o n s
c o r r e s p o n d i n g t o t h e n u c l e a r m o m e n t s w h i c h deter
m i n e t h e n u c l e a r levels.
3.1 Isomer Shift (Electric Monopole
Interaction)
T h e i s o m e r shift originates from t h e C o u l o m b i n t e r a c
tion of t h e c h a r g e d i s t r i b u t i o n s over a finite n u c l e a r
r a d i u s R in t h e excited a n d g r o u n d states a n d t h e
electron c h a r g e density a t the nucleus, effectively t h e s
electrons ( K i s t n e r a n d S u n y a r 1960, W a l k e r et al.
1961, Shirley 1964). T h e t o t a l s-electron density eva
2
l u a t e d a t t h e r e s o n a t i n g nuclei in t h e source, | y/s(0) | ,
2
a n d in t h e a b s o r b e r , | ^ A ( 0 ) | , c a n v a r y if t h e chemical
e n v i r o n m e n t influences t h e t r a n s i t i o n energies in t h e
source a n d t h e a b s o r b e r . T h e resulting isomer shift
c a n be expressed (in t h e nonrelativistic a p p r o x i m a
tion) by
2
( 5 = C ( | ^ A( 0 ) | - | ^ S( 0 ) | ) ^
(6)
w h e r e C is t h e c o n s t a n t c o n t a i n i n g n u c l e a r p a r a m e t e r s
of a given i s o t o p e a n d SR/R is t h e relative c h a n g e of
n u c l e a r r a d i u s b e t w e e n t h e excited state a n d t h e
g r o u n d state. T h e " c h e m i c a l " n a t u r e of t h e i s o m e r
shift led t o t h e occasional use of the t e r m " c h e m i c a l
shift." Because M o s s b a u e r s p e c t r o s c o p y is a relative
m e t h o d t h e s o u r c e s p e c t r u m is related t o t h e
a b s o r b e r s p e c t r u m b y a D o p p l e r m o t i o n o n e of t h e
t w o h a s t o be fixed t o d e t e r m i n e the o t h e r . F o r e a c h
M o s s b a u e r i s o t o p e a reference s t a n d a r d is needed.
5 7
-Fe h a s b e e n selected for t h e i s o t o p e F e .
3.2 Nuclear Zeeman Effect (Magnetic
Dipole
Interaction)
T h e i n t e r a c t i o n of t h e n u c l e a r m a g n e t i c dipole m o
m e n t in a m a g n e t i c field a t t h e site of t h e n u c l e u s
splits t h e n u c l e a r state with spin / i n t o sublevels w i t h
eigenvalues Em as s h o w n in Fig. 2. T h e negative sign
indicates t h a t t h e n u c l e a r m a g n e t i c m o m e n t a n d t h e
5 7
a t o m i c m a g n e t i c m o m e n t in F e a r e o p p o s i t e l y
oriented. C o n s i d e r i n g t h e m u l t i p o l a r i t y of t h e
14.4 k e V y-ray t r a n s i t i o n we h a v e t h e selection rule
Mossbauer
Spectroscopy
I n general, M o s s b a u e r s p e c t r o s c o p y exhibits a
c o m b i n a t i o n of hyperfine i n t e r a c t i o n s . T h e m a g n i
t u d e of these i n t e r a c t i o n s is d e t e r m i n e d by t h e posi
tions of t h e lines a n d t h e relative intensities give
i n f o r m a t i o n o n t h e o r i e n t a t i o n s . T h e exact e v a l u a t i o n
of m i x e d i n t e r a c t i o n s a n d o v e r l a p p i n g spectra is
s o m e t i m e s difficult a n d requires c o m p u t e r analysis.
4.
Applications
M o s s b a u e r s p e c t r o s c o p y is a typical m i c r o s c o p i c tool:
the p o i n t of o b s e r v a t i o n s is a r e s o n a t i n g nucleus. W e
c a n learn s o m e t h i n g a b o u t t h e electronic a n d m a g
netic e n v i r o n m e n t t h r o u g h t h e hyperfine i n t e r a c t i o n s
a n d a b o u t t h e v i b r a t i o n a l states of t h e a t o m s t h r o u g h
t h e D e b y e - W a l l e r factor. I n this section, typical ex
a m p l e s a r e discussed, i n d i c a t i n g t h e success, b u t also
t h e limitations, of the m e t h o d .
4.1 Electronegativity:
(b)
Figure 2
Hyperfine interaction parameters and effects:
(a) interaction of the nuclear magnetic dipole moment
with a magnetic field at the nucleus (magnetic dipole
interaction or nuclear Zeeman effect); (b) interaction of
the nuclear quadrupole moment eQ with electric field
gradient V at the nucleus (electric quadrupole
interaction)
Volta
Potential
T h i s a p p l i c a t i o n d e m o n s t r a t e s the m a c r o s c o p i c a n d
m i c r o s c o p i c view of o n e a n d t h e s a m e p r o b l e m . This
p h e n o m e n o n c a n b e a p p r o a c h e d from t w o extremes.
In o n e case, t w o m a c r o s c o p i c pieces of m e t a l A a n d
a r e b r o u g h t i n t o close c o n t a c t . Because t h e chemical
p o t e n t i a l s t h e F e r m i e n e r g y m u s t be e q u a l , c h a r g e
will m o v e t o w a r d s t h e m o r e electronegative m e t a l . In
t h e o t h e r case, a " r e s o n a n c e m e t a l " a t o m A is
i m p l a n t e d o r i n c o r p o r a t e d i n t o m e t a l B. T h e r e will be
a c h a r g e transfer b e t w e e n t h e i m p u r i t y a t o m a n d the
s u r r o u n d i n g m a t r i x . T h e i s o m e r shift tells us the
direction, t h a t is, w h e t h e r a t o m A gains o r loses
electronic c h a r g e t o t h e s u r r o u n d i n g m a t r i x . In a n
1 9 7
e x p e r i m e n t , the r e s o n a n c e a t o m A u w a s placed i n t o
19 different metallic elements ( B a r r e t t et al. 1963). By
e v a l u a t i n g t h e i s o m e r shifts, a m o n o t o n i c c o r r e l a t i o n
with t h e electronegativity of t h e m a t r i x m e t a l w a s
established. M i e d e m a a n d V a n d e r W o u d e e x t e n d e d
this idea a n d p r e s e n t e d a cellular a t o m i c m o d e l (Mie
d e m a a n d V a n d e r W o u d e 1980). Besides t h e electro
negativity difference a n d a v o l u m e c o n t r i b u t i o n (size
effect), a t e r m reflecting t h e differences in electron
density a t t h e b o u n d a r i e s of t h e a t o m i c cells w a s
i n t r o d u c e d . T h e y were able t o a c c o u n t for the
1 97
o b s e r v e d i s o m e r shift of t h e A u in a large n u m b e r of
g o l d - c o n t a i n i n g alloys.
4.2 Monomer and Dimer
Close t o t h e m e l t i n g p o i n t , a b o u t 4 a t . % iron is
soluble in c o p p e r . A t r o o m t e m p e r a t u r e , t h e solubility
of i r o n in c o p p e r is i m m e a s u r a b l y small. By r a p i d
q u e n c h i n g t e c h n i q u e s , s u p e r s a t u r a t e d alloys c a n
be o b t a i n e d . T h e M o s s b a u e r s p e c t r u m of a C u - 0 . 2
a t . % F e alloy q u e n c h e d from 1243 in w a t e r is s h o w n
in Fig. 3. T h e s p e c t r u m c a n be d e c o m p o s e d i n t o t w o
c o m p o n e n t s : a single line c o r r e s p o n d i n g t o the iso
lated i r o n a t o m s with 12 n e a r e s t - n e i g h b o r c o p p e r
atoms (monomer) and a quadrupole component
261
Mossbauer
Spectroscopy
-I
0
Velocity
(mm
s" )
Figure 3
Mossbauer spectrum of Cu-0.2at.%Fe alloy at room
temperature
representing m a i n l y i r o n n e i g h b o r i n g p a i r s (dimer)
(Krischel et al. 1980). T h e relative a r e a s of the t w o
spectral c o m p o n e n t s a r e r o u g h l y p r o p o r t i o n a l t o the
fraction of m o n o m e r s ( 8 8 % ) a n d d i m e r s ( 1 2 % ) . T h e
latter m a y include a small n u m b e r of trimers. T h e s e
values d e p e n d t o s o m e extent o n t h e q u e n c h i n g c o n
ditions.
T h e existence of t h e q u a d r u p o l e splitting for the
dimers clearly establishes t h a t a n electric field
g r a d i e n t is p r e s e n t a t the i r o n n u c l e a r site, t h a t
is, the local cubic s y m m e t r y is r e m o v e d . C o n
sidering t h e m a g n i t u d e of t h e q u a d r u p o l e inter
1
action ( A Q = 0.639 m m s " ) a n d t h e i s o m e r shift
1
( = 0.189 m m s " with respect t o -Fe) a fairly
g o o d m o d e l of t h e electronic configuration involved
c a n be o b t a i n e d .
4.3 Phase
Analysis
262
-I
+1
Velocity
( m m s ')
Figure 4
Mossbauer spectra of titanium-iron alloys annealed at
858
r a n g e of 8 5 0 - 1 0 8 0 a n d t h e n q u e n c h e d . T h e result
ing spectra are s h o w n in Fig. 4. O w i n g t o the dif
ferences in the i s o m e r shift, the spectra c a n be
d e c o m p o s e d i n t o a c o m p o n e n t representing iron dis
solved in -Ti ( h e x a g o n a l close-packed (hep)) (lowt e m p e r a t u r e p h a s e ) a n d o n e representing /?-Ti
( b o d y - c e n t r e d cubic (bec)) ( h i g h - t e m p e r a t u r e p h a s e ) .
T h e fraction of t h e c o m p o n e n t s d e p e n d s o n t h e
t e m p e r a t u r e . A s s u m i n g the s a m e D e b y e - W a l l e r fac
t o r for b o t h p h a s e s , the relative line intensities repre
sent t h e a m o u n t of iron in t h a t p a r t i c u l a r p h a s e . If the
intensities a r e r o u g h l y the s a m e , this indicates t h a t
iron a t o m s a r e evenly d i s t r i b u t e d in t h e t w o p h a s e s .
H o w e v e r , because the c o n c e n t r a t i o n of iron is c o m
paratively m u c h higher in t h e p h a s e , the n e a r
equality of t h e r e s o n a n c e intensities c o u l d be achieved
only by c h o o s i n g a s t a r t i n g c o m p o s i t i o n C 0 close t o
<\Cfi-C0\.
the e q u i l i b r i u m line Ca: \C0-C9\
A p p l y i n g t h e lever r e l a t i o n s h i p :
C 0 C
Mo
= l
(7)
Mossbauer
1100 -
4.5 Scattering
000 r -
900r-
800
_1_L
d
\0~
10
10"
Fe
concentration
(at.%)
Figure 5
-phase boundary of titanium-rich iron alloys
4.4 Amorphous
Spectroscopy
Metals
Geometry,
Surfaces
fcc(FeNiB)
tetragonal ( F e N i ) 3B
fee (FeNiB)
1
Velocity
} orthorhomboid (FeNi) 3B
(mm s )
Figure 6
Mossbauer spectra obtained
from Fe^Ni^B^: (a) in the
_ l
as-quenched ( v = 1 3 m s ) state; and (b) subsequently
annealed
263
Mossbauer
Spectroscopy
contact
I
surface
.02
I .00
L
a -
I .00
(Fe.Mo)
0.98
bulk
0
96
0.94
1 .03
Velocity
I . 02
( m m s ')
free
surface
I - 00
_i
-6
-4
L
-2
Velocity
I
0
u
2
1
4
( m m s" )
Figure 7
Mossbauer y-ray absorption and electron emission spectra
of amorphous Fe 7 8Mo 2B 20 after annealing for 3 h at 643
Polarimetry
T h e a n g u l a r d e p e n d e n c e of t h e hyperfine i n t e r a c t i o n
as observed by t h e relative line intensities (see Fig. 2)
c a n be used t o m e a s u r e o r i e n t a t i o n s of spins (spin
texture) o r o r i e n t a t i o n s of principal axes of t h e elec
tric field g r a d i e n t (principal axes texture) ( G o n s e r a n d
P f a n n e s 1974). F i g u r e 7 s h o w s a b u l k s p e c t r u m of a n
a m o r p h o u s alloy. T h e lines a r e b r o a d , b u t it is f o u n d
t h a t the second a n d fifth lines (Am = 0) a r e strongest.
T h i s indicates t h a t t h e spins a r e o r i e n t e d preferen
tially p e r p e n d i c u l a r t o t h e p r o p a g a t i o n direction of
264
Figure 8
Mossbauer x-ray emission spectra of X210Crl2 steel:
(a) before; and (b) after laser irradiation
t h e y r a y s , t h a t is, in the p l a n e of t h e a m o r p h o u s
ribbon.
T h e a n g u l a r d e p e n d e n c e of t h e split spectra is
associated with p o l a r i z a t i o n of t h e r a d i a t i o n . A p o l a r imeter for linearly a n d circularly p o l a r i z e d y rays c a n
be c o n s t r u c t e d . T o o b s e r v e r e s o n a n c e , t h e line posi
tions must be matched not only by an appropriate
D o p p l e r velocity, b u t also b y a p p r o p r i a t e p o l a r i z a
tion. W i t h such a n a p p a r a t u s , t h e birefringence
r o t a t i o n of t h e F a r a d a y - M o s s b a u e r effect c a n b e
m e a s u r e d (Pfannes a n d G o n s e r 1974).
4.7 Dynamical Effects,
Diffusion
I n general, every m e t h o d h a s its characteristic time,
effectively t h e time in w h i c h t h e i n f o r m a t i o n o n a
certain p r o p e r t y is collected a n d m e a s u r e d . I n M o s s
b a u e r s p e c t r o s c o p y , t h e characteristic t i m e o r " c l o c k "
d e p e n d s o n t h e i s o t o p e a n d is r e p r e s e n t e d by t h e m e a n
lifetime of s p o n t a n e o u s t r a n s i t i o n from t h e excited
s t a t e t o t h e g r o u n d state. T h i s t i m e s t a r t s t h e i n s t a n t
t h e excited state is r e a c h e d from higher states in t h e
s o u r c e o r in t h e a b s o r b e r w h e n t h e leading edge of t h e
y r a y arrives a t t h e nucleus. C o n s i d e r i n g t h e i s o t o p e s
1 8 7
available, o n e h a s a wide r a n g e in half-life: R e h a s a
u
197
9
119
8
5 7
Au, 10" s; Sn, 10" s; Fe,
half-life of 1 0 - s ;
7
6 7
_ 5
1 0 ~ s ; a n d Z n , 1 0 s . Half-life d e t e r m i n e s in t h e
ideal case t h e L o r e n t z i a n line w i d t h s a c c o r d i n g t o t h e
u n c e r t a i n t y principle a n d t h e " t i m e w i n d o w " for
dynamical experiments. During the "time window,"
diffusion m a y o c c u r either by j u m p s of t h e r e s o n a t i n g
a t o m s themselves ( K n a u e r a n d M u l l e n 1968) o r b y
p a s s i n g of a small a t o m like h y d r o g e n t h r o u g h neigh
b o r i n g interstitial sites of t h e r e s o n a n c e a t o m a n d
Mossbauer
Bibliography
Barrett , Grant R W, Kaplan M, Keller D A, Shirley D
A 1963 Electron transfer in dilute gold alloys. J. Chem.
Phys. 39: 1035-40
Bauer J, Gonser U, Wagner G 1986 Magnetic and
structural behavior of Fe 4 0Ni 4 0B 20 alloys as a function of
the melt-spinning parameters. Hyperfine Interact. 27:
401^1
Blasius A, Gonser U 1976 Precision phase analysis. J. Phys.
(Paris) 37(C6): 397-9
Blasius A, Preston R S, Gonser U 19795 7Mossbauer study of
the diffusion of stored hydrogen in Fe-doped titanium.
Z. Phys. Chem. (Wiesbaden) 115: 187-99
Gonser U (ed.) 1975 Mossbauer Spectroscopy, Topics in
Applied Physics, Vol. 5. Springer, Berlin
Gonser U (ed.) 1981 Mossbauer Spectroscopy II: The Exotic
Side of the Methods, Topics in Current Physics, Vol. 25.
Springer, Berlin
Gonser U (ed.) 1986 Microscopic Methods in Metals, Topics
in Current Physics, Vol. 40. Springer, Berlin
Gonser U, Ackermann M, Wagner G 1983 Magnetoelastic effects in amorphous metals due to surface crystal
lization and oxidation. / . Magn. & Magn. Mater. 31-4:
1605-7
Gonser U, Pfannes D 1974 Texture problems. / . Phys.
(Paris) 35: 113-20
Hanna S S, Heberle J, Littlejohn C, Perlow G J, Preston R
Spectroscopy
265
Neutron Radiography
N e u t r o n r a d i o g r a p h y is o n e of several m e t h o d s
e m p l o y e d for t h e visualization of i n t e r n a l details of
materials a n d s t r u c t u r e s . T h i s t e c h n i q u e utilizes n e u
t r o n s , r a t h e r t h a n o r g a m m a rays, as t h e p e n e t r a t i n g
radiation to produce a radiographic image. Neutrons
replace p h o t o n r a d i a t i o n b e c a u s e of t h e d r a m a t i c
m a n n e r in which n e u t r o n i n t e r a c t i o n s with m a t t e r
differ from t h o s e o b s e r v e d with o r g a m m a r a y s .
N e u t r o n radiography provides a new dimension to
r a d i o g r a p h i c inspection which serves t o e x t e n d a n d
complement information provided by other radio
g r a p h i c m e a n s . I n m a n y cases, t h e m e t h o d p r o v i d e s
the only m e a n s b y w h i c h certain details such as plastic
or r u b b e r c o m p o n e n t s o r v a r i a t i o n s in r e a c t o r fuel
c a n be observed.
1.
The
Neutron
N e u t r o n s a n d p r o t o n s a r e t h e b u i l d i n g b l o c k s of t h e
a t o m i c nucleus. U n l i k e t h e p r o t o n , t h e n e u t r o n is a
n e u t r a l particle w h i c h possesses n o electric c h a r g e ,
a n d it weighs slightly m o r e t h a n t h e p r o t o n , t h a t is,
1.00867 a t o m i c m a s s u n i t s . N e u t r o n s a r e u n s t a b l e
particles, h a v i n g a half-life of a p p r o x i m a t e l y 12 m i n ,
a n d decay i n t o a p r o t o n , electron a n d a n e u t r i n o .
N e u t r o n s c a n v a r y in energy from essentially zero t o
energies in excess of 20 M e V .
2. Interaction
of Neutrons
with
Matter
t r o n s a r e heavily a t t e n u a t e d by t h e lighter a t o m i c
n u m b e r elements while experiencing low a t t e n u a t i o n
b y t h e heavier elements. T h i s is b e c a u s e t h e nuclei
with w h i c h t h e n e u t r o n s i n t e r a c t possess a c o m p l e x
energy-level s t r u c t u r e . T h e m a s s a t t e n u a t i o n coeffi
cients of t h e elements for o r g a m m a rays, interacting
with t h e optical electrons, a r e illustrated b y the solid
m o n o t o n i c a l l y increasing c u r v e in F i g . 2. T h i s is
b e c a u s e t h e n u m b e r of electrons o r b i t i n g t h e a t o m i c
nucleus b e a r s a direct r e l a t i o n s h i p t o m a t e r i a l density
a n d h e n c e t o x- a n d g a m m a - r a y a t t e n u a t i o n .
3. Neutron
Production
(1)
2
Scattered radiation
Figure 1
Transmission of radiation through materials
267
Neutron
Radiography
* "
30
40
50
60
70
80
90
100
Atomic number
Figure 2
Mass attenuation coefficient as a function of atomic number of the elements
4. Neutron
Applications
O n e e x a m p l e of n e u t r o n r a d i o g r a p h y is illustrated in
Fig. 3 in w h i c h a n r a y a n d a n e u t r o n r a d i o g r a p h of
t h e s a m e specimen a r e c o m p a r e d . In t h e r a d i o g r a p h
in F i g . 3a, t h e p l a c e m e n t of t h e n e o p r e n e seal in a
stainless steel valve is n o t evident. H o w e v e r , t h e seal
c a n b e readily seen in t h e n e u t r o n r a d i o g r a p h of F i g .
3b. T h i s is d u e t o b e a m scattering by h y d r o g e n a t o m s .
O t h e r a p p l i c a t i o n s include t h e e x a m i n a t i o n of p l a s
tics, r u b b e r , adhesives, explosives o r w o o d in c o n t a i n
m e n t systems w h i c h a r e o p a q u e t o o r g a m m a r a y s .
Imaging
Being a n o n i o n i z i n g particle, t h e n e u t r o n d o e s n o t
i n t e r a c t with r a d i o g r a p h i c film t o f o r m a n i m a g e
directly, b u t m u s t be c o n v e r t e d t o s o m e t y p e of
r a d i a t i o n w h i c h will sensitize t h e film. Basically this is
a c c o m p l i s h e d in t h r e e w a y s : (a) in t h e direct i m a g i n g
m o d e in w h i c h r a d i a t i o n c a p a b l e of sensitizing t h e
film is p r o d u c e d o n n e u t r o n c a p t u r e by a c o n v e r t e r
foil; (b) t h e indirect i m a g i n g m o d e in w h i c h a n
a u t o r a d i o g r a p h is m a d e of a n i m a g e d c o n v e r t e r emit
ting delayed ionizing r a d i a t i o n t o e x p o s e t h e film; a n d
(c) t h e electronic m o d e in w h i c h a direct e x p o s u r e is
p r o d u c e d o n a n e u t r o n - s e n s i t i v e video system.
268
5.
(a)
(b)
Figure 3
Radiographs using (a) rays and (b) neutrons of a
stainless steel valve with neoprene seal
Nuclear
Magnetic
Resonance
Spectroscopy
Bibliography
1.
A t o m i c nuclei m a y possess a n g u l a r m o m e n t u m , a n d
therefore a m a g n e t i c d i p o l e m o m e n t d e p e n d i n g
u p o n their spin q u a n t u m n u m b e r I. T h e spin q u a n t u m
n u m b e r m a y h a v e values of z e r o , half-integers a n d
w h o l e integers. Nuclei w i t h 1=0 h a v e n o m a g n e t i c
m o m e n t a n d therefore d o n o t exhibit t h e N M R
p h e n o m e n o n ; this includes all nuclei with a n even
m a s s a n d a t o m i c n u m b e r . Theoretically, all of the
r e m a i n i n g nuclei c a n be o b s e r v e d b y N M R .
I n t h e classical m e c h a n i c a l d e s c r i p t i o n of N M R , a
nucleus is c o n s i d e r e d t o b e precessing a b o u t the
a p p l i e d m a g n e t i c field with t h e frequency of preces
sion given b y t h e L a r m o r e q u a t i o n :
D. A. Garrett
[ N a t i o n a l B u r e a u of S t a n d a r d s ,
Washington, D C , USA]
The NMR
Phenomenon
v0 =
/20
269
Nuclear
Magnetic
Resonance
Spectroscopy
C H ?- C H ,
\
2.6
1.2
- C H 2-
-CH,
mm
tutu
I
10
I
9
I
8
I
3
I
2
(ppm)
Figure 1
NMR spectrum of ethylbenzene showing a triplet and
quartet corresponding to the methyl and methylene
protons, respectively. Arrows indicate the possible
orientations of the protons of the neighboring group
resulting in the characteristic number and intensities of
lines
2. Chemical
Shift
In a c o n s t a n t h o m o g e n e o u s m a g n e t i c field, nuclei
c o m e i n t o r e s o n a n c e at a very specific frequency (
a t 79.5 M H z in a 1.8 field, for e x a m p l e ) . F o r t u n a
tely for the chemist, all p r o t o n s d o n o t r e s o n a t e a t
exactly 79.5 M H z . T h e very subtle differences in the
r e s o n a n c e frequency a r e d u e t o t h e differences in the
chemical e n v i r o n m e n t of t h e o b s e r v e d nuclei; t h e
difference in frequency is referred t o as the chemical
shift. F i g u r e 1 s h o w s t h e N M R s p e c t r u m of
ethylbenzene. It c o n t a i n s three sets of r e s o n a n c e lines:
a singlet ( a r o m a t i c p r o t o n s ) , a q u a r t e t (methylene
p r o t o n s ) a n d a triplet (methyl p r o t o n s ) . T h e different
positions t h a t these r e s o n a n c e lines o c c u p y in t h e
frequency s p e c t r u m relative t o a n internal s t a n d a r d
are referred t o as differences in their chemical shifts.
E a c h nucleus is s u r r o u n d e d b y a n electron cloud, the
m o t i o n of these electrons creating a s e c o n d a r y m a g
netic field which t e n d s t o o p p o s e the applied m a g n e t i c
field; chemical-shift differences arise b e c a u s e this elec
t r o n density varies, d e p e n d i n g u p o n t h e electronegati
vity of t h e a t o m s a t t a c h e d t o the nucleus a n d the type
of b o n d i n g in which it is involved. T h u s , t h e higher
t h e electron density a b o u t a nucleus, the greater the
s e c o n d a r y m a g n e t i c field (or " s h i e l d i n g " effect) a n d ,
270
3.
NMR
C o n s i d e r t h e N M R s p e c t r u m of e t h y l b e n z e n e
s h o w n in Fig. 1. T h e d o m i n a n t features of t h e spec
t r u m a r e t h e presence of a triplet a t 1.2 p p m (methyl
p r o t o n s ) a n d a q u a r t e t at 2.6 p p m (methylene p r o
t o n s ) . Differences in m a g n e t i c e n v i r o n m e n t a r e re
sponsible for t h e differences in chemical shift, t h e
effect of the nearest n e i g h b o r i n g g r o u p usually being
m o s t i m p o r t a n t . I n t h e case of t h e m e t h y l g r o u p , for
e x a m p l e , t h e n e i g h b o r i n g m e t h y l e n e g r o u p n o t only
affects t h e p o s i t i o n of t h e r e s o n a n c e line b u t causes
t h e p e a k t o b e split i n t o a triplet as well. T h e e x p l a n a
tion for this p h e n o m e n o n , called s p i n - s p i n splitting,
lies in t h e fact t h a t t h e n e i g h b o r i n g p r o t o n s m a y also
Nuclear
Table 1
Relative intensities of the lines of a multiplet
Multiplicity
0
1
2
3
4
5
singlet
doublet
triplet
quartet
quintet
sextet
Intensity
1
11
1 2 1
13 3 1
1 4 6 4 1
1 5 10 10 5 1
be in different o r i e n t a t i o n s w i t h respect t o t h e a p p l i e d
m a g n e t i c field. Since t h e p r o t o n is a nucleus w i t h
=
t w
o
I h
possible spin states exist for e a c h p r o t o n .
Depending u p o n whether the neighboring nuclear
spin is aligned with (parallel) o r o p p o s e d t o (antiparallel) t h e p r o t o n a t r e s o n a n c e , it will either in
crease o r decrease t h e n e t m a g n e t i c field experienced
by the o b s e r v e d p r o t o n . T h i s gives rise t o different
energy levels a n d t h u s different r e s o n a n c e lines. In t h e
case of the m e t h y l e n e p r o t o n s of e t h y l b e n z e n e , t h r e e
c o m b i n a t i o n s a r e possible (see F i g . 1) p r o d u c i n g a
triplet for t h e m e t h y l p r o t o n s . Likewise, t h e m e t h y
lene p r o t o n s a r e affected b y t h e three m e t h y l p r o t o n s .
T h e possible o r i e n t a t i o n s of these t h r e e p r o t o n s are:
all three aligned, t w o aligned a n d o n e o p p o s e d ( a n d
there a r e three p e r m u t a t i o n s of this o r i e n t a t i o n ) , t w o
o p p o s e d a n d o n e aligned (also with three p e r m u t a
tions), a n d all t h r e e o p p o s e d . T h e effect of t h e m e t h y l
g r o u p , therefore, is t o p r o d u c e four r e s o n a n c e lines (a
q u a r t e t ) for t h e m e t h y l e n e p r o t o n s .
S p i n - s p i n splitting is a p r i m a r y characteristic of
N M R . T h e s e i n t e r a c t i o n s a r e said t o b e electron
c o u p l e d in t h a t they o p e r a t e t h r o u g h t h e b o n d i n g
n e t w o r k ; t h e effect is q u i t e s t r o n g over t h e first few
b o n d s b u t diminishes greatly thereafter. T h e n u m b e r
of lines p r o d u c e d b y s p i n - s p i n c o u p l i n g is given by:
multiplicity = 2nl + 1
w h e r e is t h e n u m b e r of p r o t o n s in t h e n e i g h b o r i n g
g r o u p a n d lis t h e spin q u a n t u m n u m b e r ( = i ) . T h e
relative intensities of t h e lines of a m u l t i p l e t a r e
predicted by P a s c a l ' s triangle ( T a b l e 1).
T h e s e p a r a t i o n b e t w e e n t h e lines of a m u l t i p l e t is
referred t o as t h e c o u p l i n g c o n s t a n t J. T h i s value,
expressed in h e r t z , reflects t h e m a g n i t u d e of t h e s p i n spin i n t e r a c t i o n a n d is i n d e p e n d e n t of t h e a p p l i e d
m a g n e t i c field. C h a r a c t e r i s t i c c o u p l i n g c o n s t a n t s a r e
of great value in s t r u c t u r e e l u c i d a t i o n .
4. Fourier
Transform
NMR
T h e c o n v e n t i o n a l m o d e of i n s t r u m e n t o p e r a t i o n
involves v a r y i n g either t h e m a g n e t i c field o r rf signal
while h o l d i n g t h e o t h e r c o n s t a n t (field o r frequency
Magnetic
Resonance
Spectroscopy
5.
13
CNMR
O n e of t h e low-sensitivity nuclei w h i c h h a s b e c o m e a
r o u t i n e analytical t o o l for o r g a n i c chemists since t h e
1 3
a d v e n t of F T - N M R is C . T h e m a g n e t i c m o m e n t of
1 3
C is a b o u t o n e q u a r t e r of t h a t of , b u t its n a t u r a l
a b u n d a n c e is only 1 . 1 % . T h e r a r e o c c u r r e n c e of t h e
1 3
i s o t o p e greatly simplifies C N M R spectra by elimi
1 3
1 3
n a t i n g t h e s p i n - s p i n c o u p l i n g ( C - C ) which is so
d o m i n a n t in N M R spectra. F u r t h e r simplification
1 3
of C spectra is achieved b y r e m o v i n g t h e scalar
1 3
coupling between C and by double-resonance
d e c o u p l i n g o v e r t h e chemical-shift r a n g e . I n the
r e s u l t a n t s p e c t r u m , e a c h line c o r r e s p o n d s t o a m a g
netically u n i q u e c a r b o n a t o m in t h e s a m p l e . T h e
1 3
relatively large C chemical-shift r a n g e , which is
a b o u t t w e n t y times t h a t for , affords g o o d resolu
tion of even structurally q u i t e similar a t o m s . T h e
ability t o differentiate a m o n g several s t r u c t u r e s is
facilitated b y t h e fact t h a t t h e m a j o r factors g o v e r n i n g
1 3
C n u c l e a r shieldings a r e well established. Experi
m e n t a l l y , it h a s b e e n f o u n d t h a t s u b s t i t u e n t effects o n
1 3
C chemical shifts a r e largely additive. Semiempirical
m e t h o d s , therefore, a r e usually successful in predict-
271
Nuclear
Magnetic
Resonance
Spectroscopy
Time domain
Figure 2
13
C NMR spectrum of ethylbenzene showing the time-based free-induction decay (upper trace) and corresponding
frequency spectrum (lower trace)
Table 2
8
C Chemical shifts for some common organic compounds
13
Compound
30.4
204.1
(a)
CH 3CCH
J
3
a
CH2
CH2C12
CH3OH
(CH 3CH 2) 2NH
54.0
49.3
15.4
44.1
13.9
22.9
(b)
C 6H 6
CH3COH
J
a
32.0
160
128.5
20.6
LI
I
140
I
100
I
80
178.3
272
CH3
( ppm )
Figure 3
13
C N M R spectrum of ethylbenzene with (a) complete
proton decoupling, and (b) off-resonance decoupling. The
insert in (b) is an expansion of the region 123-130 ppm
Nuclear
6. Other
Nuclei
Bibliography
Becker D 1980 High Resolution NMR: Theory and Chem
ical Applications, 2nd edn. Academic Press, New York
Bovey F A 1968 Nuclear Magnetic Resonance Spectroscopy.
Academic Press, New York
Farrar C, Becker E D 1971 Pulse and Fourier Transform
NMR: Introduction to Theory and Methods. Academic
Press, New York
Harris R K, Mann (eds.) 1978 NMR and the Periodic
Table. Academic Press, New York
Levy G C, Nelson G L 1972 Carbon-13 Nuclear Magnetic
Resonance for Organic Chemists. Wiley, New York
Slichter C 1978 Principles of Magnetic Resonance, 2nd
edn. Springer, Berlin
Stothers J 1972 Carbon-13 NMR Spectroscopy. Academic
Press, New York
E. A . Williams a n d P. E. D o n a h u e
[General Electric C o r p o r a t e R e s e a r c h
and Development, Schenectady,
New York, USA]
Magnetic
Resonance
Spectroscopy
of
Solids
3cos ~ 1
3
'
273
Nuclear
Magnetic
Resonance
Spectroscopy
of
Solids
(2)
(3)
274
Cross-polarization time
Figure 1
Theoretical cross-polarization dynamics: (a) the expected
rare spin magnetization as a function of cross-polarization
time in the absence of relaxation effects (the single
exponential curve is characterized by a time constant TIS);
(b) spin (either rare or abundant) relaxation (the
exponential curve is characterized by a time constant TXp
which, in this example, is eight times the
cross-polarization time TIS)\ and (c) the expected rare spin
magnetization as a function of cross-polarization time, is
the product of curves (a) and (b) with the time axis in
units of TIS and the enhancement axis in units of y,jys
(notice that for this example, maximum enhancement is
achieved at a cross-polarization time of about 2.2 TIS and
is about 67% of the theoretical maximum)
1.0
1.0
2.0
3.0
4.0
5.0
Cross-polarization time
Figure 2
A family of curves showing the cross-polarization
magnetization as a function of cross-polarization time; in
each curve, TIS is constant and Tx is varied; the ratio
TJTiS is (a) 1.0, (b) 2.0, (c) 4.0, (d) 8.0 and (e) 16.0; axis
units are as in Fig. 1
Nuclear
Table 1
The time of occurrence and the value of the maximum
enhancement of cross-polarization for various values of
TJTIS
Magnetic
Resonance
Spectroscopy
of
Solids
(a)
Enhancement
%
TJTa
1.0
2.0
4.0
8.0
16.0
0.69
1.10
1.61
2.20
2.83
25
38
53
68
79
(1975) s h o w e d t h a t if t h e c r o s s - p o l a r i z a t i o n experi
m e n t w a s p e r f o r m e d while t h e solid s a m p l e w a s
spinning a t a sufficiently high r a t e (several t h o u s a n d
revolutions p e r second) a t a n o r i e n t a t i o n w h e r e E q n .
(1) is zero (a state k n o w n as m a g i c - a n g l e s p i n n i n g ) ,
resolution a p p r o a c h i n g t h a t of liquid s a m p l e s c a n be
o b t a i n e d . S p i n n i n g a t a r a t e larger t h a n t h e C S A
causes the C S A of e a c h individual spin t o b e a v e r a g e d
to the i s o t r o p i c chemical shift value. If t h e s p i n n i n g
r a t e is less t h a n t h e C S A , s p i n n i n g s i d e b a n d s a r e
observed. F i g u r e 3 s h o w s t h e effect of s a m p l e s p i n n i n g
rate on the carbon-13 cross-polarization magic-angle
spinning ( C P M A S ) s p e c t r u m of G e n e r a l Electric
L e x a n (bisphenol A p o l y c a r b o n a t e ) resin. It c a n b e
seen from F i g . 3 b t h a t t h e intensities of t h e s p i n n i n g
s i d e b a n d s a p p r o x i m a t e l y m i m i c t h e s h a p e of t h e
n o n s p i n n i n g line s h a p e s .
T h e s e i m p o r t a n t discoveries of Pines a n d Schaefer,
a n d the w o r k o n w h i c h they a r e b a s e d , p r o v i d e t h e
f o u n d a t i o n for t h e m o s t p o p u l a r f o r m of highresolution solid-state N M R , t h e C P M A S e x p e r i m e n t .
C o n d i t i o n s for t h e h i g h - r e s o l u t i o n o b s e r v a t i o n of
a b u n d a n t spins (i.e., p r o t o n s ) were w o r k e d o u t later
and combined magic-angle spinning with multiple
pulses d u r i n g t h e acquisition of t h e signal ( h o m o n u c lear d e c o u p l i n g ) a n d will n o t b e discussed in this
article.
1. General
300
200
IOO
-100
Figure 3
Carbon-13 cross-polarization spectra of a sample of GE
Lexan resin are shown spining at (a) 7940 Hz, (b) 3460 Hz
and (c) not spinning. All spectra were obtained with a
2.5 m cross-polarization with ycHc = = 55 kHz.
Spectrum (a) shows only minor spinning sidebands, while
(b) shows many sidebands, especially from the aromatic
resonances, whose chemical shift anisotropics are expected
to be higher. Spectrum (c) is nonspinning, showing
overlapping resonances broadened by CSA
Instrumentation
g e o m e t r y of t h e p r o b e , r o o m - t e m p e r a t u r e h o m o
geneity s h i m coils h a v e only a m o d e s t i m p a c t o n
s p e c t r u m q u a l i t y a n d h a v e been o m i t t e d o n s o m e
solids-only N M R s p e c t r o m e t e r s .
R a d i o - f r e q u e n c y field s t r e n g t h r e q u i r e m e n t s for
C P M A S N M R a r e typically 1-2 o r d e r s of m a g n i t u d e
higher t h a n for N M R of liquids, resulting in p o w e r
r e q u i r e m e n t s r a n g i n g from a l m o s t 100 W t o several
k i l o w a t t s , d e p e n d i n g o n t h e p r o b e efficiency. T h e
C P M A S p r o b e is t h e u n i q u e p a r t of a solids N M R
s p e c t r o m e t e r . Several different designs a r e c o m m e r
cially available a n d all s h a r e t h e following features:
275
Nuclear
Magnetic
Resonance
Spectroscopy
of
Solids
(a)
a s a m p l e s p i n n i n g system consisting of a r o t o r
(spinner) m a d e of a h i g h - s t r e n g t h m a t e r i a l t o
h o l d t h e s a m p l e t u r b i n e l i k e impellers a r e p a r t
of the r o t o r so t h a t it m a y be s p u n b y pressurized
gas flowing over these features;
(b)
a s t a t o r (spinner h o u s i n g ) which p r o v i d e s p r e s
surized gas t h r o u g h a b e a r i n g surface in w h i c h
the r o t o r will s p i n t h e s t a t o r is m o u n t e d in the
p r o b e so t h a t t h e s a m p l e spins a t the m a g i c angle
( ~ 54.7) relative t o t h e applied m a g n e t i c field;
and
(c)
2. Sample
Requirements
3.
Applications
276
1 3
Nuclear
4.
Magnetic
Resonance
Spectroscopy
of
Solids
Limitations
5.
Summary
13
W h i l e C - * H c r o s s - p o l a r i z a t i o n w a s t h e focus of this
15
article o t h e r nuclei c a n be o b s e r v e d , including N ,
29
119
3 1
S i , S n a n d P . It is also possible t o generate crossp o l a r i z a t i o n intensity from nuclei o t h e r t h a n . F o r
1 3
l 9
e x a m p l e , C - F C P M A S s p e c t r a c a n be o b t a i n e d
o n fluorinated p o l y m e r s . In a n u m b e r of respects,
C P M A S N M R is e x p e r i m e n t a l l y m o r e d e m a n d i n g
t h a n c o n v e n t i o n a l N M R of liquids. H o w e v e r , like
N M R of liquids, C P M A S N M R is invaluable in the
s t u d y of solids, p r o v i d i n g b o t h static (structural) a n d
d y n a m i c ( m o t i o n a l ) i n f o r m a t i o n . While there are
s o m e s a m p l e s which c a n n o t be studied by C P M A S
N M R , this t e c h n i q u e c a n be applied t o a wide variety
of m a t e r i a l s , regardless of p u r i t y , crystallinity o r o t h e r
physical a t t r i b u t e s .
cknowledgements
T h e h e l p of E. A. Williams a n d J. S m i t h in p r e p a r i n g
this article is gratefully a c k n o w l e d g e d .
See also: Nuclear Magnetic Resonance Spectroscopy
Bibliography
Alemany L B, Grant D M, Pugmire R J, Alger D, Zilm
W 1983a Cross polarization and magic angle sample
spinning NMR spectra of model organic compounds, 1.
Highly protonated molecules. J. Am. Chem. Soc. 105:
2133-41
Alemany L B, Grant D M, Pugmire R J, Alger D, Zilm
W 1983b Cross polarization and magic angle sample
spinning NMR spectra of model organic compounds, 2.
molecules of low or remote protonation. J. Am. Chem.
Soc. 105: 2142-7
Belfiore L A, Henrichs , Massa D J, Zumbulyadis N,
Roth well W , Cooper S L 1983 Molecular dynamics of
polycarbonate-diluent systems: applications of highresolution carbon-13 solid-state NMR. Macromolecules
16: 1744-53
Bloch F, Hansen W W, Packard 1947 The nuclear
induction experiment. Phys. Rev. 70: 474-85
Bryson R L, , Hatfield
G R, Early A, Palmer A R, Maciel
3
G 1983 C NMR studies of solid phenolic resins using
cross polarization and magic-angle spinning. Macromol
ecules 16: 1669-72
Dixon W 1981 Spinning-sideband-free NMR spectra.
J. Magn. Reson. 44: 220-3
277
Nuclear
Magnetic
Resonance
Spectroscopy
of
Solids
278
Optical Calorimetry
Optical c a l o r i m e t r y is a n e x p e r i m e n t a l m e t h o d used
to d e t e r m i n e t h e optical a b s o r p t a n c e o r a b s o r p t i o n
coefficient in w e a k l y a b s o r b i n g m a t e r i a l s . W h i l e
gases, liquids a n d solids m a y be studied u s i n g this
t e c h n i q u e , in practice c a l o r i m e t r i c m e t h o d s a r e m o s t
often used t o m e a s u r e t h e a b s o r p t i o n in low-loss
w i n d o w s a n d m i r r o r s . F u r t h e r m o r e , since t h e m e t h o d
relies o n m e a s u r i n g t h e small t e m p e r a t u r e rise
b r o u g h t a b o u t by t h e a b s o r p t i o n of optical energy,
laser sources a r e usually r e q u i r e d t o e n s u r e sufficient
heating. In c a l o r i m e t r y , t h e a b s o r p t i o n is d e t e r m i n e d
by m e a s u r i n g in s o m e w a y t h e t e m p e r a t u r e rise c a u s e d
by the laser r a d i a t i o n striking t h e optical c o m p o n e n t
a n d relating this increase t o p o w e r a b s o r b e d in t h e
sample. G e n e r a l l y , t h e t e m p e r a t u r e rise is simply
m e a s u r e d with a t h e r m o c o u p l e a l t h o u g h a n interferometric t e c h n i q u e h a s b e e n used t o m e a s u r e this in
crease by o b s e r v i n g t h e c h a n g e in optical p a t h as t h e
c o m p o n e n t is h e a t e d .
/.
Adiabatic
Thermocouple
mC(dT/dt)
Calorimetry
A d i a b a t i c c a l o r i m e t r y , in w h i c h a t h e r m o c o u p l e o r
t h e r m i s t o r is used t o m e a s u r e t e m p e r a t u r e a n d a laser
is used as a h e a t s o u r c e , is b y far t h e m o s t c o m m o n
calorimetric t e c h n i q u e . S a m p l e s c a n b e i l l u m i n a t e d
with as little as a few h u n d r e d milliwatts of
c o n t i n u o u s - w a v e laser p o w e r t o o b t a i n a b s o r p t i o n
6
_ 1
coefficients as low as 1 0 ~ c m . L a s e r w a v e l e n g t h s
from the millimeter t o ultraviolet region h a v e been
used to o b t a i n values of t h e a b s o r p t i o n in h i g h - p o w e r
laser w i n d o w m a t e r i a l s , e n h a n c e d reflectors, thin-film
c o a t i n g s a n d low-loss fiber-optic w a v e g u i d e s . Since
the t e c h n i q u e p r o v i d e s a n a b s o l u t e m e a s u r e of
a b s o r p t i o n w i t h o u t the need for a n y reference o r
calibrated s t a n d a r d s , a n d b e c a u s e it is extremely
sensitive a n d simple t o use, it h a s w i d e s p r e a d u s a g e .
T h e basic features of a laser c a l o r i m e t e r a r e s h o w n
in Fig. 1. T h e s a m p l e is t h e r m a l l y isolated from t h e
s u r r o u n d i n g s b y insulating p i n s (e.g., n y l o n ) a n d a
differential t h e r m o c o u p l e is a t t a c h e d t o t h e s a m p l e
a n d a n e a r b y t h e r m a l m a s s (reference p o i n t ) .
Generally, t h e c a l o r i m e t e r is e v a c u a t e d b u t , since t h e
analysis includes t h e effects of c o n d u c t i o n a n d c o n
vection h e a t losses, the m e a s u r e m e n t s c a n , in m a n y
cases, be d o n e in air. T h e small t e m p e r a t u r e rise o n
laser h e a t i n g is m e a s u r e d with a n a n o v o l t m e t e r a n d
the t e m p e r a t u r e - t i m e c u r v e is r e c o r d e d o n a stripc h a r t recorder. F r o m this c u r v e , t h e t h e r m a l rise dT/dt
can be o b t a i n e d a n d related t o t h e a b s o r p t i o n coeffi
cient using a simple h e a t - b a l a n c e relation:
= Pa = (n
\)PLPJ2n
(1)
Absorption
\ j '
- T \ - { T \ - T \ ) ( ^ ^ ^
2
= (n + \WLPJ2n
(2)
Nylon pin
^Sample
Thermocouple
J^^^^^~^
Recorder
Figure 1
Experimental arrangement for laser calorimetry. The
sample is thermally isolated with nylon pins and the
calorimeter itself (with windows) is typically evacuated
279
Optical
Calorimetry
ptL
= p&L
+ 2S
(3)
3.
Thin-Film
Absorption
360
Figure 3
Experimental thermal-rise curve for KC1 at 10.6 . The
initial slope provides the bulk absorption /?b, and from the
final bulk plus surface slope the surface absorption S can
be obtained. The initial jump is associated with light
scattered directly onto the thermocouple
t a n c e m e a s u r e d in t h e film p l u s s u b s t r a t e At w i t h
t h e a b s o r p t a n c e of t h e s u b s t r a t e a l o n e As; t h a t
is, A{= At As. I n this w a y , t h e a b s o r p t a n c e s of
single-layer
or
multilayer
antireflection
and
enhanced-reflection films h a v e b e e n m e a s u r e d for
films d e p o s i t e d o n s t a n d a r d d i s k - s h a p e d w i n d o w s a n d
m i r r o r s . T h e l o n g - b a r t e c h n i q u e h a s also b e e n used t o
o b t a i n A{ b y d e p o s i t i n g a film o n o n e e n d of t h e b a r .
T h e r m o c o u p l e s p l a c e d a t b o t h e n d s of t h e b a r , a n d in
t h e m i d d l e , p r o v i d e different t h e r m a l - r i s e curves
w h i c h m a y be a n a l y z e d t o o b t a i n A{ directly w i t h o u t
the need to subtract the substrate absorption.
T h e a b s o r p t a n c e of a thin-film c o a t i n g A{ m a y b e
o b t a i n e d calorimetrically by c o m p a r i n g t h e a b s o r p 4. Other
laser
off
laser
on
3 L
bulk
] heating
laser
off
bulk and
surface
heating
!
Figure 2
Thermal-rise curves obtained for (a) typical disk-shaped
samples and (b) long-bar samples. Data are analyzed
using the temperatures and slopes from the three regions:
(1) initial cooling, (2) laser heating and (3) final cooling
280
Optical
Calorimetric
Methods
I n s t e a d of m e a s u r i n g laser h e a t i n g with t h e r m o
c o u p l e s , t h e t e m p e r a t u r e increase m a y b e d e t e r m i n e d
by m e a s u r i n g t h e c h a n g e in o p t i c a l p a t h length of t h e
s a m p l e . I n this m e t h o d t h e s a m p l e is p l a c e d in a n
interferometer a n d illuminated with a heating b e a m
a n d a p r o b e b e a m t o m o n i t o r t h e fringe c h a n g e s o n
h e a t i n g . F r o m t h e c o m p u t e d c h a n g e in optical p a t h
length, t h e coefficient of t h e r m a l e x p a n s i o n a n d t h e
t e m p e r a t u r e coefficient of t h e refractive index, t h e
s a m p l e h e a t i n g a n d h e n c e m a y be o b t a i n e d . T h e
m e t h o d h a s a d v a n t a g e s in t h a t n o s e n s o r t o u c h e s t h e
s a m p l e ( m i n i m i z i n g scattered-light p r o b l e m s ) , a n d
relatively low s o u r c e energies m a y b e used. I n a d d i
tion, path-length changes occur quicker than thermal
diffusion, so t h a t t h e m e t h o d is faster t h a n t h e r m o
couple calorimetry. However, experimental and com
p u t a t i o n a l complexities h a v e limited w i d e s p r e a d use
of this m e t h o d .
See also: Thermal Analysis: An Overview
Optical
= c/v
Bibliography
Harrington J A, Braunstein M, Rudisill J 1977 Measuring
the infrared absorption in thin film coatings. Appl. Opt.
16: 2843-6
Hass 1978 Measurement of very low optical absorption
coefficients in bulk materials. Opt. Eng. 17: 525-9
Hordvik A 1977 Measurement techniques for small absorp
tion coefficients: recent advances. Appl. Opt. 16: 2827-33
Klein 1981 Techniques for measuring absorption coeffi
cients in crystalline materials. Opt. Eng. 20: 790-4
Rosenstock H, Hass M, Gregory D A, Harrington J A 1977
Analysis of laser calorimetric data. Appl. Opt. 16: 2837-42
J. A . H a r r i n g t o n
[Hughes Research Laboratories,
M a l i b u , California, U S A ]
Spectra
Ex=
hv
(1)
Spectroscopy
(2)
w h e r e E2 a n d Ex a r e t h e energies of the u p p e r a n d
lower energy levels, respectively, h is P l a n c k ' s c o n
s t a n t , c is t h e speed of light, is frequency a n d is
w a v e l e n g t h . T h e speed of light d e p e n d s u p o n the
refractive index of t h e m e d i u m ; c is greater in a
v a c u u m t h a n in air a n d c o n s e q u e n t l y so is .
E a c h element h a s a u n i q u e set of electronic energy
levels a n d h e n c e emits a line s p e c t r u m u n i q u e to t h a t
element. T h i s m e a n s t h a t line spectra c a n be used for
element identification. Several extensive t a b u l a t i o n s
of line s p e c t r a a r e available a n d a r e widely used for
identifying spectral lines.
2.
1. Origin of
Emission
Spectrometers
T h e m a j o r c o m p o n e n t s of a n emission s p e c t r o m e t e r
a r e t h e e n t r a n c e a n d exit slits, t h e light-dispersing
e l e m e n t (grating o r p r i s m ) a n d t h e d e t e c t o r . M o d e r n
spectrometers incorporate computers and/or micro
p r o c e s s o r s for i n s t r u m e n t c o n t r o l a n d d a t a h a n d l i n g .
In s p e c t r o m e t e r s used below a b o u t 200 n m , the
optical p a t h is u n d e r v a c u u m .
A n emission s p e c t r o m e t e r receives light from a
s o u r c e a n d spatially resolves it i n t o its c o m p o n e n t
w a v e l e n g t h s . W a v e l e n g t h r e s o l u t i o n c a n be a c c o m
plished either w i t h a p r i s m o r with a diffraction
g r a t i n g . Light travelling t h r o u g h a p r i s m is refracted,
t h a t is, its direction c h a n g e s a c c o r d i n g t o Snell's law
a n d is d e p e n d e n t u p o n its refractive index in t h e p r i s m
m a t e r i a l . Light of s h o r t e r w a v e l e n g t h s is refracted
m o r e t h a n l o n g e r - w a v e l e n g t h light, which results in
spatial s e p a r a t i o n of t h e w a v e l e n g t h c o m p o n e n t s . A t
long wavelengths, resolution becomes poor. Most
m o d e r n emission s p e c t r o m e t e r s use reflection gratings
instead of p r i s m s ; h o w e v e r , p r i s m s a r e used in s o m e
s p e c t r o m e t e r s in c o n j u n c t i o n with g r a t i n g s as o r d e r
sorters (the p r i s m a n d g r a t i n g disperse light in per
p e n d i c u l a r directions a n d f o r m a t w o - d i m e n s i o n a l
spectrum).
A reflection g r a t i n g is a set of parallel e q u i d i s t a n t
g r o o v e s o n a reflective surface, usually a m e t a l c o a t i n g
o n a glass b l a n k . B o t h m e c h a n i c a l l y ruled a n d
h o l o g r a p h i c a l l y r e c o r d e d g r a t i n g s a r e used in spec
t r o m e t e r s . T h e surface of t h e g r a t i n g b l a n k c a n be
either p l a n e o r spherical (concave).
L i g h t is diffracted by a g r a t i n g a c c o r d i n g to
= a(sin + sin )
(3)
w h e r e is t h e angle b e t w e e n t h e incident b e a m a n d
t h e g r a t i n g n o r m a l , is t h e angle b e t w e e n the dif
fracted b e a m a n d t h e g r a t i n g n o r m a l , a is the g r o o v e
s p a c i n g a n d is a n integer (the o r d e r of the s p e c t r u m ) .
Light of a given w a v e l e n g t h will be diffracted only in
t h o s e d i r e c t i o n s t h a t satisfy E q n . (3). Light of a n o t h e r
w a v e l e n g t h will a p p e a r a t a different set of angles;
t h u s t h e c o m p o n e n t s of light from t h e source are
spatially resolved.
281
Optical
Emission
Spectroscopy
Grating
Grating
normal
Figure 1
Paschen-Runge mounting of a concave grating:
A, primary slit; B, secondary slit
S p e c t r o m e t e r s c a n be classified as s i m u l t a n e o u s
(multichannel) o r sequential (single-channel, scan
ning). Sequential s p e c t r o m e t e r s a r e analytically useful
only with emission sources t h a t a r e stable over l o n g
p e r i o d s of time, such as flames a n d the inductively
c o u p l e d p l a s m a . M u l t i c h a n n e l i n s t r u m e n t s a r e used
with all emission sources. F i g u r e 1 s h o w s a simplified
optical d i a g r a m of t h e P a s c h e n - R u n g e m o u n t i n g , the
m o s t c o m m o n l y used a r r a n g e m e n t in m u l t i c h a n n e l
s p e c t r o m e t e r s : a c o n c a v e g r a t i n g is located with its
apex o n a circle (the R o w l a n d circle). T h e p r i m a r y slit
a n d s e c o n d a r y slits also lie o n t h e R o w l a n d circle.
Light from t h e emission source enters t h e spec
t r o m e t e r t h r o u g h the p r i m a r y slit A . T h e light is
dispersed by the g r a t i n g a n d focused a t the R o w l a n d
circle. E a c h diffracted w a v e l e n g t h forms a n i m a g e of
the p r i m a r y slit. A n a r r a y of s e c o n d a r y slits a l o n g
with a slit m a s k o r a set of baffles isolates t h o s e
wavelengths t h a t a r e desired for the analysis. Behind
e a c h s e c o n d a r y slit is a p h o t o m u l t i p l i e r t u b e t o c o n
vert light i n t o a n electrical signal, which is processed
by a m i n i c o m p u t e r o r a m i c r o p r o c e s s o r a n d c o n
verted i n t o c o n c e n t r a t i o n units.
F i g u r e 2 s h o w s a n optical d i a g r a m of a singlec h a n n e l s p e c t r o m e t e r b a s e d u p o n the C z e r n y - T u r n e r
m o u n t i n g , the m o s t p o p u l a r p l a n e - g r a t i n g m o u n t i n g .
W a v e l e n g t h s a r e selected by r o t a t i n g t h e g r a t i n g
a b o u t t h e axis A . I n m o d e r n m o n o c h r o m a t o r s , g r a t
ing r o t a t i o n is c o n t r o l l e d b y a c o m p u t e r . T h e sepa
r a t i o n b e t w e e n w a v e l e n g t h s (/dx), t h e reciprocal
linear dispersion, is given by
dk/dx = (a/nf)
282
cos
(4)
w h e r e / i s t h e focal length of t h e s p e c t r o m e t e r a n d is
t h e distance a l o n g t h e focal c u r v e . R e c i p r o c a l linear
- 1
1
dispersion is expressed in A m m
or n m m m ;
smaller values represent greater w a v e l e n g t h sepa
r a t i o n . E q u a t i o n (4) s h o w s t h a t larger values of
(higher spectral o r d e r s ) p r o d u c e greater w a v e l e n g t h
s e p a r a t i o n ; for this r e a s o n it is often a d v a n t a g e o u s t o
m a k e m e a s u r e m e n t s in higher o r d e r s to minimize the
interference c a u s e d by spectral lines close t o the
analysis line. T h e practical r e s o l u t i o n of a spec
t r o m e t e r is d e t e r m i n e d by t h e b a n d p a s s , which is
the p r o d u c t of the s e c o n d a r y slit w i d t h a n d dXjdx.
Light of a given w a v e l e n g t h m a y be diffracted i n t o
m o r e t h a n o n e o r d e r . Blazed gratings a r e gratings
w h o s e g r o o v e s a r e s h a p e d in such a w a y t h a t m o s t of
t h e light of a given w a v e l e n g t h is diffracted i n t o a
single o r d e r so t h a t t h e light is used m o s t efficiently. If
a g r a t i n g is blazed a t in t h e first o r d e r , it is blazed a t
/ in the nth o r d e r .
T h e m o s t c o m m o n l y used d e t e c t o r s in emission
spectrometers are photomultiplier tubes. These con
sist of a p h o t o c a t h o d e , a n electron multiplier section
( d y n o d e s ) a n d a n electron collector ( a n o d e ) , all
enclosed in a v a c u u m t u b e . In a m u l t i c h a n n e l spec
t r o m e t e r , different types of p h o t o m u l t i p l i e r t u b e s
c a n be used, o p t i m a l for e a c h spectral region. P h o t o
8
multiplier t u b e s h a v e a large d y n a m i c r a n g e (10 ), a
5
8
high amplification factor ( 1 0 - 1 0 ) a n d fast r e s p o n s e .
A l s o of interest, b u t n o t yet widely used, a r e
photodiode array detectors. A n array can contain u p
to 2000 d i o d e s in 10 m m a n d c a n be m o u n t e d in the
Figure 2
Czerny-Turner mounting of a plane grating: A, axis of
rotation of the grating perpendicular to the plane of the
figure; B, primary slit; C, secondary slit; D, collimating
mirror; E, focusing mirror
Optical
3. Emission
3.1
Sources
Flames
Emission
Spectroscopy
Flames
283
Optical
Emission
Spectroscopy
Arcs
284
a n o d e . I n m a n y a p p l i c a t i o n s a carrier such as A g C l o r
L i F is a d d e d t o t h e s a m p l e t o m a k e the v a p o r i z a t i o n
process s m o o t h e r a n d m o r e r e p r o d u c i b l e . T h e carrier
m a y facilitate t h e volatilization of t h e entire s a m p l e ,
o r it m a y p r o m o t e fractional volatilization of a n a l y t e
elements from a m a t r i x , in w h i c h case t h e t e c h n i q u e is
called carrier distillation.
A r c spectra consist p r i m a r i l y of n e u t r a l a t o m lines.
L a r g e a m o u n t s of s a m p l e a r e v a p o r i z e d , hence sensi
tivity is high, m a k i n g the a r c a useful s o u r c e for trace
analysis. Since arcs t e n d to w a n d e r a n d flicker, r e p r o
ducibilities are p o o r c o m p a r e d with t h o s e of o t h e r
light sources. T h e relative precision is s e l d o m b e t t e r
t h a n 5 % ; typical detection limits a r e 0.01-1 p p m .
Selective volatilization of a n a l y t e elements is a n
i m p o r t a n t p h e n o m e n o n in arcs. T h e spectra of m o r e
volatile elements a p p e a r s o o n e r t h a n t h o s e of less
volatile elements; therefore, i n t e g r a t i o n times m u s t be
carefully c h o s e n so t h a t t h e intensity of each a n a l y t e
element is m e a s u r e d w h e n it is greatest. Volatile
c o m p o u n d s such as c a r b o n a t e s a n d halides of t h e
alkalis, m e r c u r y , lead, zinc, c a d m i u m a n d t h a l l i u m
a p p e a r in t h e a r c s o o n after ignition; they b e c o m e
depleted from t h e s a m p l e a n d their spectra d i s a p p e a r .
N e x t a r e m e t a l s of i n t e r m e d i a t e volatility, such as
i r o n , nickel, m a n g a n e s e , c h r o m i u m a n d v a n a d i u m ,
which r e m a i n in t h e a r c c o l u m n longer. A t h i r d
g r o u p consists of refractory m e t a l s t h a t a r e c o m
pletely volatilized from t h e s a m p l e only w h e n they a r e
at low c o n c e n t r a t i o n s . T h i s g r o u p includes t h o r i u m ,
t u n g s t e n , u r a n i u m , n i o b i u m , t a n t a l u m , t i t a n i u m , zir
c o n i u m , h a f n i u m a n d m o l y b d e n u m , which form car
bides a n d c a n n o t be completely volatilized within
useful b u r n times.
A l t e r n a t i n g - c u r r e n t arcs a r e used occasionally.
Selective volatilization is lower a n d reproducibility is
better t h a n with d c arcs.
3.4 Electric
Spark
T h e a c s p a r k is t h e m o s t i m p o r t a n t source used for t h e
analysis of m e t a l s . In c o n t r a s t t o arcs, s p a r k s a r e
i n t e r m i t t e n t r a t h e r t h a n c o n t i n u o u s discharges. T h e
t e r m i n o l o g y for t h e v a r i o u s types of discharges is
confusing b u t , in general, s p a r k s a r e differentiated
from arcs by their m u c h higher c u r r e n t s a n d voltages
at b r e a k d o w n . H i g h - v o l t a g e s p a r k s initiate a t 10 0 0 0 50 000 V. N o w a d a y s , low-voltage s p a r k sources with
solid-state p o w e r supplies a r e m o r e c o m m o n ; these
sources o p e r a t e a t 3 0 0 - 1 0 0 0 V. ( T h e p e a k c u r r e n t a t
b r e a k d o w n m a y be several h u n d r e d a m p e r e s . ) T h e
high p o w e r c o n v e r s i o n in t h e s p a r k g a p causes a n
explosive v a p o r i z a t i o n of m a t e r i a l from the elec
t r o d e s . T h e a m o u n t of m a t e r i a l v a p o r i z e d is smaller
t h a n in a n arc. T h e electronic excitation is greater a n d
c o n s e q u e n t l y m o r e lines (ion lines as well as n e u t r a l a t o m lines) a p p e a r in s p a r k spectra. D e t e c t i o n limits
( 1 - 1 0 p p m ) a r e p o o r e r t h a n in t h e d c arc; o n the o t h e r
h a n d , t h e s p a r k is a better s o u r c e for d e t e r m i n i n g high
c o n c e n t r a t i o n s of elements. Typical precision (relative
Optical
s t a n d a r d d e v i a t i o n ) a t high c o n c e n t r a t i o n s is 0 . 5 - 1 % ,
which is far s u p e r i o r t o t h e best precision achievable
in a n a r c . Selective volatilization is n o t as g r e a t a
p r o b l e m in t h e s p a r k .
A s p a r k is p r o d u c e d b y c h a r g i n g a c a p a c i t o r t o the
b r e a k d o w n voltage of t h e analytical g a p . M o r e t h a n
o n e b r e a k d o w n c a n o c c u r p e r half-cycle of c h a r g i n g
c u r r e n t . In o r d e r t o o b t a i n m o r e u n i f o r m excitation
a n d better reproducibility, a c o n t r o l l e d s p a r k is used.
A c o n t r o l l e d - s p a r k circuit c o n t a i n s a device t h a t
allows only o n e b r e a k d o w n of t h e analytical g a p p e r
half-cycle, with t h e b r e a k d o w n o c c u r r i n g a t the s a m e
p o i n t in e a c h half-cycle. O n e such device is a n auxili
ary r o t a t i n g g a p driven b y a s y n c h r o n o u s m o t o r ; t h e
auxiliary g a p is closed only a t t h e p e a k of e a c h halfcycle. I n n e w e r i n s t r u m e n t s , pulse t r a n s f o r m e r s a n d
timing circuits c o n t r o l t h e b r e a k d o w n of t h e a n a l y t i
cal g a p .
A s p a r k s o u r c e is c o m m o n l y o p e r a t e d in a n i t r o g e n
or a n a r g o n a t m o s p h e r e b e c a u s e t h e exclusion of
oxygen i m p r o v e s reproducibility. I n a d d i t i o n , n i t r o
gen a n d a r g o n a r e t r a n s p a r e n t in t h e spectral region
below 200 n m t h a t includes sensitive lines of p h o s
p h o r u s , tin, selenium, arsenic a n d b o r o n .
M e t a l s a m p l e s for analysis b y s p a r k excitation c a n
be in the f o r m of r o d s o r disks cast in chill m o l d s .
S a m p l e s t a k e n from a melt m u s t be c o o l e d r a p i d l y t o
ensure h o m o g e n e i t y ; o t h e r w i s e segregation of p h a s e s
within t h e s a m p l e will c a u s e p o o r precision a n d p o o r
accuracy. R e m e l t i n g is s o m e t i m e s used t o h o m o g e n i z e
samples p r i o r t o analysis. Before m e a s u r i n g intensit
ies, p r e s p a r k i n g in t h e s p a r k s t a n d is used for m i c r o melting of t h e s a m p l e t o c o m p e n s a t e for differences in
metallurgical s t r u c t u r e .
A n interesting a p p l i c a t i o n of t h e s p a r k is on-site
m e t a l s identification with a m o b i l e s p e c t r o m e t e r in
salvage, s h i p p i n g o r s t o r a g e y a r d s , as well as o n
p r o d u c t i o n lines. A p o r t a b l e s p a r k pistol is held b y
the o p e r a t o r a g a i n s t t h e s a m p l e , w h i c h c a n be of a n y
size o r s h a p e . L i g h t from t h e s p a r k is transferred t o
the s p e c t r o m e t e r b y a fiber-optics cable several m e t e r s
long.
A device widely used for a n a l y z i n g liquids, b o t h
solutions a n d s u s p e n s i o n s , is t h e r o t a t i n g - d i s k g r a
phite electrode, o r r o t r o d e . T h e r o t a t i n g electrode
picks u p s a m p l e s from a c o n t a i n e r m o u n t e d b e n e a t h it
a n d t r a n s p o r t s t h e m i n t o the s p a r k g a p a b o v e t h e
r o t r o d e . T h i s is the m o s t i m p o r t a n t t e c h n i q u e for
d e t e r m i n i n g w e a r m e t a l s in used engine oils.
T h e s p a r k c a n also b e used t o analyze p o w d e r s .
N o n c o n d u c t i v e p o w d e r s a r e m i x e d with a c o n d u c t i v e
binder, usually g r a p h i t e , a n d pelletized in a press.
A n o t h e r w a y t o t r e a t n o n c o n d u c t i v e p o w d e r s is t o p u t
t h e m o n t o a t a p e t h a t is fed i n t o t h e s p a r k g a p .
3.5 Discharges in Gases Under Reduced
Pressure
T w o sources t h a t a r e n o t widely used in emission
spectroscopy, b u t which a r e receiving increasing at
tention, a r e the h o t h o l l o w - c a t h o d e l a m p ( H C L ) a n d
Emission
Spectroscopy
285
Optical
Emission
Spectroscopy
a n d is limited t o a m a x i m u m magnification of a b o u t
t w e n t y times (20 x ) . T h e c o m p o u n d m i c r o s c o p e
with a useful magnification r a n g e of a few times t o
over 2000 x consists of four c o m p o n e n t s : a light
source, c o n d e n s e r lens, objective lens a n d eyepiece
(ocular) (Fig. 1). T h e c o n d e n s e r collects light rays
from t h e light s o u r c e which a r e focused o n t o the
specimen. T h e objective lens (the lens nearest the
object) forms a real, magnified aerial i m a g e of
t h e object in t h e i n t e r m e d i a t e i m a g e p l a n e . T h i s real
i m a g e is further magnified b y t h e eyepiece t o form t h e
final i m a g e , which c a n be (a) viewed directly in the
eyepiece, (b) projected o n t o a viewing screen o r
p h o t o g r a p h i c film, o r (c) o b s e r v e d b y w a y of a
television system.
Bibliography
Barnes R 1976 Emission Spectroscopy. Dowden, Hut
chinson and Ross, Stroudsburg, PA
Harrison G R (ed.) 1969 Massachusetts Institute of Tech
nology Wavelength Tables, 2nd edn. MIT Press, Cam
bridge, MA
Herzberg G 1944 Atomic Spectra and Atomic Structure, 2nd
edn. Dover Publications, New York
Mavrodineanu R (ed.) 1970 Analytical Flame Spectroscopy.
Macmillan, London
Meggers W F, Corliss C H, Scribner F (eds.) 1975 Tables
of Spectral Line Intensities, 2nd edn. US Department of
Commerce, Washington, DC
Sawyer R A 1963 Experimental Spectroscopy, 3rd edn.
Dover, New York
Slavin 1971 Emission Spectrochemical Analysis. Wiley,
New York
Slickers 1981 Automatic
Emission
Spectroscopy.
Bruhlsche Universitatsdruckerei, Giessen, Germany
Zaidel' A N, Prokof ev V K, Raiskii S M, Slavnyi V A,
Schreider Ya 1970 Tables of Spectral Lines. IFI/
Plenum, New York
H . R. Sobel
[Applied R e s e a r c h L a b o r a t o r i e s ,
S u n l a n d , California, U S A ]
Optical Microscopy
T h e optical (or light) m i c r o s c o p e is a n i n s t r u m e n t t h a t
magnifies a n d resolves the s t r u c t u r e of objects. O b
jects m a y be viewed by either t r a n s m i t t e d o r reflected
light a n d by a selection of i l l u m i n a t i o n m e t h o d s . T h e
optical m i c r o s c o p e is p r o b a b l y t h e single m o s t widely
used i n s t r u m e n t in scientific research, rinding applica
tions in diverse disciplines including m a t e r i a l s science,
m i n e r a l o g y , chemistry, biology, medicine, particle
analysis a n d forensic science.
2. Numerical
Aperture
and
Resolution
1. The
Microscope
T h e m o s t e l e m e n t a r y m i c r o s c o p e is t h e simple m i c r o
scope which e m p l o y s a single lens (magnifying glass)
286
Optical
Microscopy
-~NA
0^2
mL
4. Objective-Lens
Figure 1
Ray paths and optical component locations for
(a) transmitted light, and (b) reflected light microscopes:
1, light source; 2, field diaphragm; 3, condenser lens;
4, substage condenser; 5, object (specimen); 6, objective
lens; 7, eyepiece (ocular); 8, coarse focus; 9, fine focus; and
10, aperture diaphragm (courtesy of E. Leitz)
3.
Magnification
Aberrations
Optical
Microscopy
5. Depth
of Field
A n o t h e r i m p o r t a n t p a r a m e t e r in a n y type of m i c r o s
copy is t h a t of d e p t h of field ( D O F ) , w h i c h c a n b e
d e n n e d as t h e axial d i s t a n c e in object space over
which object detail is in a c c e p t a b l e focus for a given
setting of the lens focus. T h e d e p t h of field of the light
m i c r o s c o p e is r a t h e r limited, p a r t i c u l a r l y a t t h e higher
magnifications ( N A s ) . T h e D O F ( p h o t o g r a p h i c ) is
related t o t h e N A of the objective lens, t h e w a v e l e n g t h
of i l l u m i n a t i o n a n d t h e refractive index of t h e m e d i u m
between t h e object a n d t h e front surface of t h e
objective lens b y t h e r e l a t i o n s h i p ( M c C r o n e et al.
1978):
2
D O F = ( -
NA )
1 / 2
/NA
Table 1
Typical values of photographic depth of field for green
wavelength ( = 0.54 ) illumination
Numerical
aperture
0.25
0.40
0.65
0.95
1.0
1.40
288
Depth of field
()
8
3
1
0.18
0.62
0.16
Lens
system
dry objectives
oil-immersion objectives
6. Field Diaphragm,
Aperture
Kohler
Illumination
Diaphragm
and
A c o m p o u n d light m i c r o s c o p e is fitted w i t h t w o
adjustable iris d i a p h r a g m s , e a c h of which h a s a speci
fic function. T h e field d i a p h r a g m is p o s i t i o n e d in t h e
optical system such t h a t it is i m a g e d in t h e p l a n e of t h e
specimen. T h e r e f o r e , t h e silhouette of t h e d i a p h r a g m
c a n b e o b s e r v e d s i m u l t a n e o u s l y with t h e focused
object i m a g e . T h e principal role of t h e field d i a p h
r a g m is t o i m p r o v e i m a g e c o n t r a s t b y t h e r e d u c t i o n of
internal glare in t h e optical system. It s h o u l d b e
s t o p p e d d o w n t o confine t h e d i a m e t e r o f i r r a d i a t i o n
t o only t h a t a r e a of t h e object u n d e r o b s e r v a t i o n o r
t h a t w h i c h is t o b e p h o t o g r a p h e d . T h e setting of this
d i a p h r a g m h a s n o effect o n t h e b r i g h t n e s s of t h e
object i m a g e .
T h e a p e r t u r e d i a p h r a g m is i m a g e d in t h e b a c k focal
p l a n e of t h e objective lens a n d c o n t r o l s t h e d i a m e t e r
of t h e c o n e of light t h a t enters t h e lens. T h e p r o p e r
a d j u s t m e n t of this d i a p h r a g m is essential t o t h e a t t a i n
m e n t of o p t i m u m c o n t r a s t a n d resolution. T h e i m a g e
of this d i a p h r a g m a n d t h e b a c k focal p l a n e of t h e
objectivecan b e o b s e r v e d b y l o o k i n g i n t o t h e m i c r o
scope t u b e with t h e eyepiece r e m o v e d after t h e object
h a s been focused. T h e o p t i m u m setting of this d i a p h
r a g m is a c o m p r o m i s e ; h o w e v e r , it is generally r e c o m
mended that the aperture diaphragm be stopped
d o w n t o 8 0 - 9 0 % of t h e a p e r t u r e of t h e objective lens.
A l a r g e r - d i a m e t e r setting results in e x t r a n e o u s flare in
t h e system, w h e r e a s a smaller d i a m e t e r results in
r e d u c t i o n of t h e effective N A of t h e objective lens.
Since t h e d i a p h r a g m affects t h e brightness of t h e final
i m a g e , it is c o m m o n l y i m p r o p e r l y used t o adjust light
levels t o t h e d e t r i m e n t of i m a g e quality. B o t h t h e field
a n d a p e r t u r e d i a p h r a g m s h a v e p r o v i s i o n for centering
on most microscopes.
M o s t m i c r o s c o p e s a r e e q u i p p e d t o follow t h e
Kohler principle of i l l u m i n a t i o n , which p r o v i d e s a
very uniformly illuminated field of view even with a
n o n u n i f o r m light source such a s a coiled-filament
i n c a n d e s c e n t l a m p . Kohler i l l u m i n a t i o n is o b t a i n e d
by a d j u s t m e n t of t h e l a m p c o n d e n s e r t o focus t h e
i m a g e of t h e light source o n t o t h e p l a n e of t h e
aperture diaphragm.
7. Microscope
Types
Optical
inverted-stage (Le C h a t e l i e r - t y p e ) m o d e l s . O f t h e
m a n y different k i n d s of l i g h t - m i c r o s c o p y i m a g i n g
techniques t h a t a r e available, discussion h e r e is
limited t o t h o s e t h a t h a v e significant a p p l i c a t i o n in
m a t e r i a l s science; n a m e l y , b r i g h t field, d a r k field,
polarized, interference c o n t r a s t , a n d t w o - b e a m a n d
m u l t i p l e - b e a m interference.
7.1 Bright-Field
Illumination
By far t h e m o s t c o m m o n l y used i m a g i n g t e c h n i q u e in
light m i c r o s c o p y is bright-field i l l u m i n a t i o n in which
the illuminating b e a m is a solid c o n e of light focused
o n t o t h e specimen b y a c o n d e n s e r - l e n s system either
in t r a n s m i s s i o n o r b y reflection. T h e light m a y be
unfiltered w h i t e light o r m o n o c h r o m a t i c . T h e
m e c h a n i s m of i m a g e c o n t r a s t is b y a b s o r p t i o n o r b y
scattering. In t r a n s m i s s i o n , bright-field light m i c r o s
c o p y is effective in t h e s t u d y of p a r t i c u l a t e m a t t e r
(dispersions) as well as t h e m i c r o s t r u c t u r a l c h a r a c t e r i
z a t i o n of glasses, c e r a m i c s a n d plastics in thin section.
Reflected bright-field i l l u m i n a t i o n is t h e m o s t c o m
m o n m e t h o d used t o s t u d y t h e m i c r o s t r u c t u r e of
polished a n d e t c h e d m e t a l s ( m e t a l l o g r a p h y ) a n d cera
mics ( c e r a m o g r a p h y ) a n d surface s t r u c t u r e s in
general.
7.2 Dark-Field (or Dark-Ground)
Illumination
In bright-field m i c r o s c o p y m o s t of t h e light from t h e
c o n d e n s e r lens enters t h e objective lensafter inter
acting with t h e o b j e c t t o p a r t i c i p a t e in i m a g e f o r m a
tion. T h i s system generally results in a n i m a g e w i t h a
b r i g h t field o r b a c k g r o u n d . T h e c o n d e n s i n g system
for dark-field i l l u m i n a t i o n utilizes a central circular
disk s t o p t h a t p r e v e n t s direct c o n d e n s e r r a y s from
entering t h e objective lens. O n l y t h o s e r a y s t h a t h a v e
been suitably scattered b y t h e object (by reflection,
refraction o r diffraction) e n t e r t h e objective lens t o
g e n e r a t e t h e final i m a g e . Object detail responsible for
the scattering a p p e a r s b r i g h t o n a d a r k b a c k g r o u n d o r
field. I n t h e t r a n s m i s s i o n m o d e , this system of illumi
n a t i o n finds useful a p p l i c a t i o n in t h e s t u d y of m a t e r
ials of low c o n t r a s t b u t w h i c h scatter l i g h t s u c h as
small particles o r i n t e r n a l inclusions a n d p o r e s in thin
sections. I n c i d e n t dark-field i l l u m i n a t i o n c a n often
p r o v i d e i m p r o v e d i m a g e c o n t r a s t over bright-field
m e t h o d s o n specimens with t o p o g r a p h i c a l irregulari
ties, such as etched m e t a l l o g r a p h i c a n d c e r a m o g r a p h i c specimens a n d i n t e g r a t e d circuits.
7.3 Polarized-Light
Illumination
Polarized-light m i c r o s c o p y is used in either t r a n s m i t
ted or reflected light for t h e q u a n t i t a t i v e o r q u a l i t a t i v e
c h a r a c t e r i z a t i o n a n d identification of optically a n i s o
t r o p i c m a t e r i a l s . A c o n v e n t i o n a l light m i c r o s c o p e c a n
be c o n v e r t e d i n t o a p o l a r i z i n g m i c r o s c o p e by placing
t w o p o l a r i z i n g elements in t h e optical system. T h e
first polarizer is l o c a t e d b e t w e e n t h e light s o u r c e a n d
the object p l a n e a n d c o n v e r t s u n p o l a r i z e d light i n t o
Microscopy
289
Optical
Microscopy
R e f e r e n c e mirror
Figure 2
Schematic arrangement of two-beam reflection interference
microscope. A condenser lens directs a parallel beam of
light from a monochromatic source onto a beam-splitting
prism where two coherent light beams are formed.
Separate images are formed of the specimen surface and a
reference mirror by matched objective lenses. These
images are then combined by the beam splitter, resulting
in a magnified interference pattern that is viewed through
the eyepiece
Figure 3
Schematic visualization of two-beam fringes arising from
intersection of a set of parallel, equispaced planes with the
specimen surface (courtesy of Carl Zeiss Inc.)
290
Figure 4
Comparison of fringe patterns obtained by: (a) two-beam,
and (b) multiple-beam interference microscopy; (a) shows
furrows on the surface of InSb resulting from parallel melt
traces made by a scanning laser, and (b) shows the surface
of a directionally solidified AlCu thin film
Figure 5
Schematic representation of double-beam reflection
differential interference contrast optical configuration
(courtesy of Carl Zeiss Inc.)
Optical
(b) Interference-contrast
microscopy.
A n u m b e r of
different interference-contrast systems a r e e x t a n t .
P r o b a b l y the m o s t widely used system is N o m a r s k i
differential interference-contrast ( D I C ) m i c r o s c o p y
( N o m a r s k i a n d Weill 1954, 1955). It is a n extremely
sensitive i m a g e - e n h a n c e m e n t t e c h n i q u e t h a t utilizes
the interference c o n d i t i o n s g e n e r a t e d by o p t i c a l - p a t h length differences of t w o b e a m s of c o h e r e n t p o l a r i z e d
light a n d r e n d e r s visible object detail t h a t is generally
n o t revealed by o t h e r light optical m e t h o d s . T h e
technique h a s n u m e r o u s diverse a p p l i c a t i o n s in reflec
tion a n d t r a n s m i s s i o n a n d c a n be used in b o t h blacka n d - w h i t e a n d c o l o r c o n t r a s t m o d e s ( H o l i k 1975).
In the reflection m o d e , i n c o m i n g p l a n e - p o l a r i z e d
light interacts with a birefringent p r i s m (modified
W o l l a s t o n p r i s m , after N o m a r s k i ) , which s e p a r a t e s
the polarized light i n t o t w o w a v e fronts of similar
intensities a n d v i b r a t i n g in m u t u a l l y p e r p e n d i c u l a r
planes (Fig. 5). T h e t w o c o h e r e n t p o l a r i z e d b e a m s a r e
in p h a s e a n d their lateral s e p a r a t i o n is s o m e w h a t less
t h a n the resolving p o w e r of t h e p a r t i c u l a r objective
lens used. T h e s e t w o parallel a n d p o l a r i z e d b e a m s a r e
reflected from t h e specimen surface, i m a g e d b y t h e
objective lens a n d r e c o m b i n e d b y the W o l l a s t o n p r i s m
a n d analyzer, t h e r e b y c r e a t i n g a n interference c o n
dition. P h a s e differentials b e t w e e n reflected w a v e
fronts arising from surface irregularities, o r reflection
p h a s e shifts, result in final-image interference c o n
trast. Interference-contrast i m a g e s o b t a i n e d by this
technique have a unique three-dimensional appear
ance d u e t o different light intensities o n o p p o s i t e sides
of t o p o g r a p h i c a l features. T h i s effect is often helpful
t o the m i c r o s c o p i s t in the i n t e r p r e t a t i o n of surface
structures. U n d e r favorable c o n d i t i o n s , the D I C tech
n i q u e is c a p a b l e of revealing surface irregularities of
the o r d e r of a few t e n t h s of a n a n o m e t e r , b u t , of
Microscopy
Figure 7
Mechanically polished, unetched, aluminum oxide
ceramic: (a) bright-field illumination, and
(b) differential-interference-contrast illumination
Bibliography
Figure 6
Polished and chemically etched aluminum alloy
(hydrofluoric acid: water 1:99): (a) bright-field
illumination, and (b) differential-interference-contrast
illumination
291
Optical
Microscopy
Accelerating and
focusing region
A . S. H o l i k
[General Electric C o r p o r a t e R e s e a r c h
and Development, Schenectady,
New York, USA]
7.
Instrumentation
F i g u r e 1 s h o w s a typical m a s s s p e c t r o m e t e r . T h e
r e a d e r s h o u l d be a w a r e , h o w e v e r , t h a t there a r e a
variety of i o n i z a t i o n , ion s e p a r a t i o n a n d r e c o r d i n g
m e t h o d s , each with its o w n u n i q u e a d v a n t a g e s . F o r
further insight, Kiser (1965) p r o v i d e s a c o m p r e h e n
sive discussion of the i n s t r u m e n t a t i o n a n d principles
of m a s s s p e c t r o m e t r y . Since the wide scope of o r g a n i c
m a s s s p e c t r o m e t r y is d u e in large p a r t t o t h e variety of
sample i n t r o d u c t i o n a n d ionization t e c h n i q u e s , t h e
m o r e i m p o r t a n t of these will be discussed in t h e
following.
I o n i z a t i o n of the s a m p l e is a c c o m p l i s h e d u n d e r
5
7
v a c u u m ( 1 0 " - 1 0 " m m H g ) , so t h a t the ions f o r m e d
292
Mill III
nil.
Mass (/77/e)
\
Mass spectrum
Figure 1
Simplified diagram of a mass spectrometer
h a v e relatively l o n g m e a n free p a t h s a n d c a n be
accelerated a n d m a n i p u l a t e d by electric a n d m a g n e t i c
fields to achieve t h e desired m a s s s e p a r a t i o n . T h e
simple m a s s s p e c t r o m e t e r depicted in Fig. 1 illustrates
a gaseous sample entering an electron-bombardment
ion source. H i g h - e n e r g y electrons strike the m o l
ecules, c a u s i n g the ejection of electrons to p r o d u c e
positively c h a r g e d m o l e c u l a r ions, s o m e of which
dissociate t o p r o d u c e fragment ions of lower m a s s (see
Fig. 2). T h e positively c h a r g e d ions a r e repelled from
the s o u r c e b y a small positive voltage, a n d a r e acceler
a t e d by p a s s i n g t h r o u g h a high-voltage field.
O n e n t e r i n g a m a g n e t i c field, t h e ions a r e deflected
in a circular p a t h w h i c h is d e p e n d e n t u p o n t h e m a s s of
t h e ion a n d t h e s t r e n g t h of t h e m a g n e t i c field. I o n s of
a n a p p r o p r i a t e m a s s follow t h e p a t h leading t o t h e
d e t e c t o r . A m a s s s p e c t r u m is o b t a i n e d by c h a n g i n g
the m a g n e t i c field s t r e n g t h t o successively focus ions
of high t o low m a s s o n the detector.
E l e c t r o n b o m b a r d m e n t is the m o s t c o m m o n l y used
m e t h o d of ionization. T h i s relatively h a r s h m e t h o d
yields a great deal of s t r u c t u r a l i n f o r m a t i o n in the
fragment ions f o r m e d b y dissociation of t h e m o l e c u l a r
Energy from
Figure 2
Production of molecular and fragment ions in a mass
spectrometer
Organic
Spectrum
A m a s s s p e c t r u m is a r e c o r d of t h e m a s s e s a n d relative
a b u n d a n c e s of t h e i o n s f o r m e d from a p a r t i c u l a r
c o m p o u n d . T h e m a s s s p e c t r u m m a y be p r e s e n t e d in
the form of a b a r g r a p h o r a m a s s a n d a b u n d a n c e
table. W h e n t h e general a p p e a r a n c e of a s p e c t r u m is
a n i m p o r t a n t factor in i n t e r p r e t a t i o n , o r w h e n c o m
p a r i n g spectra, t h e b a r g r a p h is preferred. T h e table
offers the a d v a n t a g e of a c c u r a t e i o n - a b u n d a n c e
presentation.
A s first o b s e r v e d b y T h o m s o n , m o s t e l e m e n t s a r e
m i x t u r e s of t w o o r m o r e stable i s o t o p e s differing b y
one or two atomic mass units. Table 1 contains the
elements c o m m o n l y f o u n d in o r g a n i c c o m p o u n d s
a n d t h e relative a b u n d a n c e s of their i s o t o p e s . O f
these, only fluorine, p h o s p h o r u s a n d i o d i n e a r e m o n o isotopic. Since t h e i o n s f o r m e d from a m o l e c u l e a r e
s e p a r a t e d a c c o r d i n g t o their m a s s e s , e a c h i s o t o p e
yields a separately identifiable ion. F o r e x a m p l e , t h e
m o l e c u l a r ion of ethyl c h l o r i d e is revealed as t w o
p e a k s s e p a r a t e d b y t w o a t o m i c m a s s u n i t s (Fig. 3a)
a n d with a n intensity r a t i o c o r r e s p o n d i n g t o t h e
relative a b u n d a n c e s of t h e t w o i s o t o p e s (3:1). T h e
higher-mass p e a k of this d o u b l e t is called t h e + 2
3 7
i s o t o p e p e a k , a n d c o r r e s p o n d s t o C 2H 5 C 1 . S u c h a
pair of p e a k s is therefore characteristic of o n e c h l o r
ine a t o m in a molecule. Likewise, a m o l e c u l a r ion
c o n t a i n i n g b r o m i n e a p p e a r s as t w o p e a k s s e p a r a t e d
Mass
Spectrometry
Table 1
Elements commonly found in organic compounds
Element
Hydrogen
Carbon
Nitrogen
Nuclide
D
C
13
C
Atomic
weight
Exact
mass
Relative
abundance
1.00797
1.00783
2.01410
12.00000
13.00336
14.0031
15.0001
15.9949
16.9991
17.9992
18.9984
27.9769
28.9765
29.9738
30.974
31.9721
32.9715
33.9679
34.9689
36.9659
78.9183
80.9163
126.904
99.99
0.01
98.90
1.10
99.60
0.40
99.76
0.04
0.20
100.00
92.20
4.70
3.10
100.00
95.02
0.76
4.22
75.77
24.23
50.50
49.50
100.00
12.01115
14.0067
1 5N
Oxygen
15.9994
1 8Q
Fluorine
Silicon
Phosphorus
Sulfur
F
Si
Si
30
Si
S
33
S
29
18.9984
28.086
30.974
32.064
3 4S
Chlorine
Bromine
Iodine
CI
C1
Br
81
Br
I
37
35.453
79.909
126.904
293
Organic
Mass
Spectrometry
Table 2
Energy values for some bonds commonly found in organic
molecules at 25 C
29
100
80
"O
c
D
>
64
Bond energy
1
(kJg" )
60
Bond type
Single bonds
40
rr
C-H
C-C
C-N
C-O
20
c - s
50
C-Si
C-F
C-Cl
C-Br
C-I
O-H
O-Si
N-H
N-N
N-O
S-H
S-S
m /e
(a)
100
80
60
108
81
40
413
346
305
358
272
285
485
339
285
213
463
372
391
163
222
347
226
Double
bonds
Triple bonds
610
615
749
536
835
890
418
607
20
50
100
m/e
A - B - C - D t - A - B - C
(b)
Figure 3
Mass spectra of (a) ethyl chloride and (b) ethyl bromide
+
: C : C : CI :
CH3
CH
M * , Propylene
Ethyl chloride
C H 2^
+.
^CH
^CH
M * , Butadiene
Figure 4
Odd-electron ions
294
CH
M * f Benzene
CH2
0 + Dt
(1)
Organic
57
100
100
Mass
Spectrometry
43
r-
Q>
c 80
"
c
60
13
.O
>
>
^ 40
20
80 h -
60
"D
C
D
40
72
Li
20
136
_il
50
L
100
50
m/e
m/e
Figure 6
Mass spectrum of 2-butanone
(a)
100
57
15
57
c 60
R - C H - R - R - C H a n d / o r C H - R (4)
60
C H - R - R - C H and/or C H - R
40
+
NH,
: 20 h -
t 50i l
100
m/e
(b)
Figure 5
Mass spectra of (a) 2-bromobutane and (b) teri-butyl
cation
4H,
(5)
'
T h e s p e c t r u m of 2 - b u t a n o n e ( F i g . 6) is representa
tive of f r a g m e n t a t i o n directed b y t h e presence of a
heteroatom.
T h e r e a r e t w o c o m m o n r e a r r a n g e m e n t fragmen
t a t i o n s o b s e r v e d in t h e m a s s spectra of m a n y o r g a n i c
c o m p o u n d s ; b o t h involve t h e transfer of a h y d r o g e n
a t o m . E l i m i n a t i o n f r a g m e n t a t i o n s a r e c o m m o n from
alcohols, a m i n e s , esters, ethers, halides a n d sulfides:
RCH2CH2CH2CHX *
T h e stabilizing influence of d o u b l e b o n d s a n d a r o
m a t i c rings results in preferred cleavage of allylic a n d
benzylic b o n d s :
R.
R C H 2C H 2C H = C H 2* + HX
(6)
w h e r e X = O H , N H 2 , O R , S H o r S R . T h e second
f r a g m e n t a t i o n , k n o w n a s t h e McLafferty r e a r r a n g e
m e n t , o c c u r s from m a n y c o m p o u n d s c o n t a i n i n g
d o u b l e b o n d s a n d aliphatic h y d r o g e n a t o m s situated
in p o s i t i o n s t o give a s i x - m e m b e r e d transfer, a s s h o w n
in E q n . (7):
(2)
H/R'
XH
chr'
(7)
R.
(3)
T h e n o n b o n d i n g electrons of h e t e r o a t o m s a d d n o
table stability t o c a r b o n i u m i o n s , resulting in t h e
c o m m o n -cleavage:
CH
T h e spectra of 2 - h e x a m o n e a n d p h e n e t o l e (Figs. 7a
a n d 7b) d e m o n s t r a t e t h e McLafferty r e a r r a n g e m e n t .
N o t e t h a t 2 - h e x a n o n e also fragments b y simple
cleavage ( F i g . 8).
295
Organic
Mass
100
Spectrometry
43
CH,
CH,
CH
60
"
c
CHX
60
58
tOH
rr
C H
20
57
85
,vv
100
m/e
C = C H
m/e
100
50
C H
= C H
CH
58
85
m/e
(a)
"
C
D
-O
60
40
0)
m/e
94
100
80
122
m/e
94
Figure 8
Fragmentation of 2-hexanone and phenetole
1. J
50
100
m/e
(b)
Figure 7
Mass spectra of (a) 2-hexanone and (b) phenetole
3. Gas Chromatography-Mass
Spectrometry
T h e d e v e l o p m e n t of m a s s s p e c t r o m e t r y d u r i n g t h e
1960s revolutionized t h e field of o r g a n i c analysis, yet
w a s still limited t o the analysis of relatively p u r e
substances. I n t h e 1970s, h o w e v e r , t h e gas c h r o m a t o
g r a p h w a s a d d e d as a n inlet t o t h e m a s s s p e c t r o m e t e r
t o f o r m a n entirely n e w i n s t r u m e n t . W i t h this i n s t r u
m e n t , t h e qualitative p o w e r of t h e m a s s s p e c t r o m e t e r
is a d d e d t o t h e q u a n t i t a t i v e capabilities of t h e gas
chromatograph. Complex mixtures can now be
analyzed b o t h qualitatively a n d q u a n t i t a t i v e l y . G a s
c h r o m a t o g r a p h y - m a s s s p e c t r o m e t r y is a n indispens
able t o o l in t h e fields of forensic a n d e n v i r o n
m e n t a l chemistry, d r u g research, m e d i c i n e , industrial
hygiene, a n d flavors a n d fragrances.
4. High-Resolution
C H 2C H
H f
20 r -
Mass
Spectrometry
296
43
Organic
Mass
Spectrometry
t e c h n i q u e c o m b i n i n g t h r e e distinct analytical m e t h o d s
i n t o o n e . T h e volatile pyrolysis p r o d u c t s a r e swept
o n t o a g a s c h r o m a t o g r a p h y c o l u m n t o be analtically
s e p a r a t e d , identified a n d m e a s u r e d by t h e m a s s
s p e c t r o m e t e r . T h i s t e c h n i q u e h a s its p r i m a r y applica
t i o n in t h e identification of t h e c o m b u s t i o n p r o d u c t s
of p o l y m e r s . I n this case, air is p a s s e d t h r o u g h the
pyrolysis c h a m b e r while t h e s a m p l e is h e a t e d t o 1 5 0 0 2000 C.
5. Pyrolysis-Mass
Bibliography
Spectrometry
6. Quantitative
Mass
Spectrometry
T h e m a s s s p e c t r o m e t e r c a n b e a very powerful q u a n t i
tative t o o l . Its i n h e r e n t function as a m a s s analyzer
offers t h e a n a l y s t t h e ability t o use stable-isotopelabelled i n t e r n a l s t a n d a r d s . Since c a r b o n is t h e p r e
1 3
d o m i n a n t element in o r g a n i c c o m p o u n d s , C is t h e
2
m o s t c o m m o n s t a b l e - i s o t o p e t a g . T h e use of H - a n d
18
0 - l a b e l l e d c o m p o u n d s is also c o m m o n . A n a l o g u e s
a n d h o m o l o g u e s a r e u s e d as i n t e r n a l s t a n d a r d s w h e n
t h e a p p r o p r i a t e stable-isotope-labelled c o m p o u n d s
a r e n o t available.
See also: Gas and Liquid Chromatography; Laser Micro
probe Mass Spectrometry; Laser Sampling Inductively
Coupled Plasma Mass Spectrometry
297
Paper and Paperboard: Destructive
Mechanical Testing
T h e p r i m a r y m e c h a n i c a l p r o p e r t i e s of p a p e r t h a t a r e
tested destructively a r e (a) its uniaxial l o a d - e l o n g a
tion ( L E ) characteristics; (b) its " b u r s t i n g s t r e n g t h , " a
kind of o m n i d i r e c t i o n a l tensile test; a n d (c) its " t e a r
ing s t r e n g t h , " a failure-line p r o p a g a t i o n test. T h e s e
three p r o p e r t i e s will be e x a m i n e d in this article in
t e r m s of the relevant fiber p r o p e r t i e s a n d p r o c e s s
variables. N o n d e s t r u c t i v e e v a l u a t i o n of p a p e r is
considered in t h e article Paper and Paperboard:
Non
destructive
Evaluation.
1. Load-Elongation
Characteristics
CD
MD
Elongation
Figure 1
Fiber load-elongation curves: fibril
orientation
e
(a) "parallel" to fiber axis, (b)-( ) at large angle to
fiber axis; drying conditions: (a) free or restrained,
(b) restrained, (c) free, (d) and (e) microcompressions
A r e a of
bonding
Figure 2
Mutually perpendicular partly boned fibers; MD, machine
direction; CD, cross direction; shading denotes bonded
area
299
Paper
and Paperboard:
Destructive
Mechanical
Testing
the L E c u r v e a n d its m i c r o c o m p r e s s i o n c o n t e n t
is a function of fiber o r i e n t a t i o n in a sheet.
Elongation
Figure 3
Paper load-elongation curves: (a) sheet of randomly
oriented fibers dried uniformly under constraint, no
microcompressions; (b) sheet containing microcompressed
fibers, showing lines (arrowed) of relaxation and second
straining; (c) sheet with failure induced by bond failure;
(d) sheet with failure induced by fiber failure; "elastic"
region; "plastic" zone; F failure point
Figure 4
Diagram of failure of bonded area (shaded): broken lines
show orientation of fibers in relaxed condition after failure
Paper
and Paperboard:
Destructive
Mechanical
Testing
Figure 5
Tearing by moving rupture line
2. Bursting
Strength
D e t e r m i n a t i o n of t h e b u r s t i n g s t r e n g t h of p a p e r is a
widely used test, p a r t i c u l a r l y in t h e p a c k a g i n g a n d
b o x industries. T h e test is, in effect, a n o m n i d i r e c
t i o n a l tensile test. T h e sheet is held in a 3.3 c m
d i a m e t e r c l a m p a n d is subjected t o a u n i f o r m pressure
from o n e side (Fig. 6). T h e results a r e related t o
v a r i o u s characteristics
of t h e
load-elongation
b e h a v i o r of the p a p e r .
It h a s been f o u n d t h a t t h e b u r s t i n g s t r e n g t h of
m a c h i n e - m a d e p a p e r s is related t o b o t h the tensile
s t r e n g t h a n d t h e failure stretch e of t h e p a p e r .
Principally, b u r s t i n g s t r e n g t h is related t o t h e M D
values of a n d e. T h i s c a n be seen from t h e following
expression for t h e b u r s t i n g s t r e n g t h :
V^CD /
L(l + % D )
3. Tearing
Strength
or
Resistance
Figure 6
Bursting strength test
301
Paper
and Paperboard:
Destructive
Mechanical
Testing
Seth R S, Page D 1980 The elastic modulus of paper: the
effects of dislocations, microcompressions, curl, crimps
and kinks. Tappi 63(10): 99-102
O. J. K a l l m e s
[ M / K Systems, D a n vers,
Massachusetts, USA]
Degree of bonding
Figure 7
Sheet tear strength as a function of degree of fiber-fiber
bonding
Increased b o n d i n g , h o w e v e r , plays a s o m e w h a t
different role. W h e n b o n d s are a d d e d t o a n u n b o n d e d
sheet, the tear s t r e n g t h initially increases with t h e
increased b o n d i n g . A t very low b o n d i n g , b o n d failure
a n d fiber p u l l o u t a r e the only m e c h a n i s m s o c c u r r i n g .
A t high levels of b o n d i n g , t h e fibers s t a r t to fail as
well, a n d the t o t a l n u m b e r of fibers involved in tear
resistance begins t o decrease. T h e energy required t o
r u p t u r e a fiber is far less t h a n t h a t r e q u i r e d to b r e a k a
large n u m b e r of b o n d s . T h u s , the tear s t r e n g t h
reaches a m a x i m u m value at a relatively low degree
of b o n d i n g a n d decreases with increased degree of
b o n d i n g (Fig. 7).
See also: Paper and Paperboard: Nondestructive Evaluation
Bibliography
Cox L 1952 The elasticity and strength of paper and other
materials. Br. J. Appl. Phys. 3: 72-9
Kallmes O, Bernier G, Perez 1977 A mechanistic theory
of the load-elongation properties of paper 1: uniform
strain theory for paper. Pap. Ind. Technol. 18: 222; 224-7
Kallmes O, Bernier G, Perez 1977 A mechanistic theory
of the load-elongation properties of paper 2: the charac
teristics of fibers taken into account. Pap. Ind. Technol.
18: 243-5
Kallmes O, Bernier G, Perez 1977 A mechanistic theory
of the load-elongation properties of paper 3: theory of the
tensile failure of Pap. Ind. Technol. 18: 283-5
Kallmes O, Bernier G, Perez 1977 A mechanistic theory
of the load-elongation properties of paper 4: experi
mental evaluation of the theory. Pap. Ind. Technol. 18:
328-31.
Page D H, Seth R S DeGrace J 1980 The elastic
modulus of paper: the controlling mechanisms. Tappi
62(9): 99-102.
Seth R S, Barbe C, Williams J C R, Page D 1982
Strength of wet webs: a new approach. Tappi 65(3): 135-8
Seth R S, Page D 1980 The elastic modulus of paper II:
the importance of fiber modulus, bonding and fiber
length. Tappi 63(6): 113-16
302
/.
Nucleonic
Technology
Paper
and Paperboard:
Nondestructive
Evaluation
Table 1
/?-Sensor limitations
Type
Instrumental
radioactive decay
drift of detector and
electronics
sensitivity to
mechanical
displacements
statistical noise
External influences
dirt accumulation
variation of air mass
in gap
composition changes
movement of sheet in
gap (passline
effect)
303
Paper
and Paperboard:
Nondestructive
T i K a line
4 . 9 5 keV
\
\
Ti edge
4 . 9 6 keV
x-ray
spectrum
average
Evaluation
\.
T1O2 a t t e n u a t i o n
coefficient
fcZ>
<<i
fcs^
clay attenuation
^/^coefficient
\
I
1
4
5
X-ray energy
6
(keV)
Figure 1
X-ray spectra and attenuation coefficients of typical ash
minerals (clay and T i 0 2 ) at low energies
2. Optical
Technology
304
d e v e l o p t h e result, b u t m o s t on-line t e c h n i q u e s
e x t r a p o l a t e from a single free-sheet m e a s u r e m e n t b y
calibration.
F o r o p a c i t y m e a s u r e m e n t , t h e c o n t r a s t definition
b a s e d o n reflection from a sheet b a c k e d b y b l a c k a n d
white b a c k i n g s c a n be c o n v e r t e d i n t o a t r a n s m i s s i o n
a l g o r i t h m , a n d m e a s u r e m e n t of a single sheet c a n b e
m a d e in a t r a n s m i s s i o n m o d e in w h i c h t h e d e t e c t o r
is covered b y a p a r t i a l reflector. I n t h e case of color
and brightness measurements, where the property
definition involves t h e reflectance from a n infinite
stack of sheets, a w h i t e o r c o l o r e d b a c k i n g is typically
used t o r e d u c e t h e e r r o r s resulting from c h a n g e s in t h e
sheet t r a n s p a r e n c y . G e n e r a l limitations of on-line
m e a s u r i n g techniques for large-scale optical p a r a m
eters a r e indicated in T a b l e 2.
T w o i n s t r u m e n t a l a p p r o a c h e s h a v e evolved for
c o l o r m e a s u r e m e n t , t h e filter c o l o r i m e t e r a n d t h e
dispersive s p e c t r o p h o t o m e t e r . I n the filter colori
meter, t h r e e filters c o r r e s p o n d i n g t o C o m m i s i o n I n
t e r n a t i o n a l de l'Eclairage ( C I E ) tristimulus , Y a n d
functions a r e used, a n d reflected light is analyzed
with a single d e t e c t o r . I n t h e dispersive s p e c t r o p h o t
o m e t e r , reflected light is dispersed b y a g r a t i n g o n t o a
d e t e c t o r a r r a y , a n d t h e multiple d e t e c t o r signals a r e
analyzed. T h e resulting spectral reflectance i n f o r m a
tion c a n be a n a l y z e d as C I E , Y a n d values. In
a d d i t i o n , signal-processing a l g o r i t h m s c a n include the
spectral characteristics of t h e s o u r c e a n d t h u s p r o v i d e
m e t a m e r i s m i n f o r m a t i o n for v a r i o u s i l l u m i n a n t s . T h e
filter c o l o r i m e t e r h a s been e x t e n d e d t o include a
s c a n n i n g m o n o c h r o m a t o r interference filter which
develops c o m p r e h e n s i v e spectral i n f o r m a t i o n c o m
p a r a b l e t o t h a t of the dispersive s p e c t r o p h o t o m e t e r .
A s a result of p o o r s t a n d a r d s , t h e e v o l u t i o n of o n
line m e a s u r e m e n t of small-scale optical p r o p e r t i e s h a s
been slow. W h i l e m e a s u r e m e n t of gloss is relatively
Table 2
Large-scale optical property sensor limitations
Type
Instrumental
source intensity drift
source spectral drift
drift of detector and
electronics
External influences
dirt accumulation
composition changes
ambient light changes
Paper
s t r a i g h t f o r w a r d , m e a s u r e m e n t of s m o o t h n e s s is inti
m a t e l y related t o t h e u l t i m a t e use of t h e p a p e r . F o r
p r i n t i n g p a p e r s , t h e q u a l i t y of t h e p a p e r surface m u s t
be c o n s i d e r e d in c o n j u n c t i o n with t h e specific p r i n t i n g
process. W h i l e off-line t e c h n i q u e s utilize air-leak
m e t h o d s for s m o o t h n e s s d e t e r m i n a t i o n , only opticalscattering t e c h n i q u e s a r e a p p r o p r i a t e on-line, a n d
c o r r e l a t i o n of these optical t e c h n i q u e s with p r i n t i n g
results is often p r o v i d e d t h r o u g h s t a n d a r d p r i n t i n g
tests.
F o r m a t i o n o r " l o o k - t h r o u g h " is a c o m p l e x , subjec
tive r e l a t i o n s h i p b e t w e e n small-scale optical density
a n d o p a c i t y (large-scale optical density). M o s t instru
m e n t s e m p l o y d e t e c t i o n of t r a n s m i t t e d light t h r o u g h a
2
small-scale a r e a of a p p r o x i m a t e l y 1 m m a n d p r o c e s s
the signal t o (a) n o r m a l i z e t h e small-scale signal with
a n o p a c i t y signal, (b) d e t e r m i n e t h e s t a n d a r d devi
a t i o n of t h e small-scale signal, a n d / o r (c) d e t e r m i n e
v a r i o u s derivatives of t h e small-scale signal.
On-line defect inspection of t h e p a p e r w e b c a n b e
p r o v i d e d with a s c a n n i n g l a s e r - b e a m device. D e t e c
tion of t h e light is p r o v i d e d t h r o u g h fiber o p t i c light
pipe t e c h n i q u e s in either t h e reflection o r t r a n s m i s s i o n
m o d e . T h e r e s o l u t i o n ( m i n i m u m defect detectable) of
2
such a n inspection system is a b o u t 1 m m t h r o u g h t h e
use of high-intensity laser b e a m s a n d fast s c a n n i n g
with r o t a t i n g multifaceted m i r r o r s .
3. Infrared
Technology
and Paperboard:
Nondestructive
0%
Evaluation
moisture
10%
absorption
"band
normalization
band
V.
0.6
08
10
1.2
1.4
Wavelength
moisture
1.6
1.8
20
22
24
()
Figure 2
Transmission spectra of paper and pertinent infrared
moisture sensor filters
1= IQ exp( OLX)
w h e r e / is the detected signal, I0 is t h e signal with the
- 1
a b s o r b e r a b s e n t , is the a b s o r p t i o n coefficient ( c m )
a n d is t h e light p a t h length in t h e w e b (cm). T h i s
light p a t h length is a function of t h e scattering p o w e r
of t h e w e b , which is itself d e p e n d e n t o n t h e scattering
cross section a n d basis weight. T h e c u m u l a t i v e effect
of these factors c a n be expressed in t e r m s of the p a t h
extension r a t i o ( P E R ) a n d n o m i n a l thickness t:
= PER./
Schematically, t h e s i t u a t i o n is s h o w n in Fig. 3 for
drafting vellum a n d n e w s p r i n t , p a p e r s of e q u a l basis
weight b u t with very different scattering cross sec
tions. Clearly, t h e n e w s p r i n t w e b , with a high scatter
ing cross section, p r o v i d e s a m u c h longer p a t h length
for light t h a n t h e drafting vellum a n d , if b o t h c o n t a i n
e q u a l a m o u n t s of w a t e r , t h e a b s o r p t i o n of light a t the
1.95 w a v e l e n g t h will be m u c h g r e a t e r in the news
p r i n t t h a n in t h e vellum.
T h i s i n h e r e n t d e p e n d e n c e of t h e m o i s t u r e sensiti
vity o n t h e scattering p o w e r of t h e sheet h a s been the
c r u x of infrared sensor d e v e l o p m e n t d u r i n g the m a t u
r a t i o n p e r i o d . C o m p e n s a t i o n / c o r r e c t i o n for this
d e p e n d e n c e h a s been a c c o m p l i s h e d t h r o u g h partially
reflecting optical geometries a n d / o r t h r o u g h m e a s u r e
m e n t s a t a d d i t i o n a l w a v e l e n g t h s . C o m p e n s a t i o n for
v a r i a t i o n s in the p a t h length i n d u c e d by v a r i a t i o n s in
scattering p o w e r is a c c o m p l i s h e d b y redirecting a n
a p p r o p r i a t e fraction of t h e o u t - s c a t t e r e d a n d t r a n s
m i t t e d light b a c k i n t o t h e w e b with partially reflecting
m i r r o r s . T h u s , in a low-scattering t r a n s l u c e n t w e b
such as vellum in w h i c h t h e P E R is close t o unity, the
s h o r t i n h e r e n t p a t h length is a u g m e n t e d by multiple
p a s s a g e s t h r o u g h t h e w e b . P r o p e r selection of the
reflectivity of t h e m i r r o r s p r o v i d e s a n identical total
p a t h length t h r o u g h b o t h n e w s p r i n t a n d vellum, t h u s
r e n d e r i n g their m o i s t u r e sensitivities e q u a l . C o m m e r
cially available sensors utilize p l a n a r o r hemispherical
305
Paper
and Paperboard:
Nondestructive
Evaluation
V-
(a)
(b)
Figure 3
Representative trajectories of light in (a) vellum
(PER = 1.2), and (b) newsprint (PER = 3.0)
m i r r o r s o n b o t h sides of the w e b t o a c c o m p l i s h t h e
c o m p e n s a t i o n . A n alternative a p p r o a c h is t o e m p l o y
m e a s u r e m e n t s of a d d i t i o n a l w a v e l e n g t h s , o n e sensi
tive t o cellulose a n d a n o t h e r as a s e c o n d n o r m a l i z a
tion w a v e l e n g t h , in o r d e r t o p r o v i d e a n i n d e p e n d e n t
m e a s u r e m e n t of t h e P E R a n d c o r r e c t t h e m o i s t u r e
m e a s u r e m e n t accordingly.
D u r i n g t h e e x p l o r a t o r y p e r i o d of infrared m e a s u r e
m e n t d e v e l o p m e n t , i n s t r u m e n t a l p r o b l e m s associated
with the i n h e r e n t instability of t h e light s o u r c e a n d
P b S infrared d e t e c t o r were solved. F o l l o w i n g the
c o n c e p t u a l design of precision s p e c t r o m e t e r s , m o s t
on-line sensor designs evolved i n t o configurations
utilizing a single d e t e c t o r a n d chopper/filter wheel t o
p r o v i d e t h e different w a v e l e n g t h s a n d n o r m a l i z e for
drift in real time. A n alternative design i n c o r p o r a t e d a
b e a m splitter a n d multiple d e t e c t o r s , e a c h with a n
a p p r o p r i a t e filter a n d t e m p e r a t u r e controller.
D u r i n g t h e m a t u r a t i o n p e r i o d , t h e i n h e r e n t sensiti
vity t o scattering p o w e r w a s resolved. In t h e o n g o i n g
refinement p e r i o d , optical i m p r o v e m e n t s a n d c o m p u
terized signal processing h a v e increased a c c u r a c y ,
e x t e n d e d the r a n g e a n d p e r m i t t e d m e a s u r e m e n t of
p a p e r s c o n t a i n i n g interfering b r o a d - b a n d a b s o r b e r s
such as c a r b o n black. T h e r e s u l t a n t m e a s u r e m e n t
a c c u r a c y achievable for p a p e r a n d p a p e r b o a r d in
typical on-line a p p l i c a t i o n s is 0 . 2 % m o i s t u r e a t low
m o i s t u r e ( 0 - 1 0 % ) a n d 2 % of t h e m o i s t u r e level u p
to the practical limit for t r a n s m i s s i o n m e a s u r e m e n t s
of 2 5 % m o i s t u r e . M e a s u r e m e n t c a n be m a d e accur
2
ately for webs u p t o 500 g m . A s u m m a r y of sensor
limitations a n d c o u n t e r a c t i n g design a p p r o a c h e s is
given in T a b l e 3.
A d a p t a t i o n of t h e basic i n s t r u m e n t a l c o n c e p t t o
reflection geometries h a s also been successful. I n such
configurations, t h e m e a s u r e m e n t is m o s t sensitive t o
2
the m o i s t u r e c o n t a i n e d in t h e w e b t o 20 g m " from
306
4. Microwave
and Radio-Frequency
Technology
M i c r o w a v e a n d radio-frequency t e c h n i q u e s h a v e been
utilized for m e a s u r e m e n t of m o i s t u r e in p a p e r since
t h e 1960s. T h e s e t e c h n i q u e s a r e n o w less widely used
t h a n infrared t e c h n i q u e s , b u t a r e o p t i m a l for certain
heavyweight paper and paperboard applications.
T h e i n t e r a c t i o n of e l e c t r o m a g n e t i c r a d i a t i o n in the
11
1 0 M 0 H z r a n g e with w a t e r molecules is c o m p l i c a t e d
by t h e b o n d i n g of t h e w a t e r in the cellulose m a t r i x .
Basic i n t e r a c t i o n p h e n o m e n a b e t w e e n e l e c t r o m a g n e
tic r a d i a t i o n a n d w a t e r a r e indicated in Fig. 4. A t
infrared frequencies, a b s o r p t i o n t h r o u g h m o l e c u l a r
v i b r a t i o n occurs; a t m i c r o w a v e frequencies, a b s o r p
t i o n t h r o u g h m o l e c u l a r r o t a t i o n o c c u r s ; a t lower
frequencies, dielectric p o l a r i z a t i o n a n d c h a r g e t r a n s
p o r t m e c h a n i s m s o c c u r a t a m a c r o m o l e c u l e level. T h e
b o n d i n g of w a t e r a n d cellulose h a s little effect o n the
Table 3
Infrared sensor limitations
Type
Instrumental
detector drift
source drift
sensitivity to
mechanical
displacements
statistical noise
External influences
dirt accumulation
composition changes
movement of sheet in
gap (passline effect)
Paper
Nondestructive
Evaluation
O - H Bond vibration,
infrared
and Paperboard:
l 4
(IO Hz)
Dipole rotation,
1 0
microwave ( Hz)
Dipole orientation,
radio-frequency/ultrahigh
frequency ( I 0
Interfacial
-I0
Hz)
p o l a r i z a t i o3 n ,
radio-frequency ( I 0 - I 0
5. Mechanical,
Technologies
6
Hz)
Figure 4
Interactions of electromagnetic radiation with water
a b s o r p t i o n of infrared r a d i a t i o n , b u t h a s a s u b s t a n t i a l
impact on microwave a n d radio-frequency interac
tions. B o u n d w a t e r , p r e v a l e n t a t low m o i s t u r e levels,
is u n a b l e t o i n t e r a c t in r o t a t i o n a l m o d e s ; as a result,
microwave absorption techniques have inadequate
sensitivity a t low m o i s t u r e levels ( < 3 % m o i s t u r e ) ,
a n d a r e t e m p e r a t u r e sensitive a t i n t e r m e d i a t e levels
( 3 - 2 0 % moisture) where
temperature-dependent
h y d r o g e n - b o n d i n g equilibria c h a n g e t h e a b s o r p t i o n
coefficient. A t high m o i s t u r e levels, w h e r e free w a t e r is
prevalent, m i c r o w a v e a b s o r p t i o n is m o s t a p p r o p r i a t e ,
a n d m e a s u r e m e n t in t h e b r o a d r e s o n a n c e a t
1 0
2 x 1 0 H z is typical.
M i c r o w a v e a b s o r p t i o n sensors typically consist of
t r a n s m i t t e r a n d receiver h o r n s , l o c a t e d o n o p p o s i t e
sides of t h e w e b , with a d d i t i o n a l h o r n s utilized t o
measure and/or minimize geometry-dependent con
structive/destructive interference effects. C o n t a c t i n g
w a v e g u i d e geometries a r e also used.
9
A t frequencies b e l o w 2 10 H z , t h e dielectric
p r o p e r t i e s of w a t e r p r o v i d e t h e basis of a m o i s t u r e
m e a s u r e m e n t w h e r e b y t h e p a p e r sheet modifies the
r e s o n a n t frequency of a m i c r o w a v e cavity. Since t h e
interacting w a t e r molecules align with t h e electric
field ( r a t h e r t h a n r o t a t i n g , as h a p p e n s at t h e a b s o r p
tion r e s o n a n c e ) , t h e dielectric i n t e r a c t i o n is m o r e
sensitive t h a n t h e a b s o r p t i o n i n t e r a c t i o n a t inter
m e d i a t e ( a b o u t 5 % ) m o i s t u r e levels. N o n c o n t a c t i n g
double-sided a n d c o n t a c t i n g single-sided r e s o n a n t
cavities are used.
Radio-frequency moisture measurements are m a d e
6
in t h e 1 0 M 0 H z r a n g e . Typically, a n electrode struc
t u r e c o n t a c t s t h e sheet a n d p r o b e i m p e d a n c e is cali
b r a t e d in t e r m s of m o i s t u r e c o n t e n t . V a r i a t i o n s in w e b
c o m p o s i t i o n , including fiber p r o p e r t i e s a n d ionic c o n
tent, c h a n g e t h e c a l i b r a t i o n a n d limit t h e a c c u r a c y of
the m e a s u r e m e n t .
Pneumatic
and
Acoustic
V a r i o u s m e c h a n i c a l , p n e u m a t i c - f l u i d i c a n d acoustic
technologies h a v e been utilized o r a r e being developed
for on-line m e a s u r e m e n t s , with t h e greatest e m p h a s i s
being o n the m e a s u r e m e n t of p a p e r / p a p e r b o a r d
caliper. U l t r a s o n i c s a r e being developed t o p r o v i d e
i n d i c a t i o n s of s t r e n g t h - r e l a t e d p r o p e r t i e s inferred
from p r o p a g a t i o n velocities.
On-line caliper m e a s u r e m e n t systems a r e t w o sided,
consisting of a t r a n s d u c e r e n e r g y - c o u p l i n g subsystem
a n d a t r a n s d u c e r h e a d - p o s i t i o n i n g subsystem. T h e
h e a d - p o s i t i o n i n g s u b s y s t e m establishes a reference
g e o m e t r y in which w e b caliper v a r i a t i o n s c h a n g e the
s e p a r a t i o n b e t w e e n t h e elements of the energyc o u p l i n g s u b s y s t e m . V a r i o u s m o d e s of energy
c o u p l i n g a r e utilized, m o s t c o m m o n l y c o u p l i n g of
e l e c t r o m a g n e t i c r a d i a t i o n t h r o u g h t h e w e b , either
of m a g n e t i c fields w i t h a split-core t r a n s f o r m e r o r
of electric fields with a radio-frequency coil a n d e d d y c u r r e n t target.
W h i l e t h e e n e r g y - c o u p l i n g t e c h n o l o g y is refined,
t h e h e a d - p o s i t i o n i n g t e c h n o l o g y is q u i t e process inter
active a n d t h e a p p l i c a t i o n t e c h n o l o g y is still m a t u r i n g .
P o s i t i o n i n g m e t h o d s c a n b e classified as two-sided
c o n t a c t i n g , one-sided c o n t a c t i n g o r n o n c o n t a c t i n g ,
w h e r e p n e u m a t i c air b e a r i n g s a r e e m p l o y e d t o separ
ate o n e o r b o t h t r a n s d u c e r h e a d s from the w e b .
P r o b l e m s related t o w e b stability, sensor s t a n d a r d i z a
tion a n d h e a d a l i g n m e n t h a v e inhibited on-line appli
c a t i o n of a n o n c o n t a c t i n g design, b u t these p r o b l e m s
a r e o v e r c o m e with a one-sided c o n t a c t i n g design in
w h i c h t h e w e b c o n t a c t s a fixed p l a t e , a n d e l e c t r o m a g
netic c o u p l i n g b e t w e e n t h e p l a t e a n d a h e a d floating
o n a n air b e a r i n g a b o v e the w e b provides the
m e a s u r e m e n t . T h e two-sided c o n t a c t i n g design
generally includes s p r i n g - l o a d e d c o n t a c t i n g a r m s a n d
a p a i r of c o n t a c t i n g surfaces m a d e of s m o o t h , wearresistant m a t e r i a l .
C o n c e p t u a l l y , t h e two-sided c o n t a c t i n g design
m e a s u r e s the d i s t a n c e b e t w e e n the p e a k s of the p a p e r
included within t h e c o n t a c t i n g a r e a , a n d is affected by
sheet c o m p r e s s i o n related t o t h e l o a d i n g of the c o n
tacting a r m s a n d by the d y n a m i c residence time of the
sheet within t h e c o n t a c t a r e a . In c o n t r a s t , the o n e
sided c o n t a c t i n g design m e a s u r e s the distance
b e t w e e n a n a v e r a g e of p e a k s a n d valleys o n the airb e a r i n g s i d e . a n d t h e p e a k s o n t h e c o n t a c t i n g side
w i t h o u t c o m p r e s s i o n effects. A e r o d y n a m i c factors are
307
Paper
and Paperboard:
Nondestructive
Evaluation
6. Correlation
and
Verification
Historically, c o r r e l a t i o n of on-line n o n d e s t r u c t i v e
m e a s u r e m e n t s with off-line reference m e a s u r e m e n t s
w a s intimately related t o sensor c a l i b r a t i o n a n d w a s
necessary t o verify t h a t " c a l i b r a t i o n shifts" did n o t
d e g r a d e the on-line m e a s u r e m e n t . A s basic sensing
technologies h a v e m a t u r e d a n d been refined, sensiti
vity t o s p u r i o u s p r o c e s s factors h a s decreased greatly,
a n d sensors a r e far m o r e stable a n d t o l e r a n t of
e n v i r o n m e n t a l a n d process c o n d i t i o n s , t h u s eliminat
ing m a n y of the causes of c a l i b r a t i o n shifts. A s a
result, c o r r e l a t i o n t e c h n i q u e s h a v e b e c o m e m o r e
sophisticated a n d a r e used p r i m a r i l y t o verify t h a t
n o i n s t r u m e n t a l o r process effects i m p a i r sensor
performance.
C u r r e n t c o r r e l a t i o n techniques c a n be classified as
static o r d y n a m i c . Static t e c h n i q u e s consist of off-web
sensor m e a s u r e m e n t s of check s a m p l e s (with k n o w n
stable p a r a m e t e r s ) a n d c a l i b r a t i o n samples (for which
new c a l i b r a t i o n c o n s t a n t s a r e t o be d e t e r m i n e d ) .
D y n a m i c t e c h n i q u e s involve (a) acquisition of w e b
samples which h a v e been m e a s u r e d on-line b y a
sensor, (b) m e a s u r e m e n t of these d y n a m i c s a m p l e s
308
Bibliography
Baum G A, Habeger C C 1980 On-line measurement of
paper mechanical properties. Tappi 63(7): 63-6
Particle-Induced
X-Ray
Emission
/.
Principle
2. Experimental
Arrangements
E x p e r i m e n t a l l y , P I X E analysis c a n b e carried o u t
using v a r i o u s a r r a n g e m e n t s . U s u a l l y , t h e s a m p l e t o b e
R. J. Pfeifer
[AccuRay Corporation, Columbus,
Ohio, USA]
Computer
Figure 1
Schematic diagram of a PIXE setup
309
Particle-Induced
X-Ray
Emission
n o w a n u m b e r of c o d e s t h a t m a k e it possible t o let a
c o m p u t e r c a r r y o u t t h e c o m p l e t e analysis of a P I X E
s p e c t r u m . It is c o n v e n i e n t t o i n t r o d u c e cross sections,
a b s o r p t i o n coefficients a n d t h e v a r i o u s e x p e r i m e n
tal p a r a m e t e r s i n t o the c o d e so t h a t t h e c o m p u t e r
p r i n t o u t consists of m a s s values of all elements
t h a t c a n be d e t e r m i n e d a n d u p p e r limits for t h o s e n o t
detected.
Ca
3. Combination
10
Energy
15
20
25
(keV)
Figure 2
A typical spectrum
310
Methods
Particle-Induced
nuclear m a s s . H e n c e , in t h e energy s p e c t r u m t h e r e a r e
p e a k s for e a c h m a s s value a n d their height is a
m e a s u r e of t h e a b u n d a n c e of t h e c o r r e s p o n d i n g n u c
lides. F o r a g o o d m a s s r e s o l u t i o n r a t h e r high p r o t o n
energies a r e r e q u i r e d . H o w e v e r , even with a n energy
of 2 - 3 M e V t h e r e s o l u t i o n is sufficient t o resolve such
elements as c a r b o n , n i t r o g e n a n d oxygen, w h i c h a r e
t h o s e usually d e t e r m i n e d b y P E S A . H e n c e , P E S A c a n
also be p e r f o r m e d s i m u l t a n e o u s l y with P I X E .
A P I X E set u p w h i c h is p r o v i d e d with a r r a n g e
m e n t s for P I G E a n d P E S A is t h u s a very powerful
i n s t r u m e n t with a u n i q u e m u l t i e l e m e n t a l capability
t h a t m a k e s it possible t o d e t e r m i n e all elements from
h y d r o g e n t o u r a n i u m . T h i s is illustrated in F i g . 3
which s h o w s typical values of t h e m i n i m u m d e t e c t i o n
limits.
4. The PIXE
Microbeam
O n e a d v a n t a g e of P I X E analysis is t h a t t h e cross
section of t h e particle b e a m c a n be adjusted. It is
possible t o cover a large p a r t of t h e s a m p l e , b u t also
to select a smaller p a r t for closer e x a m i n a t i o n . W i t h
the c o n v e n t i o n a l focusing m a g n e t s of a n a c c e l e r a t o r
facility b e a m d i a m e t e r s as small as a few t e n t h s of a
millimeter c a n b e o b t a i n e d . H o w e v e r , in recent years
the m i c r o b e a m t e c h n i q u e h a s been i m p r o v e d a n d a
spatial r e s o l u t i o n of t h e o r d e r of 0.1-1 h a s b e e n
achieved. T h i s , of c o u r s e , requires a m o r e c o m p l i
cated focusing system, usually consisting of t w o t o
four q u a d r u p o l e m a g n e t i c lenses. S u c h a m i c r o b e a m
of c h a r g e d particles h a s f o u n d m a n y a p p l i c a t i o n s . F o r
analytical p u r p o s e s a c o m b i n a t i o n with P I X E , often
called - , is t h e m o s t c o m m o n o n e . T h e r e a s o n is
t h a t a m o n g t h e analytical t e c h n i q u e s t h a t c a n be
c o m b i n e d with a m i c r o b e a m , P I X E h a s t h e highest
sensitivity.
20
40
Atomic
60
number,
Figure 3
Typical detection limits for PIXE and the complementary
nuclear techniques elastic scattering (PESA) and
gamma-ray emission (PIGE)
X-Ray
Emission
Sample
Figure 4
Schematic diagram of a PIXE microbeam
T h e principle of a P I X E m i c r o b e a m is illustrated in
Fig. 4. T h e particle b e a m from t h e accelerator is
focused o n t o the h o l e of a d i a p h r a g m , which is the
object in the b e a m - o p t i c a l system. By m e a n s of the
m a g n e t i c lenses the b e a m is focused so t h a t it gives a
demagnified i m a g e of t h e d i a p h r a g m o n the s a m p l e to
be a n a l y z e d . T h e d i a m e t e r of t h e d i a p h r a g m hole is
a d j u s t a b l e in the r a n g e 10-100 . W i t h a demagnific a t i o n factor of ten, the b e a m s p o t o n the surface of
t h e s a m p l e h a s a d i a m e t e r in t h e r a n g e 1-10 . T h i s
m e a n s t h a t t h e P I X E analysis c a n be p e r f o r m e d with a
spatial r e s o l u t i o n of this o r d e r . W i t h s o m e sacrifice in
b e a m c u r r e n t , even s u b m i c r o m e t e r r e s o l u t i o n s h a v e
been achieved.
T h e - t e c h n i q u e e n a b l e s t h e s t u d y of the
spatial d i s t r i b u t i o n of elemental c o n c e n t r a t i o n s . By
m o v i n g t h e s a m p l e step b y step in t w o p e r p e n d i c u l a r
directions a n d p e r f o r m i n g P I X E analysis at each
p o s i t i o n a m a p of t h e elemental c o n c e n t r a t i o n s is
o b t a i n e d for e a c h element. A m o r e efficient t e c h n i q u e ,
h o w e v e r , is t o sweep the b e a m in t h e s a m e m a n n e r as
in a s c a n n i n g electron m i c r o s c o p e . T h i s c a n be d o n e
with electrostatic deflection p l a t e s , as indicated in Fig.
4, o r w i t h m a g n e t i c deflection. F o r each x-ray pulse
from t h e d e t e c t o r t h e pulse height a n d the a n d y
c o o r d i n a t e s of t h e b e a m a r e r e c o r d e d a n d s t o r e d in
t h e c o m p u t e r m e m o r y . T h i s d a t a set c a n t h e n be
a n a l y z e d off-line in v a r i o u s w a y s . C o n c e n t r a t i o n
values a t different p o i n t s o r c o n c e n t r a t i o n profiles for
selected elements c a n be d e t e r m i n e d . T h e m o s t effi
cient use of t h e d a t a is t o p l o t a c o n c e n t r a t i o n m a p for
e a c h element.
It is o b v i o u s t h a t t h e P I X E m i c r o b e a m , in prin
ciple, is similar t o the s c a n n i n g electron m i c r o p r o b e .
T h e m a i n difference is t h a t t h e electron g u n is replaced
by a n a c c e l e r a t o r for p r o t o n s . T h i s , of c o u r s e , m e a n s
increased c o m p l e x i t y a n d cost. A relevant q u e s t i o n is
w h e t h e r t h e a d v a n t a g e s of t h e P I X E m i c r o b e a m are
w o r t h these e x t r a costs. T h e a n s w e r is given by the
very m u c h increased analytical sensitivity. In the
electron case there is a s t r o n g B r e m s s t r a h l u n g b a c k
g r o u n d which t e n d s t o m a s k the characteristic x-ray
311
Particle-Induced
X-Ray
Emission
I0
5.7
Sensitivity
P I X E h a s a c o m p a r a t i v e l y high relative sensitivity
which is, h o w e v e r , d e p e n d e n t o n t h e c o m p o s i t i o n of
t h e s a m p l e . T h e m o s t favorable case is t h e d e t e r m i
n a t i o n of trace elements in o r g a n i c tissue w h e r e
detection limits as low as 20 p p b h a v e been achieved.
A less favorable case is mineralogical a n d m e t a l l u r g i
cal s a m p l e s c o n t a i n i n g large a m o u n t s of h e a v y
elements, w h i c h c a n increase t h e detection limits t o
1-10 p p m .
In a b s o l u t e t e r m s the sensitivity of P I X E is very
g o o d . I n c o n v e n t i o n a l P I X E the b e a m d i a m e t e r is a
few millimeters, which gives detection limits of t h e
11
o r d e r of 1 0 " g. W i t h t h e m i c r o b e a m t e c h n i q u e a n d a
spatial r e s o l u t i o n of a b o u t 1 , d e t e c t i o n limits as
1 6
low as 1 0 " g c a n be achieved.
100
200
300
400
500
600
700
800
900
1000
Energy (keV)
Figure 5
X-ray spectrum of an organic tissue sample; excitation
with (a) 20 keV electrons and (b) 2.5 MeV protons.
p e a k s . P r o t o n s give a m u c h lower b a c k g r o u n d . T h i s is
illustrated in Fig. 5 which c o m p a r e s spectra from t h e
same o r g a n i c s a m p l e w h e n i r r a d i a t e d with 2 0 k e V
electrons a n d 2.5 M e V p r o t o n s . T h e r e is a striking
difference in sensitivity, which m e a n s t h a t in o r g a n i c
tissue the electron m i c r o p r o b e c a n n o t detect a n y trace
elements w h e r e a s this is possible with a P I X E m i c r o b e a m . In a c t u a l n u m b e r s , the d e t e c t i o n limits a r e of
the o r d e r of 0 . 1 % for the electron m i c r o p r o b e a n d
0 . 0 0 1 % for t h e P I X E m i c r o b e a m . T h i s factor of a
h u n d r e d in increased sensitivity is t h e m a i n r e a s o n for
using the - t e c h n i q u e .
T h e a d v e n t of t h e P I X E m i c r o b e a m h a s o p e n e d u p
a new field of trace element analysis o n t h e m i c r o
scopic scale. T h e greatest p o t e n t i a l is p e r h a p s in
biology a n d medicine w h e r e it is conceivable t o s t u d y
the d i s t r i b u t i o n of trace elements o n the cellular level.
H o w e v e r , this new t e c h n i q u e s h o u l d also be of im
p o r t a n c e in m a t e r i a l s science. F o r e x a m p l e , in m i c r o
electronics it is of interest t o s t u d y t h e elemental
c o m p o s i t i o n of microscopically small c o m p o n e n t s .
5.
Advantages
312
5.2 Multielemental
Capability
P I X E is a truly m u l t i e l e m e n t a l m e t h o d which c a n be
used over m o s t of the p e r i o d i c table. A n i m p o r t a n t
feature is t h a t the sensitivity varies only slightly
b e t w e e n different elements. T h i s is in c o n t r a s t t o
m a n y o t h e r analytical m e t h o d s for which there c a n b e
a very large difference in sensitivity b e t w e e n n e i g h b o r
ing elements.
5.3 Spatial
Resolution
Versatility
Particle-Induced
b u t in a n a l y z i n g m o r e delicate m a t e r i a l s , for e x a m p l e
p a p e r , it is advisable t o k e e p t h e b e a m c u r r e n t as low
as possible.
It is i m p o r t a n t t o p o i n t o u t t h a t P I X E is n o t u n i q u e
r e g a r d i n g a n y single o n e of these features. T h e r e a r e ,
for e x a m p l e , o t h e r analytical m e t h o d s t h a t a r e m o r e
sensitive a n d there a r e n o n d e s t r u c t i v e m e t h o d s with a
g o o d m u l t i e l e m e n t a l capability. T h e real s t r e n g t h of
P I X E lies in t h e c o m b i n a t i o n of so m a n y a d v a n t a
geous features.
6.
Applications
X-Ray
Emission
313
Particle-Induced
X-Ray
Emission
Figure 6
Elemental maps from a section of a spruce tree. The concentrations are shown in a grey tone scale with black denoting
the highest concentrations and white the lowest. The size of each map is about 2 mm 2 mm. The tree ring structure is
seen clearly for some elements (calcium and iron) which are characteristic of wood but not for pollution elements
314
Bibliography
Cohen D D, Clayton 1989 Ion induced x-ray emission. In:
Bird J R, Williams J S (eds.) 1989 Ion Beams for Materials
Analysis. Academic Press, Sydney, Australia, pp. 209-60
Johansson , Johansson S A , Malmqvist G, Wiman
I 1986 The feasibility of the PIXE technique in the
analysis of stamps and art objects. Nucl. Instrum. Meth
ods 14: 45-9
Phase
Johansson S A E, Campbell J L 1988 PIXE: A Novel
Technique for Elemental Analysis. Wiley, Chichester, UK
Johansson S A E, Johansson 1976 Analytical applica
tions of particle-induced x-ray emission. Nucl. Instrum.
Methods 137: 473-516
Kusko , Schwab R 1987 Historical analysis by PIXE,
Nucl. Instrum. Methods. 22: 401-6
Lovestam G, Johansson , Johansson S A , Pallon J
1990 Elemental micro patterns in tree ringsa feasibility
study using scanning proton microprobe analysis. Ambio
19:87-93.
Mitchell I V, Barfoot 1981 Particle-induced x-ray
emission analysis application to analytical problems.
Nucl. Sci. Appl. 1:99-162
Vis R D 1985 The Proton Microprobe. CRC, Boca Raton,
FL
Watt F, Grime G W (eds.) 1987 Principles and Applications
of High Energy Microbeams. Institute of Physics, Bristol,
UK
S. A . E . J o h a n s s o n
[Lund Institute of Technology,
L u n d , Sweden]
-20001
0
Diagrams
I
0 10
and Phase
Stability:
I
I
I
I
I
I
0.20 0.30 0.40 0.50 0.60 0 70
Mole fraction of chromium
Calculations
I
0 80
I
0.90
I
00
Figure 1
The effect of lattice stabilities and interaction coefficients
on the free energy curves for face-centered-cubic (fee) and
body-centered-cubic (bec) phases in the iron-chromium
system at 700
(*,-*,
T) = XiXjAG% +
+ RT(xt
AG^x,
In xt + Xj In Xj)
E
T) = xixjAG p
+ RT{xt
AG^Xj
(1)
AG^xi
In xt + Xj In Xj)
(2)
w h e r e AG^ a r e t h e i n t e r a c t i o n energies o f c o m
a a
p o n e n t s i a n d j in crystal s t r u c t u r e s a n d /?, A Gf ^ - ^
are t h e differences in energy different a l l o t r o p e s
(lattice stabilities) a n d R (x{ In xt + Xj In x) is t h e
e n t r o p y of mixing.
The temperature a n d composition dependence of
E
AG is c o m m o n l y expressed a s
T h e c a l c u l a t i o n o f p h a s e b o u n d a r y c o m p o s i t i o n is
t h u s r e d u c e d t o t h e m a t h e m a t i c a l p r o b l e m of finding
t h e free energy m i n i m u m for a n y p a r t i c u l a r c o m
b i n a t i o n o f t h e variables c o n c e r n e d , p r o v i d e d t h e
v a r i a t i o n o f free energy with t e m p e r a t u r e ( a n d a n y
o t h e r variables o f interest) c a n b e specified for each
phase. Some of the d a t a required t o evaluate the
necessary free energies (e.g., h e a t s of f o r m a t i o n ) c a n
be o b t a i n e d directly b y e x p e r i m e n t , given a p r o p e r
a p p r e c i a t i o n of t h e reference states. H o w e v e r , t o
p e r f o r m even this initial step requires a systematic
k n o w l e d g e of t h e relevant lattice stabilities, m a n y of
w h i c h will refer t o m e t a s t a b l e p h a s e s (see F i g . 1).
Since t h e r m o d y n a m i c d a t a a r e r e q u i r e d for p h a s e s
t h a t m a y b e e x p e r i m e n t a l l y inaccessible, p h a s e dia
g r a m c a l c u l a t i o n s of real systems r e m a i n e d largely a n
a l g e b r a i c c o n c e p t until a n o t a b l e b r e a k t h r o u g h w a s
achieved b y K a u f m a n a n d Bernstein (1970).
T h e y realized t h a t since t h e lattice stabilities of a n y
given element h a v e t o b e t h e s a m e in all p h a s e
d i a g r a m s t h a t c o n t a i n t h a t element, estimates of t h e
missing lattice stabilities m i g h t b e o b t a i n e d b y a p p l y
ing a n iterative p r o c e d u r e t o a series o f interrelated
p h a s e d i a g r a m s . O n c e this p r o c e d u r e w a s a d o p t e d , it
w a s f o u n d t h a t t h e t e m p e r a t u r e v a r i a t i o n of such
lattice stabilities c o u l d , in m a n y cases, b e a p p r o x i
m a t e d b y simple linear e q u a t i o n s . T h e s e lattice stabili
ties in t u r n acted a s reference states for the s u b s e q u e n t
e v a l u a t i o n o f missing i n t e r a c t i o n coefficients in m a n y
b i n a r y systems. W i t h t h e a c c u m u l a t i o n o f sufficient
d a t a , it b e c a m e possible t o g e n e r a t e empirical f o r m u
l a t i o n s t h a t allowed t h e e s t i m a t i o n o f missing p a r a m
eters, a n d t h e n u m b e r o f calculated d i a g r a m s
increased very rapidly. H o w e v e r , t h e absence of ab
315
Phase Diagrams
Calculations
1. Extension
to Metastable
Phases
0.05
0.10
0.15
0.20
0.25
Figure 3
Comparison of experimentally determined and calculated
phase boundaries between aluminum and the metastable
' Al 3Li phase in aluminum-lithium
relative c o m p l e x i t y of t h e crystal s t r u c t u r e s c o n c e r n e d
a n d t h e e x p e r i m e n t a l d a t a available. I n fact, calcula
tions c a n b e e x t e n d e d t o a m o r p h o u s p h a s e s a n d there
is m u c h m o r e scope for realistic predictions t h a n is
generally realized ( S a u n d e r s a n d M i o d o w n i k 1986).
2. Extension
to Multicomponent
Systems
E j
T) =
+
+ RT
E
Ejk
xixjAG J +xjxkAG 0L
"*
=
Eki
xkXiAGa
In + xiXjxkAG
kE i j
xt
(3)
Eijk
0.2
0.4
0.6
Mole fraction of
0.8
lithium
Figure 2
Calculated phase diagram of aluminum-lithium with
experimental data superimposed (Saunders 1989)
316
a r e t e r n a r y i n t e r a c t i o n t e r m s which a r e
where G
often relatively small o r zero.
T h i s p r o v i d e d t h e m a j o r s p u r t o t h e c r e a t i o n of a n
e x p a n d i n g d a t a b a s e , p a r t i c u l a r l y for c o m b i n a t i o n s of
3d t r a n s i t i o n elements of industrial interest ( K a u f m a n
a n d Bernstein 1970, K a u f m a n 1972). T e r n a r y sys
tems, h o w e v e r , b r i n g s o m e a d d i t i o n a l choice p a t t e r n s
for m o d e l l i n g h o w a b i n a r y c o m p o u n d with a given
crystal s t r u c t u r e e x t e n d s i n t o t h e t e r n a r y system. O n e
Phase
Diagrams
and Phase
Stability:
Calculations
suits b a s e d o n t h e r m o d y n a m i c d a t a a n d a r e c a p a b l e
of e x t e n s i o n t o m u l t i c o m p o n e n t systems. A c o n v e n
ient s u m m a r y of t h e c u r r e n t scope of p h a s e d i a g r a m
c a l c u l a t i o n s is given by t h e ten year index of the
C a l p h a d j o u r n a l for 1977-1986 ( B e r n a r d 1986).
3. Approaches
to
Modelling
A d v a n c e s in m o d e l l i n g h a v e t a k e n place in three
s e p a r a t e areas:
Figure 4
Comparison of calculated phase equilibria with
experimental data for the chromium-iron-silicon system
at 1173 (Chart et al. 1980)
way, is t o c o n s i d e r t h e c o r r e s p o n d i n g stability of
c o m p o u n d s with t h e s a m e crystal s t r u c t u r e in t h e
o t h e r t w o edge-binaries. W h e n three b i n a r y systems
c o m b i n e t o f o r m a t e r n a r y system, t h e stable c o m
p o u n d s t h a t o c c u r in o n e of t h e b i n a r y systems m a y
n o t h a v e i s o m o r p h o u s c o u n t e r p a r t s in the o t h e r edgebinaries. It t h e n b e c o m e s necessary t o h a v e a value for
the stability of t h e ( m e t a s t a b l e ) " c o u n t e r p h a s e " of t h e
s a m e crystal s t u c t u r e , a l t h o u g h this is b y definition
experimentally inaccessible.
T h i s p r o b l e m is in m a n y w a y s a n a l o g o u s t o t h a t of
e s t i m a t i n g missing lattice stabilities for t h e e l e m e n t s ,
b u t as there a r e m a n y m o r e subtle v a r i a t i o n s in crystal
s t r u c t u r e for intermetallic p h a s e s , there a r e c o r r e s
p o n d i n g l y fewer m e m b e r s of a p a r t i c u l a r crystal sym
m e t r y from which t o d r a w guidelines. Nevertheless as
d a t a b a s e s b e c a m e m o r e extensive, empirical rules
were evolved a n d utilized t o m a k e useful a p p r o x i m a
tions, even for t h e i n t r o d u c t i o n of p a r a m e t e r s for
t e r n a r y c o m p o u n d s t h a t h a v e n o c o u n t e r p a r t in t h e
c o m p o n e n t b i n a r y systems.
T h e e v o l u t i o n of meaningful empirical relation
ships a n d their r e p l a c e m e n t b y m o r e f u n d a m e n t a l
expressions clearly r e q u i r e d i n t e r n a t i o n a l c o l l a b o r a
tion. A c c o r d i n g l y t h e C a l p h a d (calculation of p h a s e
d i a g r a m s ) g r o u p w a s f o u n d e d in 1972 t o s h a r e t h e
i n f o r m a t i o n necessary t o t h e further d e v e l o p m e n t of
this r a p i d l y e x p a n d i n g t e c h n i q u e , b r i n g i n g t o g e t h e r
w o r k e r s using a variety of different m o d e l s a n d m e t h
odologies t o h a n d l e a n increasingly m u l t i d i m e n s i o n a l
problem. Whereas b o t h the Calphad G r o u p and the
C a l p h a d j o u r n a l a r e c o n c e r n e d w i t h all k n o w n m e t h
o d s (including first-principle calculations) relating t o
p h a s e stability, t h e label C a l p h a d m e t h o d refers t o a
subset of t e c h n i q u e s t h a t p r o d u c e self-consistent re-
(a)
(b)
(c)
t h e i n c o r p o r a t i o n of expressions m o r e closely
related t o t h e u n d e r l y i n g physical reality of
bonding mechanisms.
317
Phase
Diagrams
and Phase
Stability:
Calculations
CaLphad method
5
I0
I0
cluster variation
band calculations
Monte CarLo
moLecuLar dynamics
associate
sublattice
quasichemical
regular solution
AG
10'
io|
of a c o n t i n u u m of p a r t i a l l y - o r d e r e d states. T h e
m e t h o d c a n be e x t e n d e d t o o r d e r i n g in t e r n a r y sys
t e m s , b u t a t p r e s e n t it is difficult t o e x t e n d t o m u l t i c o m p o n e n t systems b e c a u s e the c o m b i n a t i o n s of site
o c c u p a n c y b e c o m e excessive. T h e basic e q u a t i o n is
o rd
= Nxixj(AWx
3W2)
-^Wx-6W2)f]
pocket calculator
number of adjustable parameters
Empirical
First principles
Semiempirical
Physical soundness
W2(f\+fl)
L
NKT
+ ^ ( ^ 1
P A + P B^
P B)
(4)
Figure 5
Overview of models and methods used to represent and
calculate thermodynamic properties (Agren 1986)
4. The Inclusion
of Chemical
Ordering
318
w h e r e Wx a n d W2 a r e first a n d s e c o n d n e i g h b o r
L
L
i n t e r a c t i o n coefficients, P A a n d P B are site o c c u p a t i o n
p r o b a b i l i t i e s o n sublattice L, a n d fx,f2,
a n d f3 a r e
L
functions of P A.
T h i s m o d e l also h a s n o p r o v i s i o n for s h o r t - r a n g e
chemical o r d e r a b o v e t h e critical o r d e r i n g t e m p e r a
t u r e , so t h a t a n u m b e r of a r b i t r a r y fitting c o n s t a n t s
h a v e t o be included t o m a t c h e x p e r i m e n t a l i n f o r m a
tion in real systems, w h e r e s h o r t - r a n g e o r d e r is
generally f o u n d t o be i n e s c a p a b l y p r e s e n t . C o n s e
q u e n t l y , a h i e r a r c h y of o t h e r t e c h n i q u e s h a s been
d e v e l o p e d t o include the effects of s h o r t - r a n g e o r d e r
( A c k e r m a n et al. 1989). A s the n a m e implies, the
cluster v a r i a t i o n m e t h o d ( C V M ) c o n s i d e r s i n t e r a c t i o n
p a t t e r n s in clusters of v a r i o u s sizes, w i t h the tetra
h e d r o n a p p r o x i m a t i o n c u r r e n t l y the m o s t p o p u l a r
m e t h o d b u t still r e q u i r i n g c o n s i d e r a b l e c o m p u t i n g
effort. I n c l u d i n g increasingly larger n u m b e r s of a t o m s
ultimately requires M o n t e C a r l o c a l c u l a t i o n s (Crusius
a n d I n d e n 1988), a c k n o w l e d g e d t o give t h e m o s t
definitive results, b u t r e q u i r i n g extensive c o m p u t i n g
time (see Fig. 5). It s h o u l d be n o t e d t h a t , despite their
m a t h e m a t i c a l rigor, all these m e t h o d s r e q u i r e s o m e
e x t e r n a l i n p u t in t h e f o r m of i n t e r a c t i o n p a r a m e t e r s
a n d c a n n o t be c o n s i d e r e d as first-principle calcula
tions unless t h e relevant i n t e r a c t i o n p a r a m e t e r s h a v e
b e e n supplied b y ab initio c a l c u l a t i o n s .
5. Incorporation
of Magnetic
Terms
Phase
i n p u t s for t h e B o h r m a g n e t o n n u m b e r () a n d t h e
C u r i e t e m p e r a t u r e (Tc), a n d a variety of p o l y n o m i a l
fitting functions a r e used t o r e p r o d u c e t h e e x p e r i m e n
tally observed c o n c e n t r a t i o n d e p e n d e n c e of these
t w o p a r a m e t e r s . M o s t of t h e available semiempirical
f o r m u l a t i o n s of m a g n e t i c free energy a r e b a s e d o n
q u a n t u m - m e c h a n i c a l f o r m u l a e of t h e e n t r o p y associ
ated with discrete m a g n e t i c spins, a n d all yield very
similar results ( M i o d o w n i k 1986). W h e r e a s p h a s e s
stabilized by chemical o r d e r i n g often h a v e very simple
stoichiometrics a n d o c c u r in s y m m e t r i c a l p o s i t i o n s in
the p h a s e d i a g r a m , t h e v a r i a t i o n of a n d Tc w i t h
c o m p o s i t i o n c a n be m a r k e d l y u n s y m m e t r i c a l , t h u s
a c c o u n t i n g for a n u m b e r o f w h a t m u s t o t h e r w i s e b e
considered highly a n o m a l o u s p h a s e d i a g r a m s . I n this
respect, the inclusion of m a g n e t i c t e r m s i n t o t h e r m o
d y n a m i c calculations h a s m u c h simplified t h e overall
classification of p h a s e d i a g r a m s from a p e d a g o g i c
p o i n t of view.
By treating m a g n e t i s m in t e r m s of localized spin, it
is possible t o c o m b i n e b o t h chemical a n d m a g n e t i c
o r d e r i n g p h e n o m e n a w i t h i n t h e B r a g g - W i l l i a m s for
m u l a t i o n ( I n d e n 1982), a l t h o u g h it is clear t h a t this is
a n even c r u d e r a p p r o x i m a t i o n t h a n w h e n this is used
for chemical o r d e r i n g a l o n e . I n c r e a s e d a c c u r a c y c a n
be p r o d u c e d by u s i n g m a t h e m a t i c a l fitting functions
t o describe t h e specific-heat a n o m a l i e s associated w i t h
o r d e r i n g effects, b u t such m e t h o d s h a v e t h e d i s a d v a n
tage t h a t they a r e u n c o n n e c t e d with a n y physical
m o d e l a n d c a n therefore n o t b e used t o m a k e p r e d i c
tions of m a g n e t i c effects in e x p e r i m e n t a l l y inaccess
ible m e t a s t a b l e p h a s e s .
6. Semiempirical
Prediction
of Heats
of
Formation
A n o t h e r a r e a in w h i c h p r o g r e s s h a s been m a d e in a
semiempirical m a n n e r is t h e a p p l i c a t i o n of p a i r p o t e n t i a l t h e o r y t o t h e relative stability of c o m p o u n d s
of t h e s a m e s t o i c h i o m e t r y in different crystal s t r u c
tures ( M a c h l i n 1977). T h i s h a s o b v i o u s a p p l i c a t i o n s
in relation t o t h e e s t i m a t i o n of t h e energies of c o u n terphases. T h e p a i r - p o t e n t i a l c a l c u l a t i o n s m a d e b y
M a c h l i n use t h e face-centered-cubic s t r u c t u r e as a
reference state a n d specifically exclude a n y d - b a n d o r
charge-transfer c o n t r i b u t i o n s . T h e results give excel
lent relative stability values for different g e o m e t r i c
v a r i a n t s of A B 3 c o m p o u n d s ( a n d o t h e r s t o i c h i o m e t
rics), n o t a b l y t h o s e t h a t o c c u r as m i x t u r e s b e t w e e n
G r o u p A a n d G r o u p elements from t h e p e r i o d i c
table. T h e s a m e t e c h n i q u e also p r o d u c e s a g o o d fit
with K a u f m a n ' s t h e r m o c h e m i c a l l y - d e r i v e d i n t e r a c
tion p a r a m e t e r s for solid s o l u t i o n s b e t w e e n t r a n s i t i o n
m e t a l s (Birnie et al. 1982), b u t this m u s t be c o n s i d e r e d
p a r t l y f o r t u i t o u s since t h e m e t h o d o l o g y specifically
excludes s t r o n g {/-electron b o n d i n g .
A different a p p r o a c h t o p r e d i c t i n g t h e stability of
intermetallic p h a s e s w a s initiated b y M i e d e m a et al.
(1975). T h i s is essentially a t w o - p a r a m e t e r m o d e l
Diagrams
and Phase
Stability:
Calculations
b a s e d o n t h e a t o m i c v o l u m e s a n d t h e w o r k function
of t h e p u r e elements in t h e form in which they
n a t u r a l l y exist u n d e r s t a n d a r d c o n d i t i o n s of t e m p e r a
t u r e a n d pressure. It is a s s u m e d t h a t t h e m a c r o s c o p i c
p r o p e r t i e s used t o define t h e t w o ruling p a r a m e t e r s
c a n be a p p l i e d o n the a t o m i c scale a t t h e b o u n d a r i e s
of modified W i g n e r - S e i t z cells. T h i s semiempirical
m e t h o d for predicting b o t h t h e degree of miscibility of
t w o e l e m e n t s a n d t h e stability of intermetallic c o m
p o u n d s is surprisingly successful, b u t d o e s n o t a priori
t a k e i n t o a c c o u n t v a r i a t i o n s in stability d u e t o crystal
s t r u c t u r e . (In this respect it is c o m p l e m e n t a r y t o
M a c h l i n ' s m o d e l , w h e r e t h e e m p h a s i s is o n t h e varia
tion of energy with crystal s t r u c t u r e a t c o n s t a n t
stoichiometry.)
T h e a p p a r e n t universality of M i e d e m a ' s m e t h o d
(de B o e r et al. 1988) h a s c a u s e d theoretical physicists
t o search for t h e f u n d a m e n t a l basis for its success.
Miedema's model extrapolates macroscopic proper
ties t o t h e a t o m i c scale w i t h o u t i n v o k i n g a n y
q u a n t u m - m e c h a n i c a l principles a n d relies strongly o n
c o n c e p t s such as a t o m i c v o l u m e a n d electronegativity.
U s i n g a b a n d s t r u c t u r e m o d e l , Pettifor (1979) h a s
s h o w n t h a t there is a s e c o n d - o r d e r a t t r a c t i v e t e r m
p r o p o r t i o n a l t o t h e s q u a r e of t h e difference in a t o m i c
energy levels, which resembles t h e electronegativity
factor used by M i e d e m a . H o w e v e r , it is n o t associated
with t h e flow of c h a r g e a n d n e i t h e r is it ionic in
c h a r a c t e r . R a t h e r it reflects t h e increase in b a n d w i d t h
c o m p a r e d t o t h e p u r e c o n s t i t u e n t s . A similar analysis
of M i e d e m a ' s second t e r m indicates t h a t the success
of his semiempirical t r e a t m e n t m a y be d u e t o a
j u d i c i o u s choice of p a r a m e t e r s t h a t reflect certain
d o m i n a n t t r e n d s in t h e p e r i o d i c table, b u t which a r e
n o t in themselves t h e real causes of t h e observed
changes. Both the methods developed by Machlin and
M i e d e m a h a v e nevertheless p r o v e d very useful in
estimating
stability
values
for
experimentally
inaccessible c o u n t e r p h a s e s , w i t h t h e p r o v i s o t h a t
t h e a c c u r a c y is n o t i n t e n d e d t o b e b e t t e r t h a n
1
2.5kJ mor .
7. Semiempirical
of
Methods
of Predicting
Entropies
Fusion
319
Phase Diagrams
Calculations
8. First-Principle
Stabilities
Calculations
of
Lattice
320
g r o u p s h a v e specialized in t h e t r a n s i t i o n m e t a l s ,
w h e r e t h e b o n d i n g c a n n o t be described b y i n t e r a t o m i c
p a i r p o t e n t i a l s . T h e </-band c o n t r i b u t i o n t u r n s o u t t o
be b y far t h e m o s t d o m i n a n t factor, t h u s a c c o u n t i n g
for t h e success of initial a t t e m p t s to give t h e relative
energies of face-centered-cubic, b o d y - c e n t e r e d - c u b i c
a n d h e x a g o n a l - c l o s e - p a c k e d s t r u c t u r e s o n the basis of
d b a n d s a l o n e . M a n y different a p p r o a c h e s h a v e b e e n
tried (Pettifor 1983, Skriver 1985, W a t s o n et al. 1985)
a n d it is very satisfying t o find t h a t they lead t o very
similar results. In general, state-of-the-art calcula
tions confirm t h e lattice stabilities previously d e d u c e d
from p u r e l y t h e r m o c h e m i c a l techniques a n d therefore
give f u n d a m e n t a l s u p p o r t for t h e semiempirical m e t h
o d o l o g y d e v e l o p e d since t h e mid-1960s. H o w e v e r ,
there r e m a i n s o m e discrepancies, w h o s e r e s o l u t i o n is
the subject of m u c h c u r r e n t activity.
9. First-Principle
Calculations
of
Interaction
Energies
C o l i n e t et al. (1988) h a v e recently c o n c e n t r a t e d o n
first-principle
c a l c u l a t i o n s of t h e effect of alloying
elements t h a t h a v e t h e s a m e crystal s t r u c t u r e . T h i s
a v o i d s t h e necessity of calculating lattice stabilities. It
h a s b e c o m e evident t h a t , even w h e n c h o o s i n g c o m
b i n a t i o n s of elements such as c h r o m i u m , m o l y b d e
n u m a n d t u n g s t e n w h i c h a r e adjacent in t h e periodic
table, it is necessary t o t a k e i n t o a c c o u n t s h o r t - r a n g e
chemical o r d e r so as t o o b t a i n r e a s o n a b l e c o r r e l a t i o n
with k n o w n t h e r m o c h e m i c a l i n t e r a c t i o n energies.
T h e s e w o r k e r s h a v e therefore calculated the g r o u n d state energy of solid solutions b y a c o m b i n a t i o n of
t i g h t - b i n d i n g a n d t h e cluster Bethe lattice m e t h o d
with the cluster v a r i a t i o n m e t h o d ( C V M ) for t h e
e v a l u a t i o n of t h e configurational e n t r o p y . T h e only
i n p u t s a r e the b a n d w i d t h a n d a single site energy for
each c o m p o n e n t . F i g u r e 6 s h o w s t h a t t h e miscibility
g a p is correctly p r e d i c t e d from first principles. I n the
c o n v e n t i o n a l t h e r m o c h e m i c a l t r e a t m e n t this a s y m
m e t r y c a n b e easily r e p r o d u c e d by s u b r e g u l a r solution
m o d e l s p r o v i d e d e x p e r i m e n t a l d a t a exists for t h e
system, b u t this m e t h o d clearly b e c o m e s m o r e a r b i
t r a r y w h e n it c o m e s t o m o d e l l i n g m e t a s t a b l e p h a s e s .
T h e p o t e n t i a l predictive capabilities of c o m b i n i n g
first-principle
lattice stabilities a n d solid-solution in
t e r a c t i o n s in the future a r e self-evident.
T h e w o r k of M o h r i et al. (1988) a n d Sluiter et al.
(1988) is representative of t h o s e g r o u p s using a c o m
b i n a t i o n of b a n d calculations of a t o m i c i n t e r a c t i o n s
a n d C V M calculations of c o r r e l a t i o n b e t w e e n site
o c c u p a n c y t o o b t a i n a free energy using n o adjustable
p a r a m e t e r s . M o h r i et al. used a local density func
t i o n a l a p p r o a c h t o o b t a i n i n t e r a c t i o n energies for t h e
p u r e elements a n d for A 3 B a n d A B stoichiometrics,
a n d t h e n e x t r a c t e d t h e necessary p a i r p o t e n t i a l s t o
calculate t h e p r o p e r t i e s of the r a n d o m s o l u t i o n . T h i s
is a n interesting v a r i a n t from t h e c o n v e n t i o n a l
Phase
2000
-\
L/s**
1200
\l
lOOOf800
0.1
0.2
0.3
0.4
0.5
0.6
_L
0.7
0.8
LL
0.9
1.0
Figure 6
Predicted miscibility gap for the chromium-tungsten
system vs the experimental values (Colinet et al. 1988)
m e t h o d of s t a r t i n g with t h e p r o p e r t i e s of a r a n d o m
solution a n d e x t r a c t i n g t h e necessary p a r a m e t e r s t o
allow a C V M o r M o n t e C a r l o c a l c u l a t i o n of t h e
o r d e r i n g characteristics. Since it a s s u m e s a rigidlattice m o d e l , this m e t h o d averages o u t t h e size of t h e
c o n s t i t u e n t a t o m s a n d therefore only gives g o o d
q u a n t i t a t i v e a g r e e m e n t w h e r e size differences a r e
small. A p p l y i n g these principles t o o t h e r b i n a r y c o m
b i n a t i o n s of c o p p e r , silver a n d gold a n d o t h e r m o r e
c o m p l e x systems will r e q u i r e a refinement of this
m e t h o d o l o g y before t h e results a r e of t h e a c c u r a c y
a t t a i n a b l e from p u r e l y t h e r m o c h e m i c a l t e c h n i q u e s ,
b u t this s h o u l d n o t b e t o o difficult.
H o w e v e r , it s h o u l d b e stated t h a t b e c a u s e alloys of
t r a n s i t i o n elements a n d n o n t r a n s i t i o n elements h a v e
in general been t r e a t e d b y different m e t h o d s , i n t e r m e tallic c o m p o u n d s t h a t involve e l e m e n t s from b o t h
g r o u p s (e.g., c a r b i d e s a n d b o r i d e s ) h a v e n o t received
the theoretical a t t e n t i o n they deserve.
10. First-Principle
Stability:
Calculations
16001400
and Phase
q u a l i t a t i v e t r e n d s , b u t a g a i n it is e n c o u r a g i n g t h a t
these a r e consistent with w h a t h a s been d e d u c e d from
semiempirical t h e r m o c h e m i c a l r o u t e s .
2200.
1800-
Diagrams
Calculations
of
of
Magnetic
Status
of Phase
Diagram
S u m m a r i z i n g these v a r i o u s s t r a n d s of i n f o r m a t i o n ,
t h e m o s t i m p o r t a n t features of m o d e r n p h a s e d i a g r a m
c a l c u l a t i o n s a p p e a r t o be:
(a)
(b)
t h e use of o p t i m i z a t i o n t e c h n i q u e s t o m a x i m i z e
t h e self-consistency of available t h e r m o c h e m i c a l
d a t a with p h a s e d i a g r a m i n f o r m a t i o n ,
(c)
(d)
t h e availability of a s p e c t r u m of t e c h n i q u e s t h a t
allow t h e e s t i m a t i o n of selected features of p h a s e
equilibria with v a r y i n g c o m b i n a t i o n s of accur
acy, time a n d cost, a n d
(e)
Entropy
C a l c u l a t i o n s of t h e e n t r o p y of m i x i n g d e p e n d solely
o n a k n o w l e d g e of site o c c u p a n c y a n d , therefore, n o
i m p r o v e m e n t c a n b e expected from a m o r e funda
mental approach. However, a proper calculation of
v i b r a t i o n a l a n d electronic t e r m s is m o r e difficult. I n
principle it is certainly possible t o calculate b o t h
v i b r a t i o n a l a n d electronic e n t r o p y t e r m s given t h e
band structure and the vibrational spectrum, but
these will themselves b e a c o m p l e x function of t e m
p e r a t u r e ( W a t s o n a n d W e i n e r t 1984). T h e calcula
tions of e n t r o p y c o n t r i b u t i o n s from these v a r i o u s
sources utilize m o d e l s t h a t a r e n o t c a p a b l e of being
treated as i n d e p e n d e n t from e a c h o t h e r , a n d until a
self-consistent m o d e l is evolved it will n o t b e strictly
accurate to add the various contributions. Current
a t t e m p t s m u s t therefore b e c o n s i d e r e d a s giving o n l y
Calculations
T h e s e v a r i o u s aspects a r e so interrelated t h a t it is
difficult t o c o n s i d e r t h e m in isolation, o r place t h e m in
a p a r t i c u l a r o r d e r of i m p o r t a n c e . F r o m a theoretical
p o i n t of view, t h e m o s t satisfactory aspect is t h e
c o n v e r g e n c e of values o b t a i n e d from t h e r m o c h e m i c a l
a n d a priori c a l c u l a t i o n s . F r o m a practical p o i n t of
view, t h e possibility of m a k i n g c a l c u l a t i o n s o n real
m u l t i c o m p o n e n t systems is a d r a m a t i c b r e a k t h r o u g h .
321
Phase Diagrams
and Phase
Stability:
Calculations
T h e capacity t o h a n d l e m e t a s t a b l e p h a s e s is a n ines
c a p a b l e necessity in b o t h cases. T h e decision as t o
which c o m b i n a t i o n of t e c h n i q u e s will lead t o the
o p t i m u m degree of a c c u r a c y a n d cost is a m a j o r
challenge t o c u r r e n t p r a c t i t i o n e r s , b o t h in relation t o
i m p r o v e d m o d e l l i n g a n d t o t h e design of m o r e flexible
a n d user-friendly software.
See also: Thermodynamic Activity: Measurement
Bibliography
Ackerman H, Inden G, Kikuchi R 1989 Tetrahedron
approximation of CVM for BCC alloys. Acta Metall. 37:
1-7
Agren J 1986 Modelling of the solidification process. Mater.
Res. Soc. Bull. September/October: 32-5
Bernard C 1986 Subject index for computer coupling of
phase diagrams and thermochemistry (Vols 1 through 10
1977-86). Calphad 10(3/4): 255-92
Birnie D, Machlin S, Kaufman L, Taylor 1982 Com
parison of pair potentials and thermochemical models
of the heat of formation for BCC and FCC alloys.
Calphad 6(2): 43-126
Chart T, Putland F, Dinsdale A 1980 Calculated ternary
phase equilibria for the Cr-Fe-Ni-Si system. Calphad
4(1): 27-46
Colinet C, Bessoud A, Pasturel A 1988 Theoretical determi
nation of thermodynamic data and phase diagrams for
BCC binary transition metal alloys. J. Phys. F18: 903-21
Crusius S, Inden G 1988 Order-disorder transitions in
hexagonal binary alloys: a Monte-Carlo analysis. In:
Komura S, Furukawa (eds.) 1988 Dynamics of Order
ing Processes in Condensed Matter. Plenum, New York,
pp. 139-49
de Boer F R, Brown R, Mattens W C, Miedema A R,
Niessen A 1988 Cohesion in metals. In: de Boer F R,
Pettifor D G (eds.) 1988 Transition Metal Alloys, Co
hesion and Structure, Vol. 1. North-Holland, Amsterdam
Grimwall G 1986 Thermophysical Properties of Materials.
North-Holland, Amsterdam
Gyorffy L, Staunton J B, Johnson D D, Pinski F J, Stocks
G 1989 Local density theory of magnetism and its
interrelation with compositional order in alloys. NATO
Symp. Alloy Phase Stability. Kluwer, Dordrecht, The
Netherlands, pp. 421-68
Hillert 1986 A call for increased generality. In: Bennett L
(ed.) 1986 Computer Modelling of Phase Diagrams.
Metallurgical Society of AIME, Warrendale, PA, pp. 118
Inden G 1974 Ordering and segregation reactions in BCC
alloys. Acta Metall. 22: 945-51
Inden G 1982 Continuous transformations in phase dia
grams. Bull. Alloy Phase Diagrams 2(4): 412-18
Kaufman L 1972 Calculation of binary phase diagrams.
National Physical Laboratory
Symp.
Metallurgical
Chemistry. Her Majesty's Stationery Office, London,
pp. 373-96
Kaufman L, Bernstein 1970 Computer Calculations of
Phase Diagrams. Academic Press, New York
Lukas L, Henig Th, Zimmerman 1977 Optimisation
of thermodynamic data. Calphad 1: 225-36
Machlin S 1977 Modified pair-potentials and phase
stability. Calphad 1(4): 361-77
322
Pole Figures
and Orientation
Distribution
Functions
Rolling direction
Rolling direction
(lll)[TT2]
(100) [011]
Figure 1
Typical direct pole figures showing times-random intensities: (a) {111} pole figure for copper cold rolled to 96% reduction;
(b) incomplete {200} pole figure for low-carbon steel cold rolled to 80% reduction and annealed. Two ideal orientations
are shown
r o d axis. T e x t u r e c o m p o n e n t s in sheets c a n be d e
scribed as being of the t y p e {hkl} <wvw>. T h e {hkl}
planes c a n be c o n s i d e r e d t o lie in the rolling p l a n e ,
with <wvw> directions parallel t o t h e rolling direction.
T e x t u r e s a r e usually r e p r e s e n t e d by direct o r in
verse pole figures. A m o r e s o p h i s t i c a t e d m a t h e m a t i c a l
description is p r o v i d e d by t h e crystallite o r i e n t a t i o n
d i s t r i b u t i o n function.
1. Direct
Pole
Figures
Direct p o l e figures a r e s t e r e o g r a p h i c p r o j e c t i o n s
which s h o w t h e d i s t r i b u t i o n of p l a n e n o r m a l s (poles)
with respect t o reference directions in a specimen.
T h u s , for rolled sheet, t h e specimen is c o n s i d e r e d t o
sit at the center of the reference sphere, with its
o r t h o g o n a l axes (rolling direction, n o r m a l direction,
transverse direction) aligned with t h e principal axes of
the sphere. T h e o r i e n t a t i o n of a n individual g r a i n in a
specimen c a n t h e n be r e p r e s e n t e d by p l o t t i n g t h e
positions of t h e a p p r o p r i a t e {hkl} poles relative t o the
reference directions (see Fig. 1). T h u s , for each grain
c o n t r i b u t i n g t o , say, a {100} pole figure, three poles
w o u l d a p p e a r o n the projection. If t h e t e x t u r e is
r a n d o m a n d all grains a r e c o n s i d e r e d , there will be
e q u a l n u m b e r s of poles in e q u a l a r e a s o n t h e surface
of the reference s p h e r e (there will n o t , h o w e v e r , be
323
Pole Figures
and Orientation
Distribution
Functions
c o m b i n e d transmissionreflection m e t h o d is neces
sary, o r s o m e form of c o m p o s i t e specimen is used. A
c o m p o s i t e specimen enables t h e w h o l e of the p o l e
figure t o be d e t e r m i n e d using t h e back-reflection
t e c h n i q u e . F o r i n c o m p l e t e p o l e figures, r a n d o m s a m
ples m a d e u p from p o w d e r s which h a v e been c o m
pressed a n d sintered t o p r o d u c e high density c a n be
used as a basis for n o r m a l i z a t i o n . Results o b t a i n e d
w i t h o u t using a r a n d o m s a m p l e c a n at best be c o n
sidered as s e m i q u a n t i t a t i v e . O n the o t h e r h a n d , w h e n
a c o m p l e t e pole figure h a s been d e t e r m i n e d , a p r o c e d
u r e for n o r m a l i z a t i o n with respect t o r a n d o m levels is
available which d o e s n o t require use of a r a n d o m
s a m p l e . This is because i n t r o d u c t i o n of a t e x t u r e d o e s
n o t a d d o r s u b t r a c t a n y poles from a c o m p l e t e p o l e
figure, b u t merely redistributes t h e m . T h e r e f o r e , a
s u m m a t i o n (or i n t e g r a t i o n ) of t h e intensities over the
w h o l e a r e a of t h e pole figure m u s t give t h e s a m e result
irrespective of w h e t h e r the m a t e r i a l is t e x t u r e d o r
r a n d o m . T h e s u m m a t i o n p r o c e d u r e c a n be used t o
define a n o r m a l i z a t i o n factor by which the m e a s u r e d
2. Inverse
Pole
Figures
Figure 2
Crystallite orientation distribution function plot for killed steel cold rolled to 70% reduction and annealed. The principal
feature is a fiber texture in the = 45 section. The random-intensity contour is shown dotted; other intensities are
multiples of the random intensity
324
Polymer
3. Interpretation
of Pole
Figures
4. Crystallite
Orientation
Distribution
Functions
T h e crystallite o r i e n t a t i o n d i s t r i b u t i o n
function
( C O D F ) expresses t h e p r o b a b i l i t y of a crystallite
h a v i n g a n o r i e n t a t i o n described by three a n g u l a r
r o t a t i o n s which relate the crystal axes t o t h e specimen
axes. T h e s e r o t a t i o n s a r e usually specified in t e r m s of
Euler angles a n d the different p r o c e d u r e s available for
calculating t h e C O D F use different a n g u l a r specifica
tions. T h e Euler angles c a n in t u r n be used t o deter
m i n e texture c o m p o n e n t s in the f o r m {hkl}(uvw}.
To
o b t a i n a C O D F , it is necessary t o c o m b i n e i n f o r m a
tion from several pole figures for different {hkl}; e a c h
p o i n t in the C O D F is o b t a i n e d by m e a n s of a series
e x p a n s i o n , each t e r m involving d a t a from t h e p o l e
figures.
T h e results of analyses of C O D F s a r e usually
represented graphically by p l o t t i n g the p r o b a b i l i t y of
a crystallite h a v i n g a given o r i e n t a t i o n in E u l e r i a n
space (an o r t h o g o n a l space, with the three Euler
angles as axes). T h e r e a r e difficulties in m a k i n g threed i m e n s i o n a l p l o t s , a n d t h u s t h e C O D F p l o t is c o n v e n
tionally p r e s e n t e d as a series of sections t a k e n n o r m a l
to o n e of the axes. A s with t h e pole figures, c o n t o u r
m a p p i n g is used, with t h e value u n i t y representing t h e
intensity of a r a n d o m s a m p l e . I n d e x i n g c h a r t s a r e
available for the identification of specific ideal orien
t a t i o n s . F i g u r e 2 s h o w s a representative e x a m p l e of a
C O D F plot. T h e C O D F is n o r m a l i z e d by s u m m i n g
the intensities over t h e w h o l e of o r i e n t a t i o n space a n d
setting the value o b t a i n e d e q u a l t o t h a t for a r a n d o m
sample.
T h e p a r a m o u n t a d v a n t a g e of t h e C O D F as a
description of t e x t u r e is t h a t it p r o v i d e s q u a n t i t a t i v e
i n f o r m a t i o n a b o u t t h e s p r e a d of o r i e n t a t i o n s in a
textured s a m p l e . A d d i t i o n a l l y , t h e severity of t e x t u r e
c a n be d e t e r m i n e d from t h e C O D F by calculating t h e
s t a n d a r d d e v i a t i o n of t h e function from t h a t of a
r a n d o m m a t e r i a l . T h e C O D F c a n also be used t o
Dielectric
Properties:
Test
Methods
Bibliography
Barrett C S, Massalski 1966 Structure of Metals, 3rd
edn. McGraw-Hill, New York
Bunge J 1982 Texture Analysis in Materials Science.
Butterworth, London
Davies G J 1976 Texture analysis and anisotropy in metals.
J. Met. 28(7): 21-8
Grewen J, Huber J 1978 Annealing textures. In: Haessner F
(ed.) 1978 Recrystallization of Metallic Materials, 2nd
edn. Dr. Riederer Verlag, Stuttgart, Germany, pp. 111-36
Hatherly M, Hutchinson W 1979 An Introduction to
Textures in Metals, Institution of Metallurgists Mono
graph No. 5. Institution of Metallurgists, London
G . J. Davies
[University of Sheffield, Sheffield, U K ]
7. Theoretical
Considerations
4
325
Polymer
Dielectric
Properties:
Test
Methods
l u m p e d circuit elements. T h e a d m i t t a n c e Ys of t h e
s a m p l e is t h u s s e p a r a t e d i n t o c a p a c i t a n c e C s a n d
conductance G *
r s = j o > C s + Gs
0)
w h e r e is t h e frequency. T h e c o m p l e x permittivity *
() is t h e n o b t a i n e d by dividing Ys b y t h e a d m i t t a n c e
Yv associated with t h e g e o m e t r i c ( v a c u u m ) c a p a c i
t a n c e C v of t h e s a m p l e :
Yv=)coC,=)coe0A/d
2
e'-)e"
( C s/ C v) - j ( G > C v)
(4)
GJcoCs
(5)
If t h e d i m e n s i o n s of t h e dielectric a p p r o a c h t h e
wavelength c o r r e s p o n d i n g t o t h e m e a s u r e m e n t fre
q u e n c y , l u m p e d circuit e l e m e n t analysis is i n a p p r o
p r i a t e . T h e s a m p l e is t h e n often i n c o r p o r a t e d i n t o a
t r a n s m i s s i o n line a n d t r e a t e d as a d i s t r i b u t e d element.
T h e s e m e a s u r e m e n t t e c h n i q u e s a r e c o m m o n in t h e
8
1 0
1 0 - 1 0 H z region. T h e p r o p a g a t i o n c o n s t a n t c o n
sists of b o t h a t t e n u a t i o n a n d p h a s e :
y=
(6)
(X+)b
= (g + Jo>c) x ( r +
dielectric
Teletype
))
conductors
(7)
T h e a t t e n u a t i o n includes a c o m p o n e n t d u e t o t h e
c o n d u c t o r s a n d a c o m p o n e n t d u e t o t h e dielectric.
T h e s e p a r a t i o n of these for a low-loss dielectric is
often difficult.
Transient
Methods
T r a n s i e n t t e c h n i q u e s a r e used t o o b t a i n c o m p l e x
permittivities a u t o m a t i c a l l y over w i d e - r a n g i n g fre
4
6
q u e n c y d o m a i n s . Systems from 1 0 ~ - 1 0 H z a r e b a s e d
o n collection of t h e dielectric's t i m e - d e p e n d e n t , inte
g r a t e d c u r r e n t r e s p o n s e t o a u n i t step pulse. T h e s e
discrete d a t a a r e t h e n t r a n s f o r m e d t o o b t a i n
f r e q u e n c y - d e p e n d e n t , c o m p l e x permittivities. T h i s
326
-^Capacitor
/(/)
Ll
Rotter
A/D
converter
I/O 14
Q{t)
Integrator
I/O 16
Figure 1
Schematic representation of a computer-controlled system
for determining complex permittivities by a transient
method
t e c h n i q u e is suited t o c o m p u t e r - c o n t r o l l e d o p e r a t i o n
(Fig. 1).
T o o b t a i n t h e frequency r e s p o n s e of t h e a d m i t t a n c e
Y]co) of a dielectric it is necessary t o t r a n s f o r m b o t h
t h e impressed v o l t a g e Vt) a n d t h e dielectric's c u r r e n t
r e s p o n s e 7S(/):
) = / )/ )
(8)
T h e t r a n s f o r m of t h e voltage c a n be f o u n d analyti
cally by a s s u m i n g t h e impressed voltage t o be a step
function:
)=0
(9)
5())/())
(10)
I(]co)=\
2.
Pulser
1/016
Computer
(3)
Temperature
monitor
Disk
(2)
w h e r e A is s a m p l e a r e a ( c m ) , d is s a m p l e thickness
1
(cm) a n d 0 = 8.85 x l O ^ F c m " . T h e n ,
8*(co)=YJY,
Temperature
control
Time base
generator
J0
()->
()
T h i s b e h a v i o r c a n n o t , h o w e v e r , be m o n i t o r e d experi
m e n t a l l y , a n d in fact d a t a a r e o b t a i n e d periodically
a n d c h a r g e , n o t c u r r e n t , is followed.
T h e d a t a a r e n o r m a l l y collected as t h e i n t e g r a t e d
c u r r e n t responses Q(tJ, w h e r e t h e times tm a r e equally
spaced in log time (e.g., 1, 2, 4, 8, . . . ) . A discrete
F o u r i e r t r a n s f o r m is used. T h e first d a t a p o i n t Q(t^)
m a y be c o n s i d e r e d t o represent i n s t a n t a n e o u s p o l a r i
zation:
Polymer
Q(tx) = p / ( O e J
j a ,/
dt
Dielectric
(12)
Properties:
Test
Methods
3.
Bridges
Null
indicotor
Figure 2
Harris low-frequency bridge
Figure 3
Schematic representation of a meter
s e p a r a t i o n of resistive a n d capacitive c o m p o n e n t s of
t h e i m b a l a n c e signal. P h a s e s e p a r a t i o n is valuable
w h e n m e a s u r i n g low-loss m a t e r i a l s subject t o capaci
tive drifts.
T h e r e a r e m a n y o t h e r sensitive bridges covering
p a r t s of t h e frequency r a n g e from 10 H z t o 1 M H z .
T h e r e a r e also m a n y i m p e d a n c e m e t e r s available
w h i c h a r e often classed as vector v o l t m e t e r s instead of
bridges. T h e y a r e useful w h e n m e a s u r i n g m o d e r a t e - t o
high-loss dielectrics. T h e s e i m p e d a n c e m e t e r s h a v e
c o m p u t e r interfacing a n d c a n a u t o m a t i c a l l y collect
dielectric d a t a over a wide frequency r a n g e .
4. Resonant
Methods
5
Precise m e a s u r e m e n t s from 10 H z t o 10 H z m a y b e
o b t a i n e d by r e s o n a n t m e t h o d s using l u m p e d circuit
6
a p p r o x i m a t i o n s , a n d a b o v e 10 H z these m e t h o d s a r e
used for m o s t low-loss p o l y m e r m e a s u r e m e n t s . T h e
c a p a c i t a n c e v a r i a t i o n m e t h o d of H a r t s h o r n a n d W a r d
(1936) gives g o o d results, a n d e x p e r i m e n t a l systems
derived from this m e t h o d a r e in wide use for p o l y m e r
research a n d q u a l i t y c o n t r o l of, for e x a m p l e , o c e a n
cable dielectrics. O n e such system (the Q m e t e r ) is
s h o w n in Fig. 3. T h e Q of t h e circuit is m o n i t o r e d
directly a n d t h e c h a n g e in Q is related t o t a n S2:
tan S2 = (CJC2)[(Ql
- Q2)IQXQ1\
(14)
w h e r e C 0 is t h e t o t a l r e s o n a n t c a p a c i t a n c e , Qx is the
m e a s u r e m e n t w i t h o u t the s a m p l e a n d Q2 is the
m e a s u r e m e n t w i t h the s a m p l e . T h e lead i n d u c t a n c e
s h o u l d n o t be i g n o r e d in a n a l y z i n g d a t a a b o v e a few
M H z , a n d for t h e m o s t a c c u r a t e m e a s u r e m e n t s the
series resistance of the leads is also i m p o r t a n t .
8
9
A r e s o n a n t t e c h n i q u e for t h e 1 0 - 1 0 H z r a n g e is
t h e r e - e n t r a n t cavity; it is useful for m o d e r a t e - t o
low-loss m a t e r i a l s . W o r k s et al. (1944) describe a n
excellent system for precise m e a s u r e m e n t s by this
t e c h n i q u e . A simplified cavity is s h o w n in Fig. 4. T h e
half-width of t h e r e s o n a n c e is m e a s u r e d either by
capacitive d e t u n i n g o r frequency v a r i a t i o n . A u t o
m a t e d systems h a v e used frequency v a r i a t i o n t o fit the
r e s o n a n c e c u r v e t o its analytical form. T h e Q of the
circuit is defined a s t h e r e s o n a n t frequency fm divided
by t h e frequency difference / b e t w e e n half-power
327
Polymer
Dielectric
Properties:
Test
Methods
High
Sample
Figure 5
A three-terminal electrode system
Sample
V///
Figure 4
Schematic representation of a re-entrant cavity
p o i n t s . If a s a m p l e is r e s o n a t e d a n d t h e n replaced b y
a n air c a p a c i t a n c e which is equivalent ( i . e . , / m is the
s a m e ) t h e s a m p l e loss is
t a n S2 = ( C 0 / C 2 ) [ ( l / f t a
=
Low
"X"
Detector
Input -
m p
l/6air)]
I)e -
(15)
significant e r r o r s , a n d e v a p o r a t e d electrodes a g a i n
c a n be used t o eliminate this. Since fringing effects a r e
significant, disk s a m p l e s w h e r e t h e electrodes e x t e n d
to the edge of the s a m p l e are n o r m a l l y c h o s e n . T h e
fringing c a p a c i t a n c e (in p F ) is t h e n given by
C e = P(0.29 - 0.58 log d)
(16)
w h e r e is s a m p l e p e r i m e t e r (cm) a n d d is s a m p l e
thickness (cm). O t h e r configurations m a y be c h o s e n
a n d A S T M D - 1 5 0 defines fringing c o r r e c t i o n s .
^distributed
* associated with t h e r e s o n a t i n g i n d u c t a n c e
a n d is i n d e p e n d e n t of t h e s a m p l e g a p . It is d e t e r m i n e d
empirically for a given cavity. E x p e r i m e n t a l l y , the use
of a vernier c a p a c i t o r causes c o u p l i n g p r o b l e m s a n d
s h o u l d be a v o i d e d . A l s o , this m e t h o d is n o t strictly a
l u m p e d circuit r e s o n a n c e . E r r o r s in fringe field c o r r e c
tions lead t o a less a c c u r a t e d e t e r m i n a t i o n of ' t h a n in
Q meters.
Qistributed
6. Microwave
8
Measurements
11
5. Electrode
328
e =m) n +
Systems
rt )]
2
" =
(17)
2(/)\ / )
(18)
']
(19)
= ( +
w h e r e is a c o n s t a n t of the e m p t y guide.
T h e e x p e r i m e n t a l s e t u p c a n be either a slotted (Fig.
6) o r n o n s l o t t e d line. N o r m a l l y a t r a n s c e n d e n t a l
e q u a t i o n m u s t be solved t o o b t a i n t h e c o m p l e x s a m p l e
p r o p a g a t i o n c o n s t a n t . W i t h p o l y m e r s it is often p o s
sible t o c h o o s e a half-wave s a m p l e since ' is k n o w n
a d e q u a t e l y . T h e m e a s u r e m e n t frequency c a n be used
as a variable in o b t a i n i n g half-wave r e s o n a n c e ; t h e
loss " m a y t h e n be o b t a i n e d in a simpler fashion.
Source
Sample
Figure 6
Transmission line (waveguide) with slotted line detector
Polymers:
M i c r o w a v e r e s o n a t o r s a r e a n a l t e r n a t i v e w a y of
d e t e r m i n i n g t h e c o m p l e x permittivity in t h e m i c r o
wave region. F o r filled r e s o n a t o r s , ' is o b t a i n e d from
the difference in Q b e t w e e n a filled a n d e m p t y cavity.
F r e q u e n c y v a r i a t i o n defines t h e r e s o n a n c e of t h e
cavity as
Q ~~ ./resonance/A/half power
In a d d i t i o n t o s t a n d a r d m i c r o w a v e t e c h n i q u e s , pulse
techniques a r e b e c o m i n g m o r e useful in s t u d y i n g
p o l y m e r s . C o m p u t e r c o n t r o l a n d analysis a r e m a k i n g
t i m e - d o m a i n t e c h n i q u e s m o r e i m p o r t a n t (Suggett
1972), a n d i m p r o v e m e n t s t o t h e e x p e r i m e n t a l a p p a r a
tus a n d d a t a analysis h a v e been m a d e . A s w i t h
low-frequency t r a n s i e n t t e c h n i q u e s , t i m e - d o m a i n
techniques a r e useful for m o d e r a t e - t o high-loss
dielectrics b u t i n a p p r o p r i a t e for low-loss dielectrics.
Bibliography
Barrie I 1965 Measurement of very low dielectric losses at
radio frequencies: new experimental technique based on
method of Hartshorn and Ward. Proc. Inst. Electr. Eng.
112: 408-15
Hartshorn L, Ward W 1936 The measurement of permit
tivity
and8 power factor of dielectrics at frequencies from
4
10 to 10 cycles per second. Proc. Inst. Electr. Eng. 79:
597-609
Hill , Vaughan W E, Price A H, Davies 1969
Dielectric Properties and Molecular Behaviour. Van Nostrand Reinhold, London
King R W 1965 Transmission Line Theory. Dover, New
York
McCrum G, Read , Williams G 1969 Anelastic and
Dielectric Effects in Polymeric Solids. Wiley, New York
Scheiber D J 1961 An ultra low frequency bridge for
dielectric measurements. J. Res. Natl. Bur. Stand. C 65:
23-42
Scott A H, Curtis L 1939 Edge correction in the determi
nation of dielectric constant. / . Res. Natl. Bur. Stand. 22:
747-75
Suggett A 1972 Time domain methods. Dielectr. Relat. Mol.
Processes 1: 100-20
von Hippel A R (ed.) 1954 Dielectric Materials and Applica
tions. Wiley, New York
Works C N, Dakin W, Boggs F W 1944 A resonant cavity
method for measuring dielectric properties at ultra-high
frequencies. Trans. Am. Inst. Electr. Eng. 63: 1092-8
G . E. J o h n s o n
[ A T & T Bell L a b o r a t o r i e s , M u r r a y Hill,
N e w Jersey, U S A ]
Electron
Microscopy
T h e i n f o r m a t i o n r e q u i r e d b y a p o l y m e r scientist is n o t
a b o u t t h e s t r u c t u r e itself, b u t a b o u t t h e r e l a t i o n s h i p
b e t w e e n t h e s t r u c t u r e a n d p r o p e r t i e s . T h u s , the in
vestigation of t h e s t r u c t u r a l details d o w n t o a m o l e c u
lar level is often necessary. It is, h o w e v e r , extremely
difficult t o resolve m o l e c u l a r s t r u c t u r e s in c o m m e r c i a l
p o l y m e r s with t h e electron m i c r o s c o p e , n o t only
b e c a u s e of their highly d i s o r d e r e d a n d a t best semicrystalline n a t u r e , b u t m a i n l y b e c a u s e of p r o b l e m s
with specimen p r e p a r a t i o n
and
electron-beam
d a m a g e . T h i s limits t h e r e s o l u t i o n in m o s t cases t o
a b o u t 5 n m , which is n o t sufficient for lattice o r
a t o m i c r e s o l u t i o n . A n e x c e p t i o n t o this rule is the
h i g h - r e s o l u t i o n electron m i c r o s c o p y of specially p r e
p a r e d single crystals of p o l y e t h y l e n e a n d paraffins
w h e r e lattice r e s o l u t i o n of less t h a n 0.5 n m h a s been
achieved ( C h a n z y et al. 1986). T h e electron m i c r o s
c o p y of c o m m e r c i a l p o l y m e r s c a n nevertheless p r o
vide s o m e very useful i n f o r m a t i o n o n the a r r a n g e m e n t
of molecules i n t o larger g r o u p s , such as crystal units
in spherulite lamellae, p h a s e s in p o l y m e r blends o r
d i s p e r s i o n of additives. It is always beneficial t o utilize
s o m e o t h e r t e c h n i q u e s a n d t o o b t a i n as m u c h a d d i
tional information on the structure and composition
of t h e specimen as possible. T h e electron m i c r o s c o p y
of p o l y m e r s s h o u l d t h u s be seen as a s o u r c e of u n i q u e
but not unlimited information.
T h e r e a r e several electron m i c r o s c o p y techniques
available, e a c h h a v i n g its o w n specific a d v a n t a g e s a n d
l i m i t a t i o n s . T h e s e t e c h n i q u e s v a r y c o n s i d e r a b l y with
respect t o the degree of difficulty with which results
c a n b e o b t a i n e d a n d t h e different i n f o r m a t i o n a b o u t
t h e p o l y m e r m i c r o s t r u c t u r e t h a t they p r o v i d e .
1. Scanning
Electron
Microscopy
T h i s t e c h n i q u e is p e r h a p s t h e easiest t o use a n d t h e
specimen p r e p a r a t i o n least d e m a n d i n g . It utilizes
s e c o n d a r y a n d b a c k - s c a t t e r e d electrons t o f o r m im
ages of surface relief. S e c o n d a r y electrons c a n only
escape from a thin surface layer a n d for this r e a s o n
low-energy electrons, typically 5 - 1 0 k e V , a r e used for
p o l y m e r s . T h e b a c k - s c a t t e r e d electron images require
t h e use of higher accelerating voltages ( 2 0 - 4 0 keV)
a n d a r e of b e t t e r q u a l i t y for specimens c o n t a i n i n g
heavier elements t h a n for p o l y m e r s .
Surfaces of b u l k specimens c a n b e p r e p a r e d easily
b y c u t t i n g , e t c h i n g o r fracturing. T o r e d u c e t h e c h a r g
ing effect i n d u c e d b y t h e incident electron b e a m , a
thin layer of gold o r o t h e r m e t a l is s p u t t e r e d o n t o the
surface in o r d e r t o increase t h e c o n d u c t i v i t y of the
specimen. T h i s results in a grainy surface s t r u c t u r e
(see F i g . lb), w h i c h is visible only a t higher magnifica
tions. T h e magnifications available o n m o s t m i c r o
scopes a n d achieved routinely, a r e usually n o t higher
t h a n x 20 000. T h i s gives a r e s o l u t i o n of a b o u t 20 n m ,
w h i c h is sufficient for m o s t a p p l i c a t i o n s , such as
fracture surface analysis (Fig. la), p o l y m e r b l e n d s
329
Polymers:
Electron
Microscopy
Figure 2
Scanning electron micrograph of a polyethylenepolycarbonate blend. The dispersion of phases is clearly
visible. The surface damage due to cutting results in the
debonding of the polycarbonate phase from the matrix
(courtesy of S. Woodisse)
2. Replica
Figure 1
Scanning electron micrograph of a low-temperature
fracture surface of a polyethylene composite. The
distribution of the filler particles can be studied in
addition to the mode of crack propagation: (a), the
fibrillated structure of a ductile fracture; (b), the same area
showing the grainy structure of the conductive gold
coating
330
Techniques
A l t h o u g h t h e s c a n n i n g electron m i c r o s c o p e ( S E M )
t e c h n i q u e c a n p r o v i d e useful i n f o r m a t i o n o n larger
i n h o m o g e n e i t i e s in p o l y m e r m a t r i c e s , it h a s a rela
tively low r e s o l u t i o n , low c o n t r a s t o n small surface
steps a n d t h e specimen surface quickly c h a n g e s as a
result of t h e e l e c t r o n - b e a m d a m a g e . M a n y m i c r o s copists, therefore, prefer t o r e m o v e t h e p o l y m e r
a n d investigate only t h e c o n d u c t i v e c o a t i n g layer in
t h e t r a n s m i s s i o n m o d e . T h e c o n t r a s t a n d the t h r e e d i m e n s i o n a l effect is preserved by e v a p o r a t i n g a h e a v y
m e t a l ( g o l d - p a l l a d i u m alloy o r p l a t i n u m ) a t a small
angle t o t h e surface ( s h a d o w i n g ) . E v a p o r a t e d c a r b o n
is used exclusively as t h e s u p p o r t i n g m a t e r i a l b e c a u s e
of its s t r e n g t h a n d t r a n s p a r e n c y . It is n o t always easy
t o r e m o v e t h e t h i n c a r b o n film from t h e b u l k p o l y m e r
Polymers:
Electron
Microscopy
3. Transmission
Electron
Microscopy
of
Thin
Films
Specimen p r e p a r a t i o n a n d b e a m d a m a g e a r e t h e t w o
m a j o r p r o b l e m s w h e n a p p l y i n g this t e c h n i q u e t o
p o l y m e r s . M a n y excellent t e c h n i q u e s for specimen
p r e p a r a t i o n of biological m a t e r i a l s h a v e been d e
veloped, b u t u n f o r t u n a t e l y o n l y very few c a n b e
utilized for p o l y m e r s , m a i n l y b e c a u s e of their c h e m
ical resistance a n d t o u g h , r u b b e r y n a t u r e . Suitable
specimens for electron m i c r o s c o p y m u s t be of even
t h i c k n e s s , less t h a n 1 thick for 100 k e V , with
u n d a m a g e d surfaces a n d of a sufficient c o n t r a s t . T w o
t e c h n i q u e s a r e available: c u t t i n g a n d solvent casting.
Figure 3
Scanning electron micrograph of a surface of a rapidly
cooled polyethylene. The morphology in the center
is revealed by electron-beam damage (courtesy of
S. Woodisse)
by dissolving t h e p o l y m e r in solvents a n d a t w o - s t a g e
replica t e c h n i q u e is m o r e c o m m o n l y used. T h e surface
relief of t h e specimen is first " c a s t e d " o r " p r i n t e d "
o n t o a n easily soluble c o m p o u n d , such as polyacrylic
acid, gelatin o r F o r m v a r , w h i c h is t h e n peeled off t h e
p o l y m e r a n d used for t h e p r e p a r a t i o n of a c a r b o n
replica.
T h e surface relief c a n b e p r e p a r e d in t h e s a m e w a y
as for t h e S E M specimens, b u t b e c a u s e a h i g h e r
resolution a n d c o n t r a s t a r e available, s o m e o t h e r
techniques c a n b e utilized. P e r h a p s t h e m o s t i m p o r t
a n t of these alternatives is surface-etching w i t h a n
oxidizing agent, such as p o t a s s i u m p e r m a n g a n a t e , in
solution with sulfuric a n d p h o s p h o r i c acids (Olley et
al. 1979). It is believed t h a t t h e a m o r p h o u s m a t r i x is
r e m o v e d p r i o r t o t h e crystalline p h a s e , t h u s revealing
the spherulite lamellae. Alternatively, t h e lamellar
s t r u c t u r e c a n b e revealed b y c u t t i n g t h e specimen a t
low t e m p e r a t u r e . T h e c r a c k , p r o p a g a t i n g in front of
the c u t t i n g knife edge, follows t h e w e a k p r o b a b l y
interlamellar regions, leaving a surface relief w h i c h is
similar t o the etched surface (Fig. 4).
T h e replication t e c h n i q u e is very r e w a r d i n g , as it
provides h i g h - c o n t r a s t m i c r o g r a p h s a n d is relatively
easy t o use. T h e d i s a d v a n t a g e of this t e c h n i q u e is t h a t
the resolution is limited b y t h e g r a i n size of t h e
s h a d o w i n g m e t a l t o a b o u t 10 n m ; this m a k e s t h e
3.1 Specimen
Preparation
(a) Cutting. A m o r p h o u s p o l y m e r s c a n b e c u t o n a n
u l t r a m i c r o t o m e w i t h a glass o r d i a m o n d knife a t a
t e m p e r a t u r e w h i c h is lower t h a n t h e glass t r a n s i t i o n of
t h e p o l y m e r ( a b o v e r o o m t e m p e r a t u r e for m o s t a m o r
p h o u s p o l y m e r s ) . A n e x a m p l e of a n acrylonitrile
b u t a d i e n e styrene ( A B S ) p o l y m e r is s h o w n in F i g . 5.
T h e b u l k p o l y m e r h a s b e e n stained with o s m i u m
Figure 4
Transmission electron micrograph of a two-stage replica
prepared from a cut, unetched surface revealing the
spherulite morphology (courtesy of S. Woodisse)
331
Polymers:
Electron
Microscopy
in w a t e r . It is n o t very easy to p r o d u c e films of even
thickness a n d the t e m p e r a t u r e of the s u b s t r a t e , as well
as t h e c o n c e n t r a t i o n of the solution, m u s t be carefully
c o n t r o l l e d . T h i s is t h e m a j o r t e c h n i q u e which p r o
vides films suitable for c r y s t a l l o g r a p h i c studies.
A n o t h e r t e c h n i q u e which c a n b e used is derived
from the e t c h i n g a n d single-stage replica p r o c e d u r e , in
which t h e p o l y m e r s u b s t r a t e is only partially dis
solved, leaving small debris of t h e crystalline p o l y m e r
a t t a c h e d t o t h e c a r b o n film. T h i s c o m b i n e s the high
c o n t r a s t of t h e surface relief with a possibility of
o b t a i n i n g diffraction p a t t e r n s a n d t h u s s t r u c t u r e related c r y s t a l l o g r a p h i c i n f o r m a t i o n ( N o r t o n a n d
Keller 1985).
3.2 Electron-Beam
Figure 5
Transmission electron micrograph of a thin section cut
from ABS copolymer. The butadiene phase is stained with
osmium tetroxide
Damage
332
Figure 6
Transmission electron micrograph of a cut section of
polyethylene, exposed to chlorosulfonic acid and stained
with osmium tetroxide. The dark lines probably
correspond to the amorphous interlamellar regions
(courtesy of S. Woodisse)
Polymers:
200
400
600
D(C
800
rrf )
Figure 7
Changes in chlorine content and specimen thickness with
exposure to the electron beam D measured by x-ray
analysis and mass loss, respectively
A)exp(-
kxD)
+ A exp(-
k2D)
w h e r e A, kx a n d k2 a r e t h e d e c a y c o n s t a n t s . T h i s
function c o r r e s p o n d s t o t w o i n d e p e n d e n t chemical
processes, w h i c h a r e different for e a c h p o l y m e r . T h e
m e a s u r e d curves (or t h e d e c a y c o n s t a n t s ) c a n t h u s be
utilized for p o l y m e r c h a r a c t e r i z a t i o n o r identification
( F i n c h a n d Vesely 1987).
It m a y be o b v i o u s from t h e e x p o n e n t i a l n a t u r e of
the decay t h a t it is n o t possible t o o b t a i n i m a g e s of
u n d a m a g e d m a t e r i a l . T h e e x p o s u r e of t h e specimen
m u s t m a t c h t h e e x p o s u r e of t h e p h o t o g r a p h i c e m u l
sion. T h i s m e a n s , for e x a m p l e , t h a t for a p o l y e t h y l e n e
specimen, 100 keV, x 10 000 magnification a n d t h e
m o s t sensitive film available, only o n e o r t w o e x p o
sures of t h e s a m e a r e a c a n be o b t a i n e d before t h e
crystallinity of the specimen is lost. T h i s is insufficient
for a n y serious c r y s t a l l o g r a p h i c s t u d y a n d new o r
i m p r o v e d t e c h n i q u e s a r e needed.
It is essential, p r i m a r i l y , t o avoid a n y u n n e c e s s a r y
p r e i r r a d i a t i o n of t h e specimen. F o r this r e a s o n focus
ing a n d a l i g n m e n t of t h e b e a m a r e often p e r f o r m e d o n
a n a r e a adjacent t o t h e a r e a of interest a n d t h e
Electron
Microscopy
4. Scanning
Transmission
Electron
Microscope
T h e s c a n n i n g t r a n s m i s s i o n electron m i c r o s c o p e
( S T E M ) h a s facilities for s c a n n i n g t h e electron b e a m
a c r o s s t h e specimen. T h e b e a m is focused t o a small
p r o b e b y c o n d e n s e r lenses a n d a highly excited objec
tive lens. D e t e c t o r s for t r a n s m i t t e d , scattered ( d a r k field) a n d s e c o n d a r y electrons a r e of t h e scintillator/
p h o t o m u l t i p l i e r t y p e a n d h a v e a low noise level with a
g o o d signal amplification. T h e d e t e c t o r efficiency is
increased with t h e accelerating v o l t a g e , which is a n
i m p o r t a n t a d v a n t a g e . It is t h u s possible t o w o r k a t
very low b e a m - c u r r e n t densities for searching a n d
focusing, a n d t o switch t o a h i g h e r c u r r e n t density for
t h e i m a g e r e c o r d i n g only. T h e excellent c o n t r o l of the
b e a m , its a c c u r a t e l o c a t i o n o n t h e specimen w i t h o u t
a n y d a m a g e t o t h e s u r r o u n d i n g regions a n d r e c o r d i n g
of i m a g e s at low c u r r e n t densities m a k e this t e c h n i q u e
ideally suited for m i c r o s c o p y of beam-sensitive m a t e r
ials in the m e d i u m magnification r a n g e (Vesely 1977).
T h e lenses below t h e specimen a r e used t o converge
t h e b e a m o n t o t h e d e t e c t o r , so t h a t a m i n i m u m
a m o u n t of intensity is lost. T o i m p r o v e t h e c o n t r a s t of
t h e system, it is also i m p o r t a n t to d e s c a n the b e a m so
t h a t only t h e t r a n s m i t t e d b e a m (or for t h e dark-field,
the diffracted b e a m ) enters t h e d e t e c t o r t h r o u g h the
a p e r t u r e . T h e d a r k field c a n be o b t a i n e d simply by
deflecting t h e b e a m below t h e specimen. T h i s d o e s n o t
r e q u i r e tilting of t h e specimen, as in c o n v e n t i o n a l
m i c r o s c o p y . A n e x a m p l e of t h e a p p l i c a t i o n of this
333
Polymers:
Electron
Microscopy
Figure 8
Scanning transmission electron micrograph of a solvent-cast and slowly crystallized polyethylene. Bright-field (a) and
three dark-field images (b), (c), (d) of the same area, using the 020 reflection, show the segmental grouping of spherulite
lamellae
t e c h n i q u e is s h o w n in F i g . 8, w h e r e a bright-field
a n d three dark-field i m a g e s of the s a m e a r e a o n a
polyethylene spherulitic film a r e s h o w n .
334
Polymers:
Electron
Microscopy
Bibliography
Figure 9
Scanning transmission electron micrograph of a
polyethylene single crystal in 110 dark-field.
Microdiffraction patterns were taken from two points in
the central area. The dark circles (0.25 m diam) show that
the loss of crystallinity is confined only to the area of
microdiffraction. One microdiffraction pattern is inserted
for illustration
focused t o a p r o b e of a selected d i a m e t e r (between
30 n m a n d 10 ) a n d a parallel b e a m c a n b e f o r m e d ,
so t h a t t h e diffraction s p o t s a r e very s h a r p . T h e
c a m e r a length c a n b e altered b y a projective lens a n d
the p a t t e r n r e c o r d e d in t h e s a m e w a y a s for c o n v e n
tional m i c r o s c o p y . T h e p r o b e d i a m e t e r m u s t b e
selected for t h e best c o m p r o m i s e b e t w e e n t h e b e a m
d a m a g e t o t h e specimen a n d t h e sensitivity o f t h e
p h o t o g r a p h i c p l a t e . Typically, for highly sensitive
p o l y m e r s t h e diffraction a r e a c a n b e a s small a s
100 n m ( L o w et al. 1978, Vesely a n d R o n c a 1985).
This is illustrated in F i g . 9, w h e r e t h e dark-field i m a g e
s h o w s clearly t h e loss of crystallinity only in t h e a r e a s
exposed t o t h e b e a m . A diffraction p a t t e r n is also
s h o w n . T h e a d v a n t a g e s of t h e microdiffraction tech
n i q u e a r e t h e a c c u r a t e p o s i t i o n i n g o f t h e electron
b e a m o n t h e a r e a of interest with n o u n w a n t e d
i r r a d i a t i o n o f t h e adjacent r e g i o n s , a small selected
a r e a for t h e diffraction a n d t h e high q u a l i t y of t h e
diffraction p a t t e r n s .
5.
Conclusion
L o w - r e s o l u t i o n electron m i c r o s c o p y ( a b o v e 20 n m ) of
a m o r p h o u s p o l y m e r s a n d surface replicas is relatively
335
Polymers:
Light
Microscopy
1. Specimen
Polymer
Electron
Light
microscopy
C o m m o n light
microscopy
microscopy
microscopy
R e f l e c t e d light
microscopy
Preparation
Microradiography
Acoustic
microscopy
Transmitted light
microscopy
Polarized
light
Common light
microscopy
Polarized light
microscopy
Ultraviolet a n d infrared
microscopy
microscopy
Interference
methods
j
Ultraviolet
fluorescence
microscopy
1
Differential
methods
Qualitative
methods
Quantitative
methods
Dark-field
microscopy
Dispersion
staining
Quantitative
methods
Phase-sensitive
methods
1
Differential
interfence
contrast
Quantitative
interference
methods
Phase contrast
Modulation
contrast
Figure 1
Main light microscopy techniques applicable to polymers and their interrelationships
336
Schlieren
microscopy
Polymers:
2. Transmitted-Light
Methods
T h e t r a n s m i t t e d - l i g h t e x a m i n a t i o n of thin sections, o r
o t h e r thin specimens, represents t h e m a i n field of
a p p l i c a t i o n of the light m i c r o s c o p e . T h e choice of
t e c h n i q u e d e p e n d s o n t h e n a t u r e of the specimen a n d
w h e t h e r qualitative o r q u a n t i t a t i v e i n f o r m a t i o n is
needed. S o m e of the m o r e i m p o r t a n t t e c h n i q u e s
s h o w n in Fig. 1 a r e discussed in Sects. 2 a n d 3. Details
of the simpler t e c h n i q u e s , such as bright-field a n d
dark-field m i c r o s c o p y , a n d their a p p l i c a t i o n s , c a n be
found in the literature ( H e m s l e y 1984, Sawyer a n d
G r u b b 1987).
Light
Microscopy
Figure 2
Microstructure of a thin section of high-density
polyethylene cooled slowly from the melt, imaged using
crossed polars
2.1 Polarized-Light
Microscopy
Polarized-light m i c r o s c o p y is recognized as o n e of
the m a i n m e t h o d s of e x a m i n i n g p o l y m e r i c materials.
T h e t e c h n i q u e s used m a y be either qualitative o r
quantitative.
(a) Qualitative methods. T h e p o l a r i z i n g m i c r o s c o p e is
n o r m a l l y used in the " c r o s s e d p o l a r s " configuration.
T h e w i d e s p r e a d use of this t e c h n i q u e stems from the
fact t h a t a l m o s t all semicrystalline p o l y m e r s , a n d
a m o r p h o u s polymers showing molecular orientation,
exhibit d o u b l e refraction, o r birefringence, effects
w h i c h are m a n i f e s t a t i o n s of optical a n i s o t r o p y . A
birefringent specimen b e t w e e n crossed P o l a r o i d
sheets (inserted a b o v e a n d below it) in the m i c r o s c o p e
will generally a p p e a r b r i g h t o r c o l o r e d against a black
b a c k g r o u n d , t h u s giving high i m a g e c o n t r a s t .
The
crystalline
microstructure
of
synthetic
p o l y m e r s , often spherulitic, h a s been studied since the
1930s, in m a n y instances by using a polarizing m i c r o
scope. Spherulites o c c u r in m a n y p o l y m e r s which are
crystallized either from t h e melt o r from a concen
t r a t e d s o l u t i o n . T h e s t r u c t u r e is essentially radially
s y m m e t r i c , b u t d i s t o r t i o n from the idealized g r o w t h
p a t t e r n m a y be p r o d u c e d by n o n r a n d o m n u c l e a t i o n
o r a n u n f a v o r a b l e t h e r m a l history. In the polarizing
m i c r o s c o p e , the result is t h a t b u l k p o l y m e r s show
well-developed spherulitic s t r u c t u r e s or, alternatively,
a m o r e g r a n u l a r a p p e a r a n c e if g r o w t h c o n d i t i o n s
h a v e been less favorable. F i g u r e s 2 a n d 3 s h o w slowcooled a n d fast-cooled samples of high-density
337
Polymers:
Light
Microscopy
Figure 3
Same polymer as in Fig. 2, but cooled rapidly. Crossed
polars were used in imaging
Figure 4
Microstructure of a thin section of slow-cooled
polypropylene imaged using crossed polars
338
Polymers:
Light
Microscopy
e x a m p l e s a r e p r e s e n t e d b y C h a p o y (1985) a n d t h e
basic i n t e r p r e t a t i o n of liquid-crystal i m a g e s is t r e a t e d
by H a r t s h o r n e (1974).
Figure 5
Complex pattern of birefringence associated with
molecular orientation in a molded polypropylene integral
hinge. A thin section was placed between crossed polars
(b) Quantitative
techniques. Birefringence (An) is t h e
n u m e r i c a l difference b e t w e e n t w o principal refractive
indices in t h e section o r specimen being e x a m i n e d .
M e t h o d s for m e a s u r i n g An u s i n g a polarized-light
m i c r o s c o p e h a v e been used t r a d i t i o n a l l y b y p e n o l o
gists a n d m i n e r a l o g i s t s a n d a r e well d o c u m e n t e d
( W a h l s t r o m 1979). A l m o s t identical t e c h n i q u e s m a y
be used o n p o l y m e r i c specimens t o c h a r a c t e r i z e spherulites o r to d e t e r m i n e t h e degree of m o l e c u l a r orien
t a t i o n in m a n u f a c t u r e d p r o d u c t s . I n t h e latter case,
b o t h o r t h o s c o p i c a n d c o n o s c o p i c ( c o n v e r g e n t light)
m o d e s of o b s e r v a t i o n a r e effective.
Typically, An is m e a s u r e d b y first d e t e r m i n i n g the
optical p a t h difference (P) for light p a s s i n g t h r o u g h
t h e specimen. T h i s is d o n e using m i c r o s c o p e " c o m
p e n s a t o r s " of w h i c h t h e r e a r e a variety, e a c h designed
t o o p e r a t e o p t i m a l l y over a p a r t i c u l a r r a n g e of P.
C o m p e n s a t o r s of t h e E h r i n g h a u s , Berek, B a b i n e t o r
B r a c e - K o h l e r (elliptic) t y p e a r e all applicable t o
p o l y m e r specimens. If t h e thickness of t h e specimen is
t, t h e n
An
Pit
339
Polymers:
Light
Microscopy
340
Figure 6
(a) Thin section of high-impact polystyrene, showing
rubber phase, imaged by phase-contrast microscopy.
(b) Same thin section imaged using transmitted-light
differential interference-contrast microscopy
Polymers:
Light
Microscopy
Transmitted-Light
Interference
Q u a n t i t a t i v e interference systems o p e r a t i n g in a
transmitted-light m o d e allow t h e precise m e a s u r e
m e n t of a n O P L . T h e precision d e p e n d s o n t h e
t e c h n i q u e used b u t c a n be as high as 1/200 of a
wavelength (i.e., a b o u t 2.5 n m ) u n d e r ideal c o n
ditions. T h e result is t h a t it is possible t o identify
p h a s e s in c o m p o s i t e s o n t h e basis of their refractive
indices a n d t o m e a s u r e the thickness of thin p o l y m e r
layers t o c o n s i d e r a b l e a c c u r a c y . T h e t e c h n i q u e h a s
f o u n d a p p l i c a t i o n in a d h e s i o n a n d m i x i n g studies,
w e a r - r a t e investigations a n d thin-film c o a t i n g o r
deposition-rate measurements.
T h e u n d e r l y i n g principle of o p e r a t i o n is t h a t t w o
c o h e r e n t waves a r e p r o d u c e d from a c o m m o n s o u r c e .
O n e is passed t h r o u g h t h e specimen o r feature of
interest a n d t h e o t h e r t h r o u g h a " r e f e r e n c e " region.
T h e relative p h a s e s of t h e w a v e s a r e t h e n c o m p a r e d by
interferometry.
3. Reflected-Light
Methods
Figure 7
Epoxy-resin fracture surface, imaged using the
reflected-light differential interference-contrast microscopy
technique
341
Polymers:
Light
Microscopy
Figure 8
Spherulitic surface of molded polypropylene, showing
surface contours. The reflected-light two-beam
microinterferometry technique was used
342
Figure 9
Cross-section of the wall of a polyester bottle externally
coated with poly(vinylidene chloride), imaged using
ultraviolet fluorescence microscopy: a, nonfluorescing
background; b, strongly autofluorescing PVDC layer;
c, weakly fluorescing polyester layer
t h e m i c r o s c o p e , it is n o w m o r e c o m m o n t o use t h e
latter, a s m o d e r n e q u i p m e n t designs in this m o d e
offer very high i r r a d i a t i o n a n d light collection
efficiencies.
A u t o f l u o r e s c e n c e m i c r o s c o p y h a s been used t o o b
serve d e g r a d a t i o n a n d its d i s t r i b u t i o n in p o l y m e r s ,
p a r t i c u l a r l y p o l y v i n y l chloride) a n d polystyrene. T h e
t e c h n i q u e c a n also be used as a m e c h a n i s m for i m a g e
contrast production. Figure 9 shows an example.
H e r e a poly(vinylidene chloride) ( P V D C ) layer h a s
been a p p l i e d t o t h e o u t e r surface of a polyester b o t t l e .
In cross-section a n d b y autofluorescence, t h e P V D C
layer is clearly distinguished as a thin, b r i g h t b a n d .
T h e p h e n o m e n o n m a y also b e used t o label individual
c o m p o n e n t s in b l e n d i n g studies, b y slightly d e g r a d i n g
t h e c o m p o n e n t w h i c h s u b s e q u e n t l y needs t o b e identi
fied. T h e d e g r a d a t i o n c a n be sufficiently mild t o leave
m o s t o t h e r p r o p e r t i e s virtually unaffected.
F l u o r e s c e n c e m i c r o s c o p y is also used in t h e identifi
c a t i o n of additives in p o l y m e r systems, either b y
autofluorescence o r b y t h e i n c o r p o r a t i o n of suitable
fluorochromes.
See also: Optical Microscopy; Polymers: Electron Micros
copy
Polymers:
Molecular
Weight
()
D. A. Hemsley
[ L o u g h b o r o u g h University of T e c h n o l o g y ,
Loughborough, UK]
()
= ^/^^
1. General
Distribution
Features
of a Molecular
Weight
T h e m o l e c u l a r weight d i s t r i b u t i o n ( M W D ) is c o n v e
niently characterized b y either t h e n u m b e r N(n) o r
weight W(n) of c h a i n s with r e p e a t i n g units (e.g., a
chain with m o l e c u l a r weight = nm0 with m0 t h e
m o l a r weight of a r e p e a t i n g u n i t ) . T h e n o r m a l i z e d
functions
N(n) =
W(n)=
()/()
()()
Distribution
Bibliography
and its
(b)
(c)
[- ()
nw=Mtyfrty
()()
Ln1V(n)
T h e a v e r a g e is
= ^/^
(d)
^/^
T h e + 1 a v e r a g e is
n
z
+1
(4)/ ( 3 ) =
(3)/
(2)
w w
H i g h e r averages (z + 2, . . . ) m a y be defined by
o b v i o u s generalization. It c a n be s h o w n t h a t
"* ^ nw< nz ^ ...
T w o of these a v e r a g e s j i a v e simple physical signific
ance: nn, the m e a n of N(n), is t h e total n u m b e r of
r e p e a t u n i t s () divided by t h e n u m b e r of m o l
ecules () a n d d e t e r m i n e s colligative p r o p e r t i e s
(e.g., o s m o t i c pressure a n d v a p o r pressure lowering);
nw, the m e a n of W(n), is t h e weighted s u m )
divided by t h e t o t a l c o n c e n t r a t i o n Zc(), with c(n) the
c o n c e n t r a t i o n (weight p e r unit v o l u m e ) of c h a i n s with
u n i t s , a n d is given by m e a s u r e m e n t s sensitive t o the
masses of t h e molecules present (e.g., light scattering
and sedimentation).
T h e b r e a d t h of a M W D is characterized by the
v a r i a n c e \ (the positive r o o t of o% is called the
s t a n d a r d d e v i a t i o n ) . W i t h a M W D , the dimensionless
reduced variance
343
Polymers:
Molecular
Weight
Dz =
Distribution
2
DN =
Dw
and its
(nJnn)-\=MW/(MW) -\
{ n J n
) - \ = ^ l ^ )
- \
(nJnz)-\
S = * ( = <?/( - *( + 2
So t h a t
SN = {Dw
Sw = (Dz
+ \){DN
+ l ) - 3(DN
2
+ \){DW
+ l ) - 3(DW
+ 1) + 2
+ 1) + 2
F o r a symmetric d i s t r i b u t i o n , SF = 0. Positive a n d
negative SF indicate a d i s t r i b u t i o n skewed t o w a r d
large a n d small n, respectively.
Indices involving higher m o m e n t s c a n be utilized t o
characterize o t h e r p r o p e r t i e s of a d i s t r i b u t i o n a n d , in
principle, a distribution is k n o w n completely if all of
its m o m e n t s are k n o w n . In practice, the e x p e r i m e n t a
list never h a s such luxury of d a t a a n d rarely h a s
i n f o r m a t i o n for indices b e y o n d Dz o r Sw.
In m a n y applications, the average of a function
() of is needed:
= ()
()/
+]
()
{) = \%
= [;
\ ()]
+
()]
m =
F{m)
0
2. Examples
Functions
of Molecular
Weight
Distribution
"-
=-^( dp
n l]
p ~)
Polymers:
Molecular
Weight
exp[ - (a
In u/u0) ]
l,2 v
Functions
F o r s o m e a d d i t i o n p o l y m e r i z a t i o n s , the S c h u l z - Z i m m
d i s t r i b u t i o n is a realistic r e p r e s e n t a t i o n of N(n). M o r e
frequently, it is used as a m a t h e m a t i c a l l y c o n v e n i e n t ,
a n d often r e a s o n a b l e , r e p r e s e n t a t i o n of N(n), w i t h o u t
a t t e m p t t o relate t h e p a r a m e t e r s to p o l y m e r i z a t i o n
variables. T h e S c h u l z - Z i m m d i s t r i b u t i o n is a general
ized form of t h e o n e - p a r a m e t e r e x p o n e n t i a l relation,
to which it reduces if the p a r a m e t e r h is unity. Since
Dz={h
+ 2)-\
. . . , the
DN = h~\ Dw={h+\y\
S c h u l z - Z i m m d i s t r i b u t i o n is s h a r p e r o r b r o a d e r t h a n
the o n e - p a r a m e t e r e x p o n e n t i a l d i s t r i b u t i o n as h is
greater o r smaller t h a n unity, respectively. T h e skew2
ness index of N(n) is positive (SN = 2/h ). In m a n y
cases (including calculation of nn, nw, nz, . . . , a n d n{a))
use is m a d e of the s t a n d a r d form (after c o n v e r s i o n of
s u m s to integrals)
/00
t/'
- 1
exp(-ku)du
du
= ocn u 0
is useful in s u m m a t i o n s with t h e P o i s s o n d i s t r i b u t i o n ,
since by c o n t i n u e d differentiation, a n y such s u m with
1
integral s c a n be r e d u c e d t o t e r m s involving " /
( 1)! = exp multiplied by functions of v.
r(t)/k
Distribution
h a n d . W i t h the former, o n e h a s DN = /^
and
SH = 0.
T h e l o g a r i t h m i c n o r m a l d i s t r i b u t i o n is a v a r i a t i o n
of t h e n o r m a l d i s t r i b u t i o n designed to eliminate the
troublesome truncation mentioned above, and can
represent a d i s t r i b u t i o n with a l o n g high-molecularweight tail. M o s t frequently, f^(ln n) is represented as
being n o r m a l l y d i s t r i b u t e d , with the result for N(n)
given
in
Table
1.
For
this
distribution,
2
DN = DW = DZ = e x p / ? - 1, so t h a t SN is positive for
DN > 0. In using the l o g a r i t h m i c n o r m a l d i s t r i b u t i o n ,
t h e s t a n d a r d form
2.2 Two-Parameter
and its
exp(v a /4)
is frequently e n c o u n t e r e d .
2.3 Three-Parameter
Function
Iw(n)=\-exp(-yr ")
2.4 Other Distribution
Functions
Weight
Distribution
A p p l i c a t i o n s of M W D functions t o i n t e r p r e t physical
p r o p e r t i e s a b o u n d ; only a few illustrative e x a m p l e s
will be given, with e m p h a s i s o n results useful in the
next section. T h e s e will involve calculations of a
physically meaningful a v e r a g e of a function ()
t h a t d e p e n d s o n a n d t h e c o n c e n t r a t i o n c(n) (weight/
vol) of -mers. In a polydisperse m i x t u r e , c = lLc(n) is
the t o t a l c o n c e n t r a t i o n a n d W{n) = c(n)/c.
In t h e following, it is a s s u m e d t h a t the p o l y m e r is
h e t e r o d i s p e r s e only in c h a i n length. O t h e r w i s e , m u l t i
v a r i a t e d i s t r i b u t i o n s m a y be needed t o represent the
m a t e r i a l (e.g., t h e b i v a r i a t e n u m b e r fractions N(n, )
for c o m p o n e n t s with r e p e a t i n g units a n d p r o p e r t y ,
which c o u l d be the n u m b e r of long c h a i n b r a n c h e s ,
etc.).
345
Polymers:
Molecular
Weight
and its
Distribution
Table 1
Some frequency used molecular weight distribution functions
Parameter
Name
N(nY
Flory-Schulz
(1-/>)/>"
Exponential
yexp(-yn)
Poisson
[v"-7("-l)!]exp(-v)
Schulz-Zimm (two-parameter
exponential)
Normal (Gaussian)
h h
yn~
l-p
1+
exp(-yn)/T(h)
, 2
h,y
[ 2 * / J r e x p [ - ( - n M) / 2 / J ]
Logarithmic normal
K//?V^)exp[-(ln /^/ }
Three-parameter exponential
my
hlmnh-
nm exp
nm9
(-Qxp
yn>)ir(hlm)
, v,
rp+i)/m]
llm
y r(h/m)
3.1 Osmotic
Pressure
W(n)
+ (>
n/RTc
= (nnmoy
n)W(m)W(n)
n
+ B c+
...
...
w h e r e the t e r m p r o p o r t i o n a l to c h a s been r e d u c e d t o
1
a s t a n d a r d a ve ra ge _(i.e., n; ),
but the average
n
B = YLB(m, n)W(m)W(n)
of the second virial coeffi
cient B(m, n) c a n n o t be e v a l u a t e d w i t h o u t represen
n
t a t i o n for B(m, n). T o illustrate t h e calculation of B ,
346
bn;?*
= ( " > ( - y, 2 ) )
With
the
Schulz-Zimm
distribution,
=
2
[(\ +h/2)/(1 + )] . O t h e r m o r e
realistic
m o d e l s h a v e been studied t o represent m o r e c o m p l e x
n
b e h a v i o r of B
3.2 Light
Scattering
F o r a dilute p o l y m e r s o l u t i o n , t h e Rayleigh r a t i o R0 a t
zero scattering angle involves s u m s over the c o m
ponents:
Polymers:
Molecular
Weight
and its
Distribution
One-parameter functions
2
\+p
l-p
l+4p+p
(\-p)(l+p)
2
y
1 + 11/? -h l i p +
2
(l-p)(\+4p+p )
3
y
1 + 3v + v
1 +
4
y
2
1 + 7v + + v
+ 3v + v2
l a
y- m2
+ a)] '
Two-parameter functions
(h+\)
(h + 2)
(ft+ 3)
>>
1.
1 + 3Qg/Aim)
, 2l
\+(/)
2
l + 6Qg//i m) + 3 Q g / WJ
\ + 3(fi/nm)
nm exp 3 /2
y- \T(h+\+a)IT(h
exp 5 /2
+ \)f
nm exp(* + 2)/? /2
mexp 7^ /2
Three-parameter function
T[(h + 2)m]
l,m
y T[(h
/?0 =
[(6 + 3)m]
llm
+ \)/m]
y T[{h
+ 2)/m]
j>
- 2 m ^ Z Z 5 ( m , n)mnW(m)W(n)
1
l s
= K m 0) - + 2 5
c - . . .
...]
where t h e t e r m p r o p o r t i o n a l t o c is expressed a s a
s t a n d a r d a v e r a g e (e.g., nw), b u t w h e r e e v a l u a t i o n of
B
LS
= ~ (9
n)mnW(m)W(n)
LS
x/2
= n- \ZB (n,
n)nW{n)]
r p + 3)/m]
LS
=
=
Rq = R q(n)
Kcm^nP(u)W{n)
[1+(^ /3); /?
LS
bn~^
{nJn{X_yl2)Y-
in which
c o n t a i n s n{a) with a = 1 y/2. U s e
of
the
Schulz-Zimm
distribution
gives
2
= ( + 1)*[(2 + h - /2)/(2 + )] , so t h a t for
2
0
( ) ^ ( ) + ...]
v
W i t h several m o l e c u l a r m o d e l s , R^(n) = r , so t h a t
2
L S
this m o d e l , B /B
= [(1 + - y/2)/(l + )] , which
LS
n
d e m o n s t r a t e s t h e general result t h a t 2? ^ 2?
F o r d a t a e x t r a p o l a t e d t o infinite dilution, t h e
d e p e n d e n c e o n scattering angle is given b y
2
R%(n) = Knm0c(n) P(u), w h e r e u = R^{n)q d e p e n d s o n
t h r o u g h t h e r o o t - m e a n - s q u a r e r a d i u s of g y r a t i o n
=
Rg'> Q (4/) sin 0/2 is t h e m o d u l u s of t h e scattering
vector. E v a l u a t i o n of
tfc/tf^Kmo)-
and
B
r[(h+\+a)lm]
rp+l)/m]
llm
1 / m
LS
u : [ W 0C I ^ ( / I )
2
^/i?
[(/ + 4)/w]
R G = n- lR G
(n)nW(n)
= rn\ +
2+
w i t h = (njnw(ni2
)
w h e r e = 1 a n d
+e)/n
involves n{a) with = 2 + . F o r integral ,
m a y be
347
Polymers:
Molecular
Weight
and its
Distribution
3.3 Intrinsic
Viscosity
T h e specific viscosity &() of a very dilute solution is
given by &() = [n]nc(n\ w h e r e t h e intrinsic viscosity
a
[] usually o b e y s a p o w e r - l a w relation [] = kn , so
t h a t n{a) with a = oc a p p e a r s :
C =
fo] = V
M ^ ( " )
K )
"()
/
-
w ( z / " h - )
3.4 Size-Exclusion
Figure 1
Examples of W(n) for logarithmic exponential ( ) and
Gaussian (- - ) and Schulz-Zimm (
) distribution
functions for the indicated DN = njnn - 1. The latter with
DN = 1 also represents the exponential and Flory-Schulz
functions. All curves were calculated with nn = 100, but are
essentially unchanged with other nn, except in some cases
for very small nn
expressed in t e r m s of s t a n d a r d averages. F o r e x a m p l e ,
with flexible coil c h a i n s u n d e r F l o r y - t h e t a c o n d i t i o n s
LS
n
2
(B
= B = 0), = 1 a n d R G = rnz a n d for rodlike
2
W i t h flexible c h a i n s
c h a i n s , v = 2 a n d R G = rnzn2+l.
LS
u n d e r c o n d i t i o n s with B > 0, will usually be n o n integral, with 0 < ^ 0.2. In this case, a specific W(n)
is needed t o e v a l u a t e , for e x a m p l e , with t h e S c h u l z Z i m m d i s t r i b u t i o n , = ( 3 + h + e)/(h + 2 ) T ( 3 + h).
O v e r a wider r a n g e of q, for the flexible coil
LS
2
u n d e r c o n d i t i o n s with B = 0, P(u) = (2/u )
[w - 1 + exp - u],
and
for
a
rodlike
chain,
2
2
2
P(u) = x~ [xSi(2x) sin x], w h e r e u = x /3 a n d Si is
the sine integral. E a c h of these c o n t a i n t e r m s t h a t
require e v a l u a t i o n of a function t h a t is n o t a p o w e r law relation. T h u s , for the coil, m a k i n g use of the
2
relation R G(n) = rn,
z
?o Rq = Kcnwm0[2/q
rnw 2/q*r nnnw
A 2
+ (2lq r nJLn-
exp(-
rq n)W(n)]
( 5)
= ([]
W{n)
t h a t a r e available if t h e c a l i b r a t i o n b e t w e e n [] a n d
Ve is k n o w n . T h u s , a n a p p a r e n t njnn r a t i o w o u l d be
calculated as
(nJnn)App
A^A^s- i)
l 2
(2m0y q r
K/"JAPP
- ( , ) - [ - ( ^ )
+
348
Chromatography
= (nJnn)T(h
+ 2 + S)T(h - ) / ( +
2)Y(h)
Polymers:
p a r a m e t e r s ; t h e coefficient k is also a p p r o x i m a t e d
by a n estimate kA t o p e r m i t c a l c u l a t i o n o f t h e experi
m e n t a l q u a n t i t i e s B$ = (k^^+^Af*
and apparent
]
l)
averages (ns)A = B^ /B^~
(e.g., this o b t a i n s if t h e
c o r r e l a t i o n of Af vs Ve for a s t a n d a r d p o l y m e r is used
t o analyze t h e d a t a for the u n k n o w n p o l y m e r , so t h a t
kA a n d ola a r e p u t e q u a l t o t h e c o r r e s p o n d i n g p a r a
m e t e r s kc a n d a c for t h e s t a n d a r d ) . I n this case, with
the S c h u l z - Z i m m d i s t r i b u t i o n ,
+
to),
s'App
*A /nn
~h
h + s(\ +)
h+s
T[h + s{\ + )]
T[h-d
s(\+S)]
A s a n e x a m p l e , if d a t a o n b e n z e n e s o l u t i o n s o f poly
vinyl acetate) were a n a l y z e d with t h e Vt relation
for polystyrene (in benzene), t h e n for a p o l y m e r with
A = l , ( f l J A eP = 1.54(HW)~-X, illustrating t h e e r r o r
that can be introduced.
3.5 Photon Correlation Light
Scattering
Time-resolved light scattering using p h o t o n cor
relation m e t h o d s give t h e intensity a u t o c o r r e l a t i o n
(2)
functions # ( , ) o f t h e c o u n t r a t e in s a m p l i n g
intervals of d u r a t i o n . F o r a p p r o p r i a t e experi
m e n t a l c o n d i t i o n s (including e x t r a p o l a t i o n t o infinite
dilution):
[g
( 2 )
( r , ) - 1 ]
1 /2
= ^ ( H ) e x p ( -
/^))
with DT(n) t h e
where ~\) is given b y q DT(n),
t r a n s l a t i o n a l diffusion coefficient a n d Qq(n) is t h e
fraction of t h e scattering d u e t o the c o m p o n e n t with
c o h e r e n c e time rq{n). F o r i n d e p e n d e n t scatterers (i.e.,
infinite dilution), Q(n) = Rq(n)/Rq. T h u s , analysis o f
2
1 /2
[g 1 ] requires t h e extensive u s e o f m o d e l s (e.g.,
random-flight, rodlike) t o p e r m i t e v a l u a t i o n o f t h e
d e p e n d e n c e of Qq(n) a n d Jin) o n in d a t a i n t e r p r e
t a t i o n . F o r e x a m p l e , t h e first c u m u l a n t Kl e q u a l
(2)
to - (i)d 1[# () - \]/d In a s goes t o zero c a n b e
evaluated t o give
2
kTq
4nns(rnn) ^
- ( 1
^ / 3 ^}
"'
/?
21
( + 2)
if P(u) is a p p r o x i m a t e d b y t h e G u i n i e r relation
exp( w/3), a n d t h e expression DT(n) =
kT/4^sRG(n)
for t h e random-flight c h a i n is used, with Ro(n) rn.
T h e result reveals t h e effects o f i n t r a m o l e c u l a r inter
2
ference (e.g., t h e factor (1 + q rnn/3h), w h i c h is a p
2
p r o x i m a t e l y unity for q <^ rnn/3) a n d t h e c o m p l e x
d e p e n d e n c e o n polydispersity, even for t h e m o s t
(2)
primitive features of ( ) .
4. Determination
Distribution
of the Molecular
Weight
M e t h o d s of c h a r a c t e r i s i n g a M W D m a y involve
physical s e p a r a t i o n of c o m p o n e n t s , with s u b s e q u e n t
Molecular
Weight
and its
Distribution
c \n)
= c0AM
e x p ( - ABM)/[\
- e x p ( - BM)]
2
with c0 t h e initial c o n c e n t r a t i o n , A = (r m )/
2
2
2
2
(b - m ) a n d = (dpldc)w\b
- m )/RT w h e r e is
t h e s o l u t i o n density. F o r a h e t e r o d i s p e r s e solute
t h e a v e r a g e ( m e a s u r a b l e ) c o n c e n t r a t i o n a t r is
(r)
{r)
( ) s o t h a t analysis o f c a s a function of r
c(r) = c
p r o v i d e s a m e a n s t o s t u d y N(n), either by inversion o f
( r)
{r)
c t o o b t a i n N(n) o r by analysis o f c t o d e d u c e nw, nz,
(r)
etc. I n practice, d e v i a t i o n s from t h e idealized c (n)
given a b o v e c a u s e d b y s o l u t i o n compressibility (es
pecially with o r g a n i c solvents) a n d h y d r o d y n a m i c a n d
t h e r m o d y n a m i c i n t e r a c t i o n s a m o n g t h e solute m o l
ecule m a k e s the analysis less a t t r a c t i v e . M o r e o v e r , the
m e t h o d is inherently time c o n s u m i n g . C o n s e q u e n t l y ,
it is used m u c h less frequently t h a n size-exclusion
c h r o m a t o g r a p h y (see later).
S e d i m e n t a t i o n velocity affords a n alternative cen
trifugal coefficient s(n)9 e q u a l t o
M(dp/dc)DT(n)/RT
for a s o l u t i o n a t infinite dilution. T h e s p r e a d i n g o f the
b o u n d a r y b e t w e e n s o l u t i o n a n d solvent a s the b o u n d
a r y m o v e s down_the cell (for positive dp/dc) c o n t a i n s
i n f o r m a t i o n o n N(n). I n practice, c o n v e r s i o n o f t h e
(r)
e x p e r i m e n t a l d a t a dc /dr t o N(n) is h a m p e r e d b y t h e
349
Polymers:
Molecular
Weight
and its
Distribution
* /,(* J = (iWi(nw)
+ "
j=
Wj(nw)
S(VC)=
S^ \Ve)g(Ve-u)
u=V\
S (Ve)
00
1 2/
= (In)'
J-
ds
00
c)
S (Ve)
x 2
[HI(H-bx)] l S(V^xV[b\lA(H-bx)]
i
w h e r e 2bi = - d In Sffl/dx ]^
.Ve G i v e n (which m a y
C)
v a r y with F e ) , & (VJ m a y be e s t i m a t e d for each S(Ve).
See also: Liquid Chromatography Mass Spectrometry;
Organic Mass Spectrometry
Bibliography
Cramer 1946 Mathematical Methods of Statistics. Prince
ton University Press, Princeton, NJ, Chaps. 15-20, pp.
166-255
Fujita 1975 Foundations of Ultracentrifugal Analysis.
Wiley, New York
Giddings J C 1979 Field-flow fractionation of polymers:
one-phase chromatography. Pure Appl. Chem. 51: 145971
Guzman G 1961 Fractionation of high polymers.
In: Robb J C, Peaker F W (eds.) 1961 Progress in
High Polymers, Vol. 1. Academic Press, New York, pp.
113-93
Peebles L Jr 1971 Molecular Weight Distribution in
Polymers. Interscience, New York
Slade Jr (ed.) 1975 Polymer Molecular Weights. Dekker,
New York
Tung L (ed.) 1977 Fractionation of Synthetic Polymers,
Dekker, New York
Zelen M, Severs C 1964 Probability functions. In: Abramovitz M, Stegun I A (eds.) 1964 Handbook of Mathema
tical Functions, Applied Mathematical Series No. 55.
National Bureau of Standards, Washington, DC, Chap.
26, pp. 925-95
G . C. Berry
[Carnegie M e l l o n University, P i t t s b u r g h ,
Pennsylvania, U S A ]
Polymers:
= b Kc[MP(q)
+ cS(q)]
w h e r e c is t h e p o l y m e r c o n c e n t r a t i o n , is its m o l e c u
lar weight, A' is a c o n v e r s i o n factor a n d b is t h e
c o n t r a s t length ( t h e difference b e t w e e n solvent a n d
solute scattering l e n g t h ) . T h i s l e n g t h c a n b e e n h a n c e d
by isotopic s u b s t i t u t i o n of t h e p r o t o n s ( d e u t e r a t i o n )
w i t h o u t m a j o r p e r t u r b a t i o n of t h e system. Selective
labelling (i.e., s u b s t i t u t i o n ) is also achieved b y
this m e t h o d . Small-angle n e u t r o n scattering m a d e
possible t h e e x p e r i m e n t a l investigation of m a n y situa
tions w h i c h w e r e p r e v i o u s l y o n l y discussed t h e o r e t i c
ally; a recent review of this subject is given b y Stein
a n d H a n (1985).
/.
Phonons
Neutron
Scattering
CyozT .
V a l u e s of d less t h a n 3 were derived from
o b s e r v a t i o n s in r u b b e r s a n d p o l y e t h y l e n e . It w a s of
interest t o test t h e density of states directly b y inelastic
i n c o h e r e n t n e u t r o n scattering. T h e e x p e r i m e n t s w e r e
i n t e r p r e t e d , h o w e v e r , for large values of a n d t h e
q u e s t i o n of t h e c h a r a c t e r i s t i c d i m e n s i o n w a s left
u n a n s w e r e d . It h a s b e e n revived lately b y t h e sugges
t i o n t h a t t h e index d c o u l d reflect t h e fractal d i m e n
sion of p o l y m e r coils ( S t a p e l t o n et al. 1980). V a n
H o v e singularities were identified for v a r i o u s m o t i o n s
of t h e c h a i n : a n t i p a r a l l e l t r a n s l a t i o n s in t h e c a n d b
axial d i r e c t i o n s , a n d r o t a t i o n s a g a i n s t e a c h o t h e r
( T w i s l e t o n a n d W h i t e 1972). Crystalline stiffness c o n
s t a n t s w e r e d e t e r m i n e d from t h e d i s p e r s i o n curves.
T h e s e c o u l d b e m e a s u r e d for t h e first t i m e within t h e
Brillouin z o n e ; d a t a h a v e suggested t h e presence of a
soft m o d e ( F e l d k a m p et al. 1968).
2. Small-Angle
Scattering:
Amorphous
Polymers
T h i s section is c o n c e r n e d w i t h t h e g e o m e t r y of flexible
coils. F u n d a m e n t a l q u e s t i o n s a r e raised a b o u t t h e
a s y m p t o t i c s t a t e of such l o n g m o l e c u l e s .
Before small-angle n e u t r o n scattering b e c a m e
available, t h e r e w a s n o physical m e t h o d t o d e t e r m i n e
t h e size of a flexible p o l y m e r coil in t h e melt. T h e first
e x p e r i m e n t t o b e c a r r i e d o u t u s i n g small-angle n e u
t r o n s c a t t e r i n g consisted of m e a s u r i n g t h e a v e r a g e
as
a
s q u a r e r a d i u s of g y r a t i o n </?g>
function of t h e
m o l e c u l a r weight M w . Different g r o u p s of c o w o r k e r s
o b t a i n e d similar results for p o l y s t y r e n e , p o l y m e t h a crylate a n d p o l y e t h y l e n e , respectively. T h e o b s e r v e d
v a r i a t i o n of </g> w i t h M w indicates a r e l a t i o n s h i p
< / ? G > c c M w , typical o f a r a n d o m w a l k . T h e result h a d
b e e n p r e d i c t e d b y F l o r y , o n t h e basis of t h e r m o
d y n a m i c s ( t h e e n t r o p y p e r u n i t v o l u m e decreases as
t h e size of molecules increases). A n interesting struc
t u r a l p r o p e r t y of m e l t s w a s p o i n t e d o u t b y d e G e n n e s .
It is o b s e r v e d in t h e n e u t r o n s c a t t e r i n g p a t t e r n of a
m e l t m a d e of identically labelled coils t h a t t h e m a x i
m u m s c a t t e r e d intensity is smaller t h a n t h e c o r r e s
p o n d i n g theoretical intensity d u e t o t h e s a m e set of
n o n i n t e r a c t i n g c h a i n s . T h i s c o r r e l a t i o n hole is evid
ence of a n a m o r p h o u s p o l y m e r m e l t s t a t e , as o p p o s e d
to an ordered structure.
T h e m a n n e r in w h i c h flexible coils o c c u p y space in
a given e n v i r o n m e n t ( R a u m e r f u l l u n g ) is a p r o b l e m of
m a j o r interest w h i c h c a n b e s t u d i e d b y n e u t r o n scat
tering. T o a first a p p r o x i m a t i o n t h e following selfsimilar r e l a t i o n h o l d s t r u e for t h e a v e r a g e s q u a r e d
d i s t a n c e b e t w e e n a n y t w o m o n o m e r s /, j of a single
coil in a g o o d solvent:
<
= |/-;|
(/,;=1,...,>
w h e r e A is a c o n s t a n t a n d is t h e excluded v o l u m e
index. W e n o w d e p a r t f r o m t h e swollen state b y
l o w e r i n g t h e t e m p e r a t u r e T, b y increasing t h e c o n c e n
t r a t i o n c o r b y increasing t h e (linear) size of t h e
351
Polymers:
Neutron
Scattering
T
< * G > *
1/4
>- 2/5
light scattering,
n e u t r o n scattering,
n e u t r o n scattering,
c->0
Ty/N>\
c->0
It w a s observed t h a t b o t h the swollen a n d the u n s w o l len state coexist o n the s a m e coil. Such structures a r e
characterized by so-called " b l o b s " (de G e n n e s ) ; these
are the sequences of m o n o m e r s s e p a r a t i n g swollen
a n d unswollen states. Different types of b l o b s a r e
found d e p e n d i n g o n the p a r a m e t e r , the best k n o w n
being the " t h e r m a l " b l o b . T h e n e u t r o n scattering
e x p e r i m e n t is able t o detect " c o n c e n t r a t i o n " b l o b s .
M o r e detailed i n f o r m a t i o n o n the flexible coil c o n
figuration is o b t a i n e d from n e u t r o n scattering experi
m e n t s by studies o n partially labelled coils. W e are
n o w c o n c e r n e d with the uniformity of the coil
e x p a n s i o n a l o n g itself, in a g o o d solvent, at zero
c o n c e n t r a t i o n . It is generally agreed t h a t , b e y o n d a
first a p p r o x i m a t i o n , this e x p a n s i o n is n o t u n i f o r m
(the coefficient A d e p e n d s in fact o n /, j). T h e o r y
asserts t h a t a coil p o r t i o n is m o s t strongly pulled b y
excluded v o l u m e forces w h e n located in the m i d d l e of
the coil, in between t w o b r a n c h e s (des Cloizeaux
1980). F r o m t h e results of n e u t r o n scattering experi
m e n t s ( L o d g e et al. 1983), the issue w a s m a d e clear.
T h e size of a labelled coil p o r t i o n was m e a s u r e d
successively in the central p a r t of a large coil, at the
p e r i p h e r y a n d w h e n isolated. T h e values f o u n d were
59 A, 56 A a n d 50 A, respectively. A n o t h e r p r o m i s i n g
n e u t r o n scattering e x p e r i m e n t using partially labelled
m a t e r i a l is t h a t of R a w i s o a n d c o w o r k e r s of the C R M
(Centre de R e c h e r c h e s des M a c r o m o l e c u l e s ) , S t r a s
b o u r g . T h r e e different polystyrene s a m p l e s h a v e been
p r e p a r e d , the p r o t o n s being replaced by d e u t e r i u m ,
respectively o n the entire coil, o n the b a c k b o n e a n d
o n the p h e n y l side g r o u p s only. T h e t r u e a s y m p t o t i c
form factor of the coil b a c k b o n e c a n n o w be deter
m i n e d experimentally a n d c o m p a r e d with m o d e l cal
culations. A s a result, a new precise e v a l u a t i o n of the
persistence length (due to the local chemical structure)
c a n be o b t a i n e d .
3. Small-Angle
Scattering:
Poly
electrolytes
Copolymers,
Networks,
352
4. Small-Angle
Scattering:
Crystalline
Polymers
I n t e r p r e t a t i o n s of n e u t r o n scattering results o b t a i n e d
in this field h a v e been eagerly d i s p u t e d . A t first, the
a p p l i c a t i o n of isotopic labelling revealed s o m e diffi
culties. D e u t e r a t e d a n d n o n d e u t e r a t e d coils segregate
d u r i n g crystallization, w h e n this process is long c o m
p a r e d with m o l e c u l a r diffusion times. Q u e n c h i n g ,
however, yields a h o m o g e n e o u s d i s t r i b u t i o n . N e u t r o n
scattering w a s used t o d e t e r m i n e t h e coil configu
r a t i o n s within a n d in b e t w e e n crystallites. D a t a s h o w
t w o different configurations ( Y o o n a n d F l o r y 1979).
W h e n crystallization occurs in the melt, r a n d o m
reentry prevails (Sadler a n d Keller 1976, Summerfield
et al. 1978). W h e n , h o w e v e r , crystallization occurs in
dilute solution, the coil r a d i u s of g y r a t i o n is f o u n d t o
be smaller t h a n t h e equivalent r a d i u s in m e l t - g r o w n
crystallites. T h i s o b s e r v a t i o n , t o g e t h e r with the
observed i n t e r m e d i a t e form factor, suggests m o d e r a t e
adjacent reentry a n d possible superfolding of t h e coil.
Scattering by crystallites m a d e of small linear m o l
ecules indicates a c o r r e l a t i o n hole a t large w a v e
vectors: reentry occurs at sites further r e m o v e d t h a n
nearest n e i g h b o u r s .
Polymers:
5. Polymer
Dynamics
A n i m p o r t a n t s t u d y at the I L L w a s m a d e using a
n e u t r o n spin e c h o s p e c t r o m e t e r t o d e t e r m i n e c h a r a c
teristic diffusive m o d e s of a p o l y m e r coil in dilute
solution ( R i c h t e r et al. 1978). T h e r e l a x a t i o n time x(q)
for the observed c o n c e n t r a t i o n fluctuation correla
tions w a s f o u n d t o be in a g r e e m e n t with t h e disper
sion relation p r e d i c t e d earlier by de G e n n e s ,
=
3
~\)
DRhq , characteristic of flexible coil m o t i o n s
in a solution with solvent backflow. T h i s relation w a s ,
however, first confirmed b y light scattering experi
m e n t s ( A d a m a n d D e l s a n t i 1977). T h e t w o results
m a y be c o m p l e m e n t a r y , b u t the q u e s t i o n is raised of
a n a p p r o p r i a t e use for the n e u t r o n scattering. T h e
n e u t r o n spin e c h o s p e c t r o m e t e r h a s been used t o
p r o v i d e a set of d a t a for diffusion coefficients in lowmolecular-weight melts, as a function of m o l e c u l a r
weight (Higgins 1982). T h e r e w a s s o m e h o p e of
detecting r e p t a t i o n m o d e s in t h e r m a l B r o w n i a n
m o t i o n , b u t t h e time scale h e r e is i n a p p r o p r i a t e .
R e a l - t i m e n e u t r o n scattering e x p e r i m e n t s were set
u p for t h e s t u d y of stress r e l a x a t i o n a t c o n s t a n t strain
in p o l y s t y r e n e melts ( B o u e et al. 1982). H e r e , the
r e t u r n t o e q u i l i b r i u m c a n be slowed d o w n by c o n t r o l l
ing the t e m p e r a t u r e n e a r (above) t h e glass-transition
t e m p e r a t u r e Tg. M o r e o v e r , q u e n c h i n g t h e s a m p l e
freezes the coil c o n f i g u r a t i o n a t given times t. Several
tests c o u l d be m a d e c o n c e r n i n g either t h e R o u s e
llA
r e p r e s e n t a t i o n of t h e d a t a as a function of qt
or
alternatively the i n d e p e n d e n c e of the relaxation times
with the w a v e vector q.
Results of a quasi-elastic i n c o h e r e n t scattering
e x p e r i m e n t b y c o u n t e r i o n diffusive m o t i o n s a r e
also w o r t h m e n t i o n i n g . T h e diffusion coefficient of
t e t r a m e t h y l a m m o n i u m in t h e presence of p o l y i o n s
(sulfonated
polystyrene)
is
found
to
be
1
Z) = 3 . 7 x l O ^ c n v V (Nallet et al. 1983). T h i s is
lower by a factor of four t h a n t h e m e a s u r e d value of
_ 5
2
_1
in t h e presence of B r " . T h i s
D= 1.5 x 1 0 c m s
reference reflects t h e larger electric field g r a d i e n t s
associated with p o l y i o n s .
6. Concluding
Note
Neutron
Scattering
Bibliography
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353
Polymers:
Neutron
Scattering
Being a s c a t t e r i n g t e c h n i q u e , a R a m a n s p e c t r u m m a y
b e t a k e n from a n y s a m p l e of a r e a large e n o u g h t o
scatter a focused laser b e a m ( a p p r o x i m a t e l y 50
d i a m e t e r ) . F i b e r s , films, p o w d e r s , gels a n d crystalline
solids of p o l y m e r s h a v e b e e n e x a m i n e d w i t h success.
S o m e of t h e v i b r a t i o n a l b a n d s m o s t sensitive t o
c h a n g e s in p o l y m e r c o n f o r m a t i o n a r e w e a k in
infrared a b s o r p t i o n , b u t a r e t h e m o s t intense lines
in R a m a n . F u r t h e r m o r e , w a t e r , as t h e n a t u r a l solvent
in t h e b o d y a n d also a relatively w e a k s c a t t e r e r in
R a m a n , c a n b e u s e d in s o l u t i o n studies. T h i s aspect is
very i m p o r t a n t in s t r u c t u r a l studies of b i o p o l y m e r s .
T h e origin of t h e n o r m a l R a m a n effect c a n b e
u n d e r s t o o d in t e r m s of t h e classical t r e a t m e n t of
m o l e c u l a r v i b r a t i o n s . T h i s t h e o r y is b a s e d o n t h e idea
t h a t i n c i d e n t e l e c t r o m a g n e t i c r a d i a t i o n w i t h fre
q u e n c y v 0 i n d u c e s a v a r i a b l e d i p o l e m o m e n t given
by:
= <xE0 COS 2nVjt
(1)
w h e r e En a n d Em a r e t h e energies a s s o c i a t e d w i t h
v i b r a t i o n a l states a n d m, respectively. Since these
energy levels a r e c h a r a c t e r i s t i c of t h e chemical a n d
physical s t r u c t u r e s of p o l y m e r s , R a m a n s p e c t r o s c o p y
h a s been utilized as a c h a r a c t e r i z a t i o n m e t h o d for
these m a t e r i a l s .
(2)
w h e r e is t h e m o l e c u l a r polarizability, E0 is t h e
a m p l i t u d e of t h e i n c i d e n t electric field a n d v, is t h e
frequency of t h e ith n o r m a l v i b r a t i o n . T h e m o l e c u l a r
p o l a r i z a b i l i t y is n o t a c o n s t a n t , since it d e p e n d s o n t h e
m o l e c u l a r c o n f o r m a t i o n , w h i c h c h a n g e s w i t h displa
c e m e n t of t h e nuclei d u r i n g n o r m a l v i b r a t i o n s . T h e r e
fore, t h e p o l a r i z a b i l i t y is usually expressed as:
= 0 + ' c o s 2nvtt
(3)
w h e r e aj is t h e c h a n g e in t h e polarizability w i t h
respect t o t h e d i s p l a c e m e n t of t h e ith n o r m a l c o o r d i n
ate. T h e r e f o r e t h e i n d u c e d d i p o l e m o m e n t c a n b e
expressed as
p = (X0E0 c o s 2 0 /
+ 0 c o s 2 0 / c o s 2nvtt
= oc0E0 COS 2nv0t
(4)
+ a j i s 0 c o s 2 ( 0 + ,)/
+ ((0 c o s 2 ( 0 - v f ) i
1. Raman
Effect
in Polymer
Science
R a m a n first o b s e r v e d t h e inelastic s c a t t e r i n g p r o c e s s
of p h o t o n s from m a t t e r in 1928 a n d w a s a w a r d e d t h e
N o b e l Prize in 1930 for this discovery. I n t h e s u b s e
q u e n t y e a r s , i n s t r u m e n t a t i o n difficulties a n d s t r i n g e n t
sample requirements m e a n t that R a m a n spectroscopy
r e m a i n e d a fairly exotic t e c h n i q u e . W i t h a d v a n c e s in
i n s t r u m e n t a t i o n , p a r t i c u l a r l y after t h e a d v e n t of t h e
laser, R a m a n s p e c t r o s c o p y h a s d e v e l o p e d i n t o a p r o
m i n e n t b r a n c h of m o l e c u l a r s p e c t r o s c o p y . Since t h e
early 1970s, R a m a n s p e c t r o s c o p y (i.e., analysis) h a s
been used extensively in t h e investigations of p o l y m e r
structure and composition.
T h e i m p o r t a n c e of R a m a n s p e c t r o s c o p y in investig
ating polymer structures c a n n o t be overestimated.
354
(5)
F r o m classical e l e c t r o d y n a m i c s c a n oscillate n o t
only w i t h t h e frequency v 0, b u t also w i t h frequencies
v 0 v, a n d v 0 + v,.. T h e last t w o t e r m s a r e k n o w n as t h e
S t o k e s a n d a n t i - S t o k e s t r a n s i t i o n s in a R a m a n spec
t r u m . It s h o u l d b e e m p h a s i z e d t h a t c e r t a i n s y m m e t r i c
v i b r a t i o n s w i t h large c h a n g e s in t h e polarizability
t e n s o r a r e s t r o n g in R a m a n b u t m a y b e w e a k in
infrared. T h e s e v i b r a t i o n s i n c l u d e c o n f o r m a t i o n a l l y
sensitive skeletal v i b r a t i o n s w h i c h a r e i m p o r t a n t in
structural characterization.
I n strict t e r m s , a q u a n t u m m e c h a n i c a l t r e a t m e n t is
n e e d e d in o r d e r t o derive t h e full t h e o r y of R a m a n
scattering. R a m a n intensity a s s o c i a t e d w i t h t h e ith
v i b r a t i o n is often expressed as
2
h =
2 (0 -
vtfhN
*\[1-(-,/*)
(a') /0
(6)
Polymers:
Raman
Spectroscopy
Figure 1
Schematic diagram of a Raman spectrometer
H e r e t h e v i b r a t i o n a l p a r t of t h e t o t a l w a v e function of
the molecule is t a k e n a s t h a t of t h e h a r m o n i c oscil
l a t o r of frequency v, a n d r e d u c e d m a s s ; is t h e
n u m b e r of scatterers; I0 is t h e intensity of t h e incident
laser source; a n d ('), is t h e derivative of t h e c o m
p o n e n t of t h e polarizability t e n s o r associated with t h e
/th v i b r a t i o n a l t r a n s i t i o n .
2, Experimental
Aspects
T h e principal type of R a m a n i n s t r u m e n t a t i o n h a s
n o w b e c o m e fairly s t a n d a r d i z e d a n d is s h o w n s c h e m a
tically in Fig. 1. A n u m b e r of i n s t r u m e n t s w i t h
exceptional optical p e r f o r m a n c e a r e available c o m
mercially. T h e R a m a n s p e c t r o m e t e r s usually incor
p o r a t e a n a r g o n - i o n laser as t h e excitation s o u r c e .
This laser is c a p a b l e o f p r o v i d i n g lasing lines o f
sufficient p o w e r with w a v e l e n g t h s v a r y i n g from u l t r a
violet t o t h e green 5145 A line for i l l u m i n a t i o n . T h e
high fluorescent b a c k g r o u n d o b s e r v e d in s o m e
R a m a n spectra generally arises from i m p u r i t i e s in t h e
sample. I n these cases, t h e excitation w a v e l e n g t h s
should be shifted t o below t h e energy of t h e electronic
transition of t h e impurities. Y e l l o w o r red lasing lines
from k r y p t o n o r h e l i u m - n e o n gas lasers a r e available
for this p u r p o s e , a n d t h e g r a t i n g a n d p h o t o m u l t i p l i e r
are selected t o m a x i m i z e d e t e c t i o n efficiency.
D o u b l e o r triple m o n o c h r o m e t e r s a r e usually
e m p l o y e d in t a n d e m t o s e p a r a t e t h e scattered R a m a n
355
Polymers:
Raman
Spectroscopy
h a n d l e d by inexpensive m i c r o p r o c e s s o r systems.
T h e s e m i c r o p r o c e s s o r s are q u i t e powerful m a c h i n e s
offering versatile e x p e r i m e n t a l c o n t r o l a n d c o m p u t a
tional capabilities. H o w e v e r , if high precision is
needed, the c o m p u t a t i o n a l speed of m i c r o p r o c e s s o r s
is insufficient. F u r t h e r m o r e , even t h o u g h the h a r d
w a r e c a n be o b t a i n e d at quite r e a s o n a b l e prices,
software d e v e l o p m e n t c a n b e c o m e the single m o s t
costly item. T h e r e f o r e , a R a m a n d a t a collection sys
t e m designed a r o u n d the d a t a r e d u c t i o n or e v a l u a t i o n
p r o g r a m s available o n a higher level c o m p u t e r system
is usually desirable. D a t a transfer between v a r i o u s
c o m p u t e r s c a n usually be a c c o m p l i s h e d by c o n c u r r e n t
execution of linking p r o g r a m s with m i n i m a l h a n d
shaking.
3. New Applications
of Raman
Spectroscopy
356
Spectroscopic
Characterization;
Bibliography
Koningstein J A 1972 Introduction to the Theory of the
Raman Effect. Reidel, Dordrecht, The Netherlands
Shepherd I W 1977 Raman polarization techniques in the
study of macromolecules. Adv. Infrared Raman Spectrosc.
3: 127-66
Polymers:
and
Stabilization
test
conditions
Intensity of t e s t
service
conditions
Figure 1
Schematic representation of the relationship between test
conditions and service life
p o l y m e r c o m p o s i t i o n s a r e usually e v a l u a t e d by
m a t e r i a l s - o r i e n t e d tests before i n c o r p o r a t i o n i n t o a
finished p r o d u c t .
7. Measurement
of Thermal
Stability
E a r l y in t h e d e v e l o p m e n t of synthetic p o l y m e r s , c o n
siderable research effort w a s directed t o w a r d s their
p y r o l y t i c b e h a v i o u r . Tests t o m e a s u r e the d e c o m p o s i
tion t e m p e r a t u r e were b a s e d o n weight loss d u r i n g
h e a t i n g , either in v a c u u m o r in a n inert a t m o s p h e r e .
In a n a l t e r n a t i v e p r o c e d u r e , the p r e s s u r e developed by
volatile f r a g m e n t s from t h e p o l y m e r w a s d e t e r m i n e d .
Test s a m p l e s in sealed, e v a c u a t e d t u b e s were h e a t e d a t
p r o g r a m m e d rates of t e m p e r a t u r e increase a n d
c h a n g e s in s a m p l e weight m e a s u r e d . A l t h o u g h these
tests m a d e i m p o r t a n t c o n t r i b u t i o n s t o t h e s t r u c t u r a l
analysis of p o l y m e r s , t h e c o n d i t i o n s used a r e n o t
e n c o u n t e r e d in m o s t a p p l i c a t i o n s . T h e r m a l d e g r a d a
tion of p o l y m e r s in t h e presence of oxygen, however,
is c o m m o n t o all p o l y m e r s a n d several i m p o r t a n t tests
h a v e b e e n used t o m e a s u r e this effect.
1.1 Milling
Tests
T h e earliest tests for stability t o t h e r m a l o x i d a t i o n
o r i g i n a t e d in t h e s t u d y of t h e a g i n g of n a t u r a l r u b b e r .
In milling tests, r u b b e r s a m p l e s were passed conti
n u o u s l y b e t w e e n h e a t e d rolls, held a t close clearance.
T h e c o m b i n a t i o n of m e c h a n i c a l energy a n d h e a t
357
Polymers:
and
Stabilization
358
c h a m b e r t o a b s o r b a n y w a t e r evolved as the s a m p l e
oxidizes.
Small s a m p l e s c a n be used in oxygen u p t a k e
m e a s u r e m e n t s , b u t s a m p l e thickness m u s t be carefully
c o n t r o l l e d . If t h e s a m p l e s a r e t o o thick, diffusion of
oxygen i n t o t h e p o l y m e r b u l k m a y b e c o m e the c o n
trolling r a t e factor. R e p r o d u c i b l e results c a n be
o b t a i n e d a b o v e t h e m e l t i n g r a n g e of t h e p o l y m e r ,
p r o v i d e d t h a t s a m p l e thickness d o e s n o t c h a n g e
significantly.
Originally, o v e n s were used for this test b u t m o r e
u n i f o r m s a m p l e t e m p e r a t u r e s a r e o b t a i n e d in a n oil
b a t h o r in a m e t a l block drilled t o a c c o m m o d a t e
s a m p l e t u b e s a n d c o n t r o l devices a n d h e a t e d b y
external h e a t e r s . T h e r a t e of o x i d a t i o n is m e a s u r e d
either volumetrically o r m a n o m e t r i c a l l y . W i t h t h e
former method, sample tubes are connected to a
b u r e t t e w h i c h is fitted with a levelling b u l b t o m a i n
t a i n a t m o s p h e r i c p r e s s u r e . It is possible t o follow
oxygen u p t a k e m a n o m e t r i c a l l y , b u t t h e r a t e of reac
tion is p r e s s u r e d e p e n d e n t , decreasing s h a r p l y as the
p r e s s u r e falls in t h e r e a c t i o n vessel.
O x y g e n u p t a k e m e a s u r e m e n t s h a v e several a d v a n
tages over the basic o v e n aging test. T h e r a t e of
r e a c t i o n with o x y g e n is followed c o n t i n u o u s l y a n d
there is n o i n t e r r u p t i o n in t h e test t o w i t h d r a w s a m
ples. Since s a m p l e size is very small, m a n y tests c a n be
r u n s i m u l t a n e o u s l y . H o w e v e r , it is advisable t o r u n
e a c h s a m p l e in d u p l i c a t e to c o m p e n s a t e for v a r i a t i o n s
in t h e m a t e r i a l . T h i s m e t h o d is widely used in e v a l u a t
ing t h e relative effectiveness of stabilizers. T h e p o i n t
of failure is t a k e n as t h e time a t w h i c h o x i d a t i o n
b e c o m e s a u t o c a t a l y t i c a n d is usually r e p o r t e d as the
i n d u c t i o n p e r i o d (i.e., time interval b e t w e e n the start
of t h e test a n d t h e intercept of t h e steady-state r a t e
e x t r a p o l a t e d b a c k t o t h e time axis).
M e c h a n i c a l , dielectric o r aesthetic failure d o n o t
a l w a y s coincide w i t h t h e i n d u c t i o n p e r i o d . A b e t t e r
c o r r e l a t i o n with a c t u a l failure c a n be o b t a i n e d b y first
d e t e r m i n i n g t h e level of o x i d a t i o n a t which a critical
p r o p e r t y exceeds t h e a l l o w a b l e limit, a n d t h e n deter
m i n i n g the time r e q u i r e d t o react with this a m o u n t of
oxygen.
1.4 Thermal
Analysis
T h e r m o a n a l y t i c a l t e c h n i q u e s h a v e been a d a p t e d t o
t h e m e a s u r e m e n t of t h e r m a l d e g r a d a t i o n , b o t h in t h e
a b s e n c e a n d in t h e presence of oxygen. C o m m e r c i a l
e q u i p m e n t is available for t h e r m o g r a v i m e t r i c analysis
( T G A ) , differential t h e r m a l analysis ( D T A ) a n d dif
ferential s c a n n i n g c a l o r i m e t r y ( D S C ) . E a c h of these
m e t h o d s h a s been used in t h e m e a s u r e m e n t of o x i d a
tive d e g r a d a t i o n in p o l y m e r s .
M o d e r n T G A is a n a d a p t a t i o n of early m e t h o d s
used t o s t u d y t h e pyrolysis of p o l y m e r s . T h e a p p a r a
t u s consists of a highly sensitive b a l a n c e enclosed in a
glass vessel. T h e test c h a m b e r m a y b e e v a c u a t e d o r
filled w i t h a n inert gas for m e a s u r i n g t h e t e m p e r a t u r e
Tc a t w h i c h p o l y m e r d e c o m p o s i t i o n t a k e s place. T h e
Polymers:
7.5 Chemiluminescence
200
300
400
500
Temperature (C)
600
700
Figure 2
TGA scans for the thermal degradation of typical
polymers: (a) polyvinyl chloride), (b) polyethylene, and
(c) a polyamide
test is p r o g r a m m e d t o a selected r a t e of t e m p e r a t u r e
increase a n d s a m p l e weight is m o n i t o r e d c o n t i
n u o u s l y . T y p i c a l T G A d a t a a r e s h o w n in F i g . 2 for
the t h e r m a l d e g r a d a t i o n of several different p o l y m e r s .
T G A is a l s o used t o m e a s u r e t h e r a t e o f t h e r m a l
o x i d a t i o n . F o r these m e a s u r e m e n t s t h e s a m p l e is
h e a t e d i s o t h e r m a l l y usually in t h e 2 0 0 - 2 6 0 C r a n g e .
A n inert a t m o s p h e r e is m a i n t a i n e d o v e r t h e s a m p l e
until t h e test t e m p e r a t u r e is r e a c h e d a n d t h e inert g a s
is r a p i d l y replaced w i t h oxygen a t this p o i n t . W e i g h t
c h a n g e s a r e p l o t t e d a g a i n s t time. F o r stabilized
p o l y m e r s , t h e r e is n o significant weight c h a n g e until
the stabilizer is e x h a u s t e d . O x i d a t i o n t h e n t a k e s place
a n d there is a r a p i d gain in weight. T h e p e r i o d
between t h e i n t r o d u c t i o n o f o x y g e n a n d t h e o n s e t o f
r a p i d o x i d a t i o n is t a k e n a s t h e i n d u c t i o n p e r i o d .
D T A is b a s e d o n t h e principle o f a difference in
temperature response between the polymer a n d a n
inert c o n t r o l d u r i n g h e a t i n g . T h e r m o c o u p l e s in c o n
tact with b o t h p o l y m e r a n d c o n t r o l detect t h e t e m p e r
a t u r e differential AT. A s t r o n g e x o t h e r m indicates t h e
onset o f t h e a u t o c a t a l y t i c r e a c t i o n a n d t h e t i m e
required t o r e a c h this p o i n t defines t h e i n d u c t i o n
p e r i o d (see F i g . 3).
D S C is a n a d a p t a t i o n o f c o n v e n t i o n a l a d i a b a t i c
calorimetry. T h e test is n o t a s a c c u r a t e a s c o n v e n
tional c a l o r i m e t r y , b u t is a d e q u a t e for m e a s u r i n g t h e
t h e r m a l d e g r a d a t i o n o r o x i d a t i o n of p o l y m e r s . O x i d a
tive d e g r a d a t i o n a p p e a r s a s a s t r o n g e x o t h e r m in t h e
D S C m e a s u r e m e n t . T h e r m o m e c h a n i c a l analysis is
used t o m e a s u r e c h a n g e s in a m e c h a n i c a l p r o p e r t y
d u r i n g h e a t i n g . T o r s i o n a l b r a i d a n d volatilization
analyses h a v e also b e e n used t o m e a s u r e t h e r m a l
degradation,
b u t these t e c h n i q u e s
have
had
only limited a p p l i c a t i o n in m e a s u r i n g p o l y m e r
degradation.
and
Stabilization
Measurements
L i g h t is e m i t t e d d u r i n g t h e o x i d a t i o n of m a n y
polymers producing the p h e n o m e n o n of chemilumi
nescence. L i g h t emission is a t t r i b u t e d t o radicali n d u c e d r e a c t i o n s in t h e p o l y m e r m a s s . T e s t samples
a r e h e a t e d a t c o n s t a n t t e m p e r a t u r e u n d e r a s t r e a m of
o x y g e n . A s d e g r a d a t i o n p r o c e e d s , e m i t t e d light is
focused b y a lens system o n t o a p h o t o m u l t i p l i e r . T h e
q u a n t i t y o f e m i t t e d light is p l o t t e d a g a i n s t time. T h i s
t e c h n i q u e h a s been used t o detect d e g r a d a t i o n in t h e
latter stages o f t h e r e a c t i o n , b u t it m a y also b e used t o
detect early r e a c t i o n s o c c u r r i n g d u r i n g t h e i n d u c t i o n
p e r i o d . Since t h e q u a n t i t y o f light e m i t t e d early in t h e
r e a c t i o n is very small, it is necessary t o magnify t h e
effect. T h i s m a y b e d o n e either b y r a p i d l y replacing a n
inert a t m o s p h e r e with o x y g e n o r b y briefly exposing
t h e s a m p l e t o ultraviolet (uv) r a d i a t i o n . T h i s modifi
c a t i o n of t h e m e t h o d c o u l d b e useful in t h e early
d e t e c t i o n of o x i d a t i v e d e g r a d a t i o n . C h e m i l u m i n e s
cence c a n b e used t o e v a l u a t e b o t h t h e r m a l a n d
p h o t o o x i d a t i o n in p o l y m e r s .
Resistance
E l a s t o m e r s w h i c h c o n t a i n ethylenic u n s a t u r a t i o n in
the backbone chain are degraded rapidly by ozone
w h e n held u n d e r stress. R e s i s t a n c e t o o z o n e a t t a c k is
usually m e a s u r e d b y l a b o r a t o r y tests. A s t a n d a r d
m e t h o d h a s b e e n established b y t h e A m e r i c a n Society
for T e s t i n g a n d M a t e r i a l s ( A S T M ) . I n this test, s a m
ples a r e p l a c e d in a n a l u m i n u m c h a m b e r a n d held a t a
p r e s c r i b e d level o f stress. T e m p e r a t u r e is m a i n t a i n e d
a t 4 0 - 5 0 C while a m i x t u r e o f 500 p p b of o z o n e in
o x y g e n is p a s s e d o v e r t h e s a m p l e s . C r a c k s , which
a l w a y s f o r m p e r p e n d i c u l a r t o t h e direction o f applied
stress, indicate t h e o n s e t of d e g r a d a t i o n . T h e s e c r a c k s
oxygen
introduced
I
- induction period
Temperature
Figure 3
Typical DTA scan for the thermal oxidation of a
stabilized polymer
359
Polymers:
and
Stabilization
3.
Weather ability
Tests
T h e d e g r a d a t i o n w h i c h occurs in p o l y m e r s d u r i n g
o u t d o o r e x p o s u r e is m e a s u r e d by either o u t d o o r o r
i n d o o r tests. T h e simplest of t h e o u t d o o r tests consists
of exposing samples at locations selected for their
high intensity of solar r a d i a t i o n . S a m p l e s a r e ex
a m i n e d periodically for evidence of d e g r a d a t i o n such
as d i s c o l o r a t i o n o r surface c r a c k i n g . W h e n m o r e
precise d a t a a r e required, s a m p l e s c a n be r e m o v e d
from the e x p o s u r e r a c k s a n d c h a n g e s in m e c h a n i c a l ,
electrical o r chemical p r o p e r t i e s m e a s u r e d .
O u t d o o r e x p o s u r e c o n d i t i o n s h a v e been s t a n d a r d
ized by the A S T M . T h e angle at which s a m p l e s a r e
m o u n t e d h a s been established as 45 with s a m p l e s
facing d u e s o u t h . M a t e r i a l t o be used in c o n s t r u c t i n g
the e x p o s u r e r a c k s a n d the n a t u r e of t h e u n d e r l y i n g
surface a r e also specified. A p p l i c a t i o n of these s t a n
d a r d s p r o v i d e s a r e a s o n a b l e c o r r e l a t i o n b e t w e e n dif
ferent l o c a t i o n s , b u t t h e time t o failure is usually only
a b o u t half t h a t e n c o u n t e r e d in service. A s o m e w h a t
higher level of acceleration is o b t a i n e d by c o n t i
n u o u s l y r o t a t i n g samples to follow t h e s u n ' s p a t h .
T h e s e s o l a r - t r a c k i n g devices a r e c o m p l i c a t e d a n d re
q u i r e c o n s i d e r a b l e m a i n t e n a n c e . F u r t h e r m o r e , there
is little a d d i t i o n a l acceleration over
fixed-angle
exposure.
T h e highest level of acceleration in a n o u t d o o r test
h a s been r e p o r t e d for devices which, in a d d i t i o n t o
solar t r a c k i n g , use a series of polished m e t a l m i r r o r s
to a c c u m u l a t e solar r a d i a t i o n a n d t o direct it t o the
surface of test samples. In these devices, k n o w n as
E M M A ( e q u a t o r i a l m o u n t with m i r r o r s for accelera
tion) devices, samples m a y r e a c h fairly high t e m p e r a
tures. A n air s t r e a m or a w a t e r jet is used to c o n t r o l
the t e m p e r a t u r e , b u t the c o n t r i b u t i o n of t h e r m a l
d e g r a d a t i o n m a y still exceed t h a t which occurs o u t
d o o r s . H o w e v e r , test results c a n be o b t a i n e d in a b o u t
o n e - t e n t h the time r e q u i r e d for n o r m a l o u t d o o r
exposure.
Results o b t a i n e d with a n y o u t d o o r test a r e subject
to w e a t h e r variability. F u r t h e r m o r e , e x p o s u r e is
limited t o daylight h o u r s a n d this seriously restricts
the level of acceleration. T h e s e factors h a v e stimu
lated d e v e l o p m e n t of devices t o m e a s u r e w e a t h e r ability in a l a b o r a t o r y e n v i r o n m e n t . T h e devices for
i n d o o r testing a r e k n o w n as w e a t h e r o m e t e r s .
T h e basic c o m p o n e n t of a w e a t h e r o m e t e r is a n
artificial source for uv r a d i a t i o n . S a m p l e s , m o u n t e d
o n r a c k s , r o t a t e slowly a r o u n d t h e light source. It is
very i m p o r t a n t t o use a light source with a uv spec
t r u m closely resembling t h a t of the sun. C a r b o n a n d
360
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George G A 1981 Use of chemiluminescence to study the
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Gray V E, Cadoff C 1967 Survey of techniques for
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weatherability of plastics. Appl. Polym. Symp. 4: 61-83
Polymers:
Tests for
developing
Flammability
developed
W . L. H a w k i n s
[ M o n t c l a i r , N e w Jersey, U S A ]
1. Fire Development
Regimes
Time
Figure 1
Idealized fire development curve showing the three regimes
of fire growth ( Underwriters Laboratories, Melville,
New York. Reproduced with permission)
B u n s e n b u r n e r o p e r a t e in t h e incipient regime. T h e
p e r f o r m a n c e of a p o l y m e r in small-scale tests m a y
relate t o its p e r f o r m a n c e in a n incipient fire, b u t such
tests a r e n o t reliable p r e d i c t o r s of p e r f o r m a n c e in
d e v e l o p i n g o r fully d e v e l o p e d fires b e c a u s e they d o
n o t s i m u l a t e t h e t h e r m a l e n v i r o n m e n t of these larger
fires.
F l a m m a b i l i t y tests t h a t o p e r a t e in t h e developing
regime typically h a v e higher-energy ignition sources
t h a n incipient tests, a r e usually larger in scale a n d
often p r o v i d e c o n t a i n m e n t so t h a t h e a t loss is res
tricted t o p r o v i d e a severe t h e r m a l e n v i r o n m e n t .
P e r h a p s t h e m o s t widely used test in this regime is the
A S T M E 8 4 surface flame s p r e a d test w h i c h utilizes a
1.4 m l o n g ignition flame a n d a test s a m p l e 7.6 m long.
F l a m m a b i l i t y tests t h a t o p e r a t e in t h e fully d e
veloped regime typically h a v e high-flux ignition
sources a n d p r o v i d e for c o n t a i n m e n t of energy a n d
full i n v o l v e m e n t of test s a m p l e s . G e n e r a l l y , they a r e
used t o m e a s u r e t h e fire e n d u r a n c e of s t r u c t u r a l
e l e m e n t s such as walls.
In t h e section t h a t follows, s o m e of t h e widely used
flammability
tests a p p l i c a b l e t o p o l y m e r s h a v e been
selected a n d g r o u p e d a c c o r d i n g t o t h e regime of fire
intensity w h e r e they a r e m o s t applicable.
2. Incipient
Regime
Tests
361
Polymers:
Tests for
Flammability
Opening
(2.5
cm
Support
diameter)
rod
Pilot
flame
Figure 2
Apparatus for measuring ignition temperatures by ASTM
D1929
m i x t u r e of o x y g e n a n d n i t r o g e n , t h a t is r e q u i r e d t o
support combustion. Materials can then be rank
o r d e r e d w i t h t h e f l a m m a b l e m a t e r i a l s h a v i n g low
oxygen indices (below t h e 21 % 0 2 in t h e air) a n d fireresistant o n e s h a v i n g indices c o n s i d e r a b l y a b o v e 21 % .
It is c o m m o n p r a c t i c e t o specify a m i n i m u m oxygen
index of 2 8 % for fire-resistant m a t e r i a l s .
T h e o x y g e n index test is o n e of t h e m o s t widely
used flammability tests. I t is easy t o r u n , r e p r o d u c i b l e
a n d , m o s t i m p o r t a n t l y , yields a q u a n t i t a t i v e result
r a t h e r t h a n a pass/fail result for assessing t h e flamma
bility of m a t e r i a l s . It is a n excellent test for q u a l i t y
c o n t r o l a n d research, b u t p r o v i d e s insufficient infor
m a t i o n for p r e d i c t i n g t h e p e r f o r m a n c e of a m a t e r i a l in
a d e v e l o p i n g fire.
Several factors affecting t h e o x y g e n i n d e x test h e l p
explain t h e p o o r c o r r e l a t i o n b e t w e e n oxygen index
test results a n d d e v e l o p i n g fire p e r f o r m a n c e . U n l i k e a
d e v e l o p i n g fire, t h e r e is m i n i m a l energy feedback
f r o m t h e flame t o t h e p o l y m e r s u b s t r a t e t h e oxygen
level is adjusted so t h e flame is o n t h e verge of
extinguishing. T h i s s i t u a t i o n is in c o n t r a s t t o a large
fire w h e r e r a d i a t i v e feedback is t h e d o m i n a n t m o d e of
energy transfer.
T h e o x y g e n i n d e x decreases with increasing s a m p l e
t e m p e r a t u r e . F o r e x a m p l e , t h e oxygen index of a
p o l y c h l o r o p r e n e c o m p o u n d c o n t a i n i n g clay a n d car
b o n b l a c k a s t h e p r i n c i p a l additives is 3 3 % a t r o o m
t e m p e r a t u r e a n d 1 9 % a t 300 C ( J o h n s o n 1974). T h e
o x y g e n index also decreases w i t h decreasing s a m p l e
t h i c k n e s s . A n o t h e r factor is t h a t t h e r m o p l a s t i c m a t e r
ials often d r i p a n d flow a w a y from t h e flame. Since t h e
melted t h e r m o p l a s t i c carries h e a t a w a y , a higher
o x y g e n c o n c e n t r a t i o n is n e e d e d t o m a i n t a i n c o m b u s
t i o n a n d a h i g h e r o x y g e n i n d e x results. I n a real fire,
t h e r m o p l a s t i c s will often d r i p a n d b u r n in a m o l t e n
pool.
I n U L 9 4 , Tests for Flammability
of Plastic
Mater
ials for Parts in Devices and Appliances ( U n d e r w r i t e r s
Sample -
19 m m
Flame ^
Burner ~
2+
Figure 3
Apparatus for measuring oxygen index by ASTM D2863
362
Figure 4
The UL94 vertical test setup
Polymers:
mm
Specimen
Tests for
Flammability
Figure 5
L a b o r a t o r i e s 1980), m e t h o d s a r e p r o v i d e d for b o t h
vertical a n d h o r i z o n t a l testing. I n t h e vertical test (see
Fig. 4), a B u n s e n b u r n e r with a 19 m m flame is
applied t o test specimens 13 c m l o n g , 13 m m in w i d t h
a n d u p t o 13 m m in thickness. T h e b u r n e r is placed
u n d e r t h e s a m p l e for 10 s, t h e n w i t h d r a w n until
flaming ceases a n d reapplied for a n a d d i t i o n a l 10 s.
T h e d u r a t i o n of flaming c o m b u s t i o n after each flame
a p p l i c a t i o n is used t o r a t e m a t e r i a l s as 9 4 V - 0 if
flaming c o m b u s t i o n averages 5 s o r less w i t h o u t d r i p
p i n g flaming particles a n d 94 V - l if flaming c o m b u s
tion averages 25 s o r less w i t h o u t d r i p p i n g flaming
particles. M a t e r i a l s t h a t p r o d u c e d r i p p i n g flaming
particles t h a t ignite surgical c o t t o n a r e r a t e d 94 V-2.
3. Developing
Regime
Tests
Figure 6
The Steiner tunnel furnace for measuringflamespread and smoke developed by A S T M E84
363
Polymers:
Tests for
Flammability
Smoke detector
Combustion gas igniter
Plaque sample
Heating elements
Environmental
chamber
To gas supply
Pilot flame
Air inlet
Figure 7
The Ohio State University heat-release-rate calorimeter
(ASTM E906)
e x h a u s t d u c t of t h e tunnel. T h e a r e a u n d e r t h e p e r c e n t
a t t e n u a t i o n vs time curve for red o a k in a 10 m i n test
is assigned a value of 100. T h e s m o k e values of o t h e r
m a t e r i a l s a r e r e p o r t e d relative t o t h e red o a k value of
100.
T h e c o m b i n a t i o n of a large ignition flame, with a
heat-release r a t e of 88 k W , a n d a n insulated furnace
which r e r a d i a t e s h e a t o n c e it is h e a t e d u p p r o v i d e s a
severe test e n v i r o n m e n t . M e a s u r e m e n t s m a d e b y
P a r k e r (1977) indicate t h a t t h e s a m p l e in t h e flame
i m p i n g e m e n t a r e a is subjected t o 4 0 - 6 0 k W m "
incident h e a t flux.
M a t e r i a l s with a flame s p r e a d classification of 25 o r
less (less t h a n 1.5 m flame s p r e a d ) a r e generally
r e g a r d e d b y b u i l d i n g c o d e s a s p r o v i d i n g a high degree
of fire safety. T h e c o r r e l a t i o n of a low
flame-spread
classification w i t h g o o d fire p e r f o r m a n c e w a s e s t a b
lished for cellulosic ( w o o d ) m a t e r i a l s , b u t recent ex
periences w i t h t h e r m o p l a s t i c f o a m s s h o w t h a t A S T M
E 8 4 s h o u l d n o t b e e m p l o y e d a s t h e sole s o u r c e of fire
h a z a r d r a t i n g for p o l y m e r i c m a t e r i a l s .
T h e r a t e a t which a m a t e r i a l b u r n s (i.e., t h e r a t e a t
which it releases h e a t ) is a n i m p o r t a n t
flammability
p r o p e r t y since it is a m e a s u r e of fire intensity. R a t e of
h e a t release c a l o r i m e t e r s m e a s u r e rates of h e a t a n d
s m o k e release of a m a t e r i a l subjected t o a n externally
applied h e a t flux. U n l i k e m o s t o t h e r fire tests which
utilize only o n e e x p o s u r e c o n d i t i o n , heat-release-rate
c a l o r i m e t e r s allow t h e incident h e a t flux t o b e varied
from test t o test a n d , h e n c e , t h e influence of flux o n
release r a t e s c a n b e d e t e r m i n e d .
I n t h e O h i o State University ( O S U ) calorimeter (see
Fig. 7), w h i c h is used in A S T M E906 {Test Method for
Heat and Visible Smoke Release Rates of Materials
and Products), incident flux c a n be varied from a level
- 2
characteristic of a n incipient fire ( 0 - 1 0 k W m ) o n
t h r o u g h t h o s e characteristics of developing fires, u p t o
values associated w i t h fully d e v e l o p e d fires ( 8 0 2
l O O k W m " ) . R o w a n a n d L y o n s (1978) h a v e p u b
lished s o m e e x p e r i m e n t a l results t h a t d e m o n s t r a t e t h e
i m p o r t a n c e of externally i m p o s e d h e a t flux o n t h e
b u r n i n g b e h a v i o r of m a t e r i a l s . F i g u r e 8 s h o w s p e a k
heat-release rates vs incident applied flux for a series
of fire r e t a r d a n t p o l y u r e t h a n e a n d p o l y i s o c y a n u r a t e
f o a m s . T h e r a t e of b u r n i n g generally increases with
increasing incident flux a n d for flame r e t a r d a n t
250 r
!!"!!
11
364
Figure 9
The influence of externally applied flux on total smoke
emissions for various polymers (courtesy of Professor
. E. Smith, Ohio State University)
Polymers:
Tests for
Flammability
Photodetector
Light
source
Z ) s^ ( F / L ^ ) l o g ( 1 0 0 / r )
Radiant
heater
Figure 10
National Bureau of Standards smoke chamber (ASTM
E662)
w h e r e V is t h e c h a m b e r v o l u m e , L is t h e optical p a t h
length, A is t h e e x p o s e d specimen a r e a a n d is the
p e r c e n t t r a n s m i t t a n c e of t h e light b e a m .
T h e r e a r e several differences b e t w e e n s m o k e
m e a s u r e m e n t s in t h e N B S c h a m b e r a n d in the O S U
release-rate c a l o r i m e t e r . T h e N B S c h a m b e r is n o r
mally r u n a t only o n e s t a n d a r d i z e d flux. T h u s it
c a n n o t be related t o a real fire s i t u a t i o n w h e r e m a t e r
ials a r e e x p o s e d t o a s p e c t r u m of fluxes. T h e N B S
c h a m b e r m e a s u r e s t o t a l s m o k e b y a c c u m u l a t i n g it
within t h e b o x w h e r e a s t h e O S U c a l o r i m e t e r o p e r a t e s
with a n air flow t h r o u g h t h e c o m b u s t i o n c h a m b e r a n d
t o t a l s m o k e is d e t e r m i n e d b y i n t e g r a t i o n of the in
s t a n t a n e o u s s m o k e values. B o t h test m e t h o d s r e p o r t
s m o k e in optical density, w h i c h is linearly related t o
h u m a n visibility t h r o u g h s m o k e . B o t h m e t h o d s differ
greatly from t h e A S T M E 8 4 s m o k e m e a s u r e m e n t ,
w h e r e t h e a m o u n t of s m o k e g e n e r a t e d is d e p e n d e n t
o n t h e flame s p r e a d value of t h e m a t e r i a l tested.
4. Fully Developed
Regime
Tests
Time
(h)
Figure 11
The ASTM El 19 time-temperature curve for testing the
fire endurance of structures
Bibliography
American Society for Testing and Materials 1966 Sym
posium on Fire Test MethodsRestraint and Smoke 1966,
365
Polymers:
Tests for
Flammability
1.
T h e tensile b e h a v i o u r of a p o l y m e r is p r o b a b l y t h e
m o s t f u n d a m e n t a l m e c h a n i c a l p r o p e r t y used in t h e
e v a l u a t i o n of p o l y m e r s . T h e basic m e t h o d is
e m p l o y e d t o d e t e r m i n e yield s t r e n g t h , u l t i m a t e
s t r e n g t h a n d e l o n g a t i o n p r o p e r t i e s as well as v a r i o u s
m o d u l i w h i c h a r e i m p o r t a n t in designing with
polymers. T h e stress-strain diagram obtained can
also be used t o m e a s u r e t h e ability of a p o l y m e r t o
a b s o r b energy. T h i s is p a r t i c u l a r l y useful w h e n testing
vulcanized e l a s t o m e r s .
T h e tensile s t r e n g t h of a m a t e r i a l is the r a t i o of the
force a p p l i e d t o t h e m a t e r i a l a t r u p t u r e t o its original
cross-sectional a r e a . T h i s p r o p e r t y is typically called
t h e u l t i m a t e tensile s t r e n g t h , t h a t is, t h e s t r e n g t h a t
b r e a k , a n d is usually expressed in m e g a p a s c a l s . T h e
c o r r e s p o n d i n g extension is called the u l t i m a t e strain
o r u l t i m a t e e l o n g a t i o n a n d is typically given as a
percentage.
366
Tensile
Properties
Polymers:
Load
cell
Moving
crosshead
Test
sample
Moving
crosshead
Direction
of t r a v e l
Properties
Direction
of travel
Test
_
sample
Loadcell
Stationary
crossheaa
Stationary
crosshead
(a )
Figure 1
Schematic arrangements for determination of mechanical
properties of polymers: (a) tensile and (b) flexural
T h e e q u i p m e n t r e q u i r e d consists of a m a c h i n e
h a v i n g a m o v i n g a n d a fixed c r o s s h e a d t o w h i c h
c l a m p i n g fixtures a r e affixed t o h o l d t h e specimen.
O n e of t h e c l a m p s is a t t a c h e d t o a l o a d cell w h i c h m a y
be m o u n t e d o n either c r o s s h e a d . T h e m o v a b l e c r o s s h e a d c a n b e driven a t a c o n s t a n t r a t e w h i c h c a n b e
-1
1
varied from 0.25 m m m i n
t o 1250 m m m i n " o r
1
s o m e t i m e s u p t o 25 000 m m m i n " . O t h e r types of
e q u i p m e n t a r e able t o a p p l y a c o n s t a n t r a t e of l o a d i n g
to a specimen.
T h e l o a d o r resistance of t h e specimen t o d e f o r m a
tion is c o n t i n u o u s l y r e c o r d e d a n d t h e extension deter
m i n e d by use of a n e x t e n s o m e t e r c o n n e c t e d directly t o
the specimen o r b y m e a s u r i n g t h e d i s t a n c e b e t w e e n
g a u g e m a r k s o n t h e specimen d u r i n g t h e p r o g r e s s of
the test. T o p r e v e n t failure of t h e s a m p l e in t h e grips,
the test specimens usually h a v e a r e d u c e d cross sec
tion a n d are s o m e t i m e s referred t o as " d u m b - b e l l " o r
" d o g - b o n e " specimens. F i g u r e la illustrates t h e speci
m e n l o a d e d in tension. T h e force is r e c o r d e d u p t o t h e
p o i n t of r u p t u r e . T h e s e r e a d i n g s a r e c o n v e r t e d t o
stresses a n d a r e p l o t t e d a g a i n s t strain. F i g u r e 2 illus
trates typical s t r e s s - s t r a i n d i a g r a m s for t h e m a j o r
types of p o l y m e r .
A s stated, t h e tensile s t r e n g t h is t h e r a t i o of force t o
unit a r e a a n d is expressed a s follows:
Strain, e
Strain, e
Figure 2
Tensile curves for polymeric materials: (a) semicrystalline
polymer (
stress-strain curve, tangent modulus
of elasticity); (b) amorphous ductile polymer (
stress-strain curve, secant modulus of elasticity);
(c) amorphous brittle polymer (
stress-strain curve,
offset modulus); and (d) crosslinked rubber
(
stress-strain curve, 300% modulus)
F e a t u r e s t o b e n o t e d a r e yielding, n e c k i n g a n d
strain h a r d e n i n g . Semicrystalline p o l y m e r s such as
p o l y e t h y l e n e a n d p o l y p r o p y l e n e s h o w yielding, fol
l o w e d b y n e c k i n g , t h e n a n increase in s t r e n g t h before
r u p t u r e , as in F i g . 2a. F i g u r e 2 b s h o w s a ductile
p o l y m e r such as plasticized p o l y v i n y l chloride) w h i c h
s h o w s yielding a n d e l o n g a t i o n before failure. F i g u r e
2c s h o w s t h e b e h a v i o r of a brittle p o l y m e r such a s
p o l y s t y r e n e ; t h e s t r e s s - s t r a i n c u r v e s h o w s n o yield
p o i n t a n d low e l o n g a t i o n before failure. C r o s s l i n k e d
r u b b e r s b e h a v e as in F i g . 2d.
T h e m o d u l u s m a y also b e o b t a i n e d from t h e s t r e s s strain o r l o a d - d e f o r m a t i o n c u r v e . T h e m o d u l u s value
m o s t frequently used in design is Y o u n g ' s m o d u l u s E,
w h i c h is d e t e r m i n e d from t h e initial slope of the
s t r e s s - s t r a i n curve:
e = ( / - / 0) / / 0
= /
= F/A
0)
(2)
(3)
T h e d a s h e d line in F i g . 2a is a n e x t r a p o l a t i o n of t h e
initial linear p o r t i o n of t h e c u r v e for t h e c a l c u l a t i o n of
E.
O t h e r m o d u l u s values c o m m o n l y r e p o r t e d a r e t h e
secant m o d u l u s , t a n g e n t m o d u l u s a n d , in t h e case of
e l a s t o m e r s , t h e 3 0 0 % m o d u l u s ; t h e stress a t 3 0 0 %
e l o n g a t i o n is a c o m m o n l y r e p o r t e d p r o p e r t y . T h e s e
367
Polymers:
Properties
(4)
2. Flexural
Properties
R = kL /6d
(5)
D = 0.05 L /6d
(7)
EB = L m/4bd
(8)
3. Compressive
Strength
(6)
368
= 3PL/2bd
4. Time-Dependent
Properties
C r e e p a n d stress r e l a x a t i o n a r e i m p o r t a n t p r o p e r t i e s
of p o l y m e r s , since they m u s t be c o n s i d e r e d in t h e
design of a n y fabricated p a r t subjected t o c o n s t a n t
l o a d o r d e f o r m a t i o n . T h e influence of the e n v i r o n
m e n t t o which t h e p a r t is e x p o s e d m u s t also be t a k e n
i n t o c o n s i d e r a t i o n , including n o t only t h e v a r i a t i o n s
Polymers:
(a)
(c )
-/
time^O
= /?
-/
Creep
time =
[+/
0
'h
time = h
Stress relaxation
Figure 3
Time-dependent properties: (a) creep curves, strain vs time
(log hours) under load (; (b) creep modulus time (log
hours) at temperatures Tt\ (c) stress relaxation, stress time
(log hours) under deformation ,; and (d) schematic
representations of creep and stress relaxation
in t e m p e r a t u r e b u t also p o t e n t i a l e x p o s u r e t o c h e m
ical agents w h i c h m i g h t accelerate fracture in service.
C r e e p occurs w h e n t h e p o l y m e r is subjected t o a
c o n s t a n t stress below t h e yield stress o r fracture stress
of a m a t e r i a l . After a n initial d e f o r m a t i o n 0 which is
p r o p o r t i o n a l t o the applied stress , the m a t e r i a l
c o n t i n u e s to e l o n g a t e o r d e f o r m u n d e r t h e a p p l i e d
load until fracture o c c u r s . F r a c t u r e m a y be either
ductile o r brittle. T h e strain a t a n y time is a function
of the original strain which o c c u r s u p o n l o a d i n g plus
the t i m e - d e p e n d e n t c o m p o n e n t of strain. T h e strain
d e p e n d s o n t h e level of stress a n d t h e t e m p e r a t u r e a t
which the test is carried o u t . A general expression for
t i m e - d e p e n d e n t strain is
e(t) = e0(o) +
F[t g(o)]
(9)
Properties
a r e m a d e at c o n s t a n t t e m p e r a t u r e so t h a t t h e strain is
a function of stress a n d time h ( h o u r s ) at the test
t e m p e r a t u r e T. M e a s u r e m e n t s m a d e at several tem
p e r a t u r e s , including t h o s e expected in practice, allow
service life to be p r e d i c t e d , t a k i n g i n t o a c c o u n t the
v a r i a t i o n of creep with t e m p e r a t u r e as well as load.
F o r design p u r p o s e s t h e m o d u l u s is used t o predict
d e f o r m a t i o n u n d e r applied stress; h o w e v e r , since it
h a s been s h o w n t h a t the strain increases with time, it
follows t h a t t h e m o d u l u s also c h a n g e s with time. T h i s
c h a n g e is d e t e r m i n e d by dividing the applied stress
by t h e strain a t time h a n d p l o t t i n g the m o d u l u s Ecr
a g a i n s t time. T h e m o d u l u s value is called the creep
m o d u l u s . F i g u r e 3b illustrates this p r o p e r t y for a
Tx.
series of t e m p e r a t u r e s , w h e r e T4> T3> T2>
Stress r e l a x a t i o n is the decrease in stress with time
for a m a t e r i a l subjected t o c o n s t a n t d e f o r m a t i o n . It is
related t o creep. In this case t h e s a m p l e is strained t o a
p r e d e t e r m i n e d level a n d the r e d u c t i o n in force is
m e a s u r e d as a function of time. A stress relaxation
c u r v e is s h o w n in F i g . 3c. I n this case t h e stress is
p l o t t e d against time (In h) for a series of strain levels ,
where 4 > 3 > 2 >
A s c h e m a t i c a r r a n g e m e n t for t h e d e t e r m i n a t i o n of
creep a n d stress r e l a x a t i o n is s h o w n in Fig. 3d. In this
e x a m p l e t h e c r e e p is t h e increase in length a t time h
c a u s e d b y force F0. T h e stress r e l a x a t i o n indicates a
decrease in stress, F0 > Fh, at time h resulting from a
c o n s t a n t deflection .
F u r t h e r discussion o n t i m e - d e p e n d e n t p r o p e r t i e s is
to be f o u n d in N e l s o n (1974a, b ) , T u r n e r (1974), Levy
(1979) a n d W a r d (1983).
5. Impact
Properties
T h e i m p a c t b e h a v i o r of p o l y m e r s is a c a u s e for
c o n c e r n a m o n g designers b e c a u s e t h e p e r f o r m a n c e of
fabricated p a r t s subjected t o i m p a c t l o a d s or t o
d e f o r m a t i o n at high strain rates is often difficult t o
predict. It is also a c o m p l i c a t e d m a t t e r to develop
tests w h i c h c a n a c c u r a t e l y m o d e l t h e a c t u a l use c o n
d i t i o n s for t h e m a t e r i a l u n d e r c o n s i d e r a t i o n . In m a n y
cases failure occurs a t i m p a c t l o a d s far below the
i n h e r e n t s t r e n g t h o r t o u g h n e s s of the m a t e r i a l . T h e s e
p r o b l e m s h a v e led t o a large n u m b e r of m e t h o d s for
d e t e r m i n i n g the i m p a c t p r o p e r t i e s of p o l y m e r s a n d
likewise a large n u m b e r of m a c h i n e s of increasing
s o p h i s t i c a t i o n t o m e a s u r e the b e h a v i o r of p o l y m e r s
subjected t o i m p a c t l o a d i n g c o n d i t i o n s . I n s t r u m e n t e d
i m p a c t testing m a c h i n e s h a v e b e c o m e p o p u l a r in
recent years b e c a u s e m o r e i n f o r m a t i o n is g e n e r a t e d
r e g a r d i n g t h e m o d e of failure. T h e s e techniques h a v e
been a p p l i e d t o tensile i m p a c t , C h a r p y i m p a c t a n d
falling weight i m p a c t tests, a m o n g o t h e r s .
In t h e i n s t r u m e n t e d i m p a c t tests, a l o a d - t i m e
( d e f o r m a t i o n ) c u r v e is g e n e r a t e d as well as a n indica
tion of t h e energy r e q u i r e d t o cause failure. A typical
c u r v e from a n i n s t r u m e n t e d C h a r p y test is s h o w n in
369
Polymers:
Properties
Figure 4
Impact properties and testing: (a) curves for force
(
) and energy ( ) from instrumented impact test;
(b) schematic of pendulum-type impact tester;
(c) specimen Charpy impact test; and (d) specimen
configuration and loading arrangement for tensile impact
test
l/2
YPmLa /BW
(10)
w h e r e L , a, W a n d a r e the d i m e n s i o n s (m) of t h e
specimen s h o w n in Fig. 4c a n d Y is a g e o m e t r i c a l
factor related t o t h e n o t c h d e p t h - t h i c k n e s s r a t i o
1 / 2
a/W. T h e units of Kk a r e M P a m . T h e i m p a c t
2
strength (kJ m " ) is calculated from t h e failure energy
4 by
Is = EJB(W-a)
(11)
F i g u r e 4d s h o w s a tensile i m p a c t s a m p l e in a typical
test fixture. Tensile i m p a c t s t r e n g t h is also calculated
from t h e energy of failure a n d cross-sectional a r e a of
t h e specimen
h = EJWt
(12)
w h e r e W is the w i d t h a n d t t h e thickness of t h e
2
specimen. T h i s q u a n t i t y also h a s u n i t s of k J m ~ .
Tensile i m p a c t a n d C h a r p y i m p a c t s t r e n g t h s a r e
d e t e r m i n e d o n p e n d u l u m - t y p e i m p a c t m a c h i n e s with
test fixtures a p p r o p r i a t e for t h e specific m e t h o d . A
typical a r r a n g e m e n t for t h e C h a r p y test is s h o w n in
Fig. 4 b . M a n y types of falling weight i m p a c t tests a r e
also available, d e p e n d i n g o n t h e t y p e of specimen a n d
test d a t a r e q u i r e d . D a t a m a y b e r e p o r t e d in v a r i o u s
forms, such as kilojoules p e r m e t e r , kilojoules for 5 0 %
370
Handling
A d v a n c e s in c o m p u t e r t e c h n o l o g y , such as t h e wide
s p r e a d availability of m i n i c o m p u t e r s a n d m i c r o
c o m p u t e r s , h a v e led t o a r a p i d g r o w t h in a u t o m a t e d
d a t a h a n d l i n g in t h e l a b o r a t o r y . It is n o w possible
t o interface m a n y pieces of e q u i p m e n t t o a single
c o m p u t e r so t h a t d a t a is collected from e a c h simul
t a n e o u s l y . Software is available t o calculate such
p r o p e r t i e s as tensile s t r e n g t h , elastic m o d u l u s , flexural
modulus and impact properties, a m o n g others. The
d a t a c a n b e a n a l y z e d statistically a n d curves gener
a t e d t h r o u g h t h e use of p r i n t e r - p l o t t e r e q u i p m e n t .
T h e s e systems h a v e i m p r o v e d d a t a h a n d l i n g a n d
have reduced the materials characterization required.
F u r t h e r discussions of basic systems m a y be f o u n d in
C h u d z i c k i a n d P e a k e (1984) a n d H o l l a n d (1985).
See also: Elastomers: Tests for Mechanical Properties
Bibliography
American Society for Testing and Materials 1977 Standard
Test Method for Tensile, Compressive and Flexural Creep
and Creep-Rupture of Plastics, ASTM Designation D2990-77. ASTM, Philadelphia, PA
American Society for Testing and Materials 1979 Standard
Test Method for Tensile-Impact Energy to Break Plastics
and Electrical Insulating Materials, ASTM Designation
D-1822-79. ASTM, Philadelphia, PA
American Society for Testing and Materials 1980a Standard
Test Method for Compressive Properties of Rigid Plastics,
ASTM Designation D-695-80. ASTM, Philadelphia, PA
American Society for Testing and Materials 1980b Standard
Test Method for Rubber Properties in Tension, ASTM
Designation A-412-80. ASTM, Philadelphia, PA
American Society for Testing and Materials 1981a Standard
Test Methods for Flexural Properties of Unreinforced and
Reinforced Plastics and Electrical Insulating Materials,
ASTM Designation D-790-81. ASTM, Philadelphia, PA
American Society for Testing and Materials 1981b Standard
Test Methods for Impact Resistance of Plastics and Elec
trical Insulating Materials, ASTM Designation D-256-81.
ASTM, Philadelphia, PA
American Society for Testing and Materials 1982 Standard
Test Method for Tensile Properties of Plastics, ASTM,
Designation D-638-82a. ASTM, Philadelphia, PA
Brown R 1986 Physical Testing of Rubber, 2nd edn.
Elsevier, Amsterdam
Carlowtz 1972 Tabellarische Ubersicht uber die Prufung
von Kunststoffen, 4th edn. Umschau, Frankfurt, Ger
many, pp. 6-23; 26-31
Chudzicki J, Peake R J 1984 Unified approach to
computer-aided polymer characterization. Plastics in a
Polymers:
Tests for
Specific h e a t m e a s u r e m e n t s h a v e b e c o m e a c o m m o n
place t o o l for c h a r a c t e r i z i n g t h e b e h a v i o r of
p o l y m e r s . W i t h this k i n d of t h e r m a l d a t a t h e m a c r o
scopic b e h a v i o r of semicrystalline a n d
glassy
p o l y m e r s c a n b e s t u d i e d a n d often c o r r e l a t e d w i t h
o t h e r c o m p l e m e n t a r y m e t h o d s s u c h as d y n a m i c
m e c h a n i c a l , dielectric a n d n u c l e a r m a g n e t i c r e s o
n a n c e investigations of t h e s a m e p o l y m e r systems. I n
this m a n n e r it is often possible t o g a i n insight i n t o t h e
m i c r o s c o p i c origin of t h e o b s e r v e d t h e r m a l effects. A
n u m b e r of t h e r m a l m e t h o d s h a v e b e e n d e v e l o p e d t o
s t u d y n o t only p o l y m e r s b u t also t h e additives w h i c h
are usually b l e n d e d w i t h t h e m t o i m p r o v e t h e c h e m
ical a n d physical p r o p e r t i e s of t h e resin ( T u r i 1981).
1. Specific
Heat
Q=
T h e chief function of c a l o r i m e t r y in t h e a b s e n c e of
chemical c h a n g e is t h e d e t e r m i n a t i o n of t h e specific
h e a t C; this is m e a s u r e d as t h e h e a t Q a b s o r b e d b y a
system o n raising t h e t e m p e r a t u r e by 1 K :
C=Q/AT
CAT+
(1)
(2)
A n a d i a b a t i c c a l o r i m e t e r for p o l y m e r research h a s
b e e n described by K a r a s z a n d O'Reilly (1966). It
c o v e r s t h e r a n g e 1 5 - 6 0 0 w i t h a n a c c u r a c y of 0 . 1 0.2 % . T h i s t y p e of c a l o r i m e t e r , w h i c h h a s h e a t i n g
1
r a t e s of less t h a n T C m i n " a n d large e q u i l i b r a t i o n
times a t t h e e n d of e a c h h e a t i n g interval, is being
r e p l a c e d for p o l y m e r studies b y d y n a m i c c a l o r i m e t e r s
w i t h significantly faster h e a t i n g r a t e s .
T h e s e latter c a l o r i m e t e r s h a v e a b a n d o n e d the a d i a
b a t i c principle in favor of a h e a t leak w h i c h is the
s a m e for b o t h t h e s a m p l e a n d a reference. N u m e r o u s
i n s t r u m e n t s of this so-called heat-flux type calori
m e t e r a r e n o w c o m m e r c i a l l y available
A different a p p r o a c h t o d y n a m i c differential calori
m e t r y w a s r e p o r t e d by O ' N e i l l (1964), w h o described
a differential s c a n n i n g c a l o r i m e t e r ( D S C ) . T h i s differs
f r o m p r e v i o u s differential c a l o r i m e t e r s b y m a i n t a i n
ing t h e s a m p l e a n d reference a t identical t e m p e r a
t u r e s . T h e differential h e a t i n p u t p e r s e c o n d dq/dt
necessary t o achieve this c o n d i t i o n is m o n i t o r e d dir
ectly. T h i s differential, d u r i n g h e a t i n g with a r a t e
q = dT/dt, is p r o p o r t i o n a l t o t h e differential specific
heats:
m
XQ
- mCprc{t)q
(3)
E n d o t h e r m i c o r e x o t h e r m i c events a r e m e a s u r e d
directly as a function of t i m e . T h e e n t h a l p y of a
p r o c e s s is simply t h e a r e a a b o v e o r b e l o w t h e h e a t
c a p a c i t y o r i s o t h e r m a l baseline o n a p l o t of the
differential h e a t i n p u t p e r s e c o n d a g a i n s t time:
AH=j(dQ/dt)dt
(4)
In p r a c t i c e t h e specific h e a t a t c o n s t a n t p r e s s u r e Cp of
a n u n k n o w n b e t w e e n a lower t e m p e r a t u r e limit ,
a n d a n u p p e r t e m p e r a t u r e limit T2 c a n b e m e a s u r e d in
a D S C b y c o m p a r i n g t h e o r d i n a t e d i s p l a c e m e n t D% of
t h e u n k n o w n a n d t h a t of a s a m p l e of k n o w n specific
h e a t (usually a s a p p h i r e , A 1 2 0 3 , disk) w i t h t h e baseline
b e h a v i o r of t h e e m p t y D S C . T h e specific h e a t of the
s a m p l e c a n t h e n b e c a l c u l a t e d f r o m t h e following
expression:
Cps = ( ^ A h O , / ^ s ) ( ^ s / ^ A b O ) ) C M
Measurements
Properties
dQ/dt = ( m C
Thermal
h 30
(5)
371
Polymers:
Tests for
Thermal
Properties
A l 20 3
//
//
280
300
320
340
360
Temperature (K)
Figure 1
Comparative DSC scan of an unknown polymeric
material and a sapphire standard against an empty
sample
1
container produced by heating at 20 C min
a n d the u n k n o w n s a m p l e is t h e n p r o g r a m m e d
t h r o u g h t h e s a m e t e m p e r a t u r e s e q u e n c e . If t h e o r d i
n a t e displacement h a s been c a l i b r a t e d with a s t a n d a r d
such as i n d i u m with a k n o w n AHf value p r i o r t o t h e
Cp r u n , t h e s t a n d a r d s a p p h i r e r u n m a y be eliminated
or only carried o u t as a check of a c c u r a c y . By these
techniques C values with accuracies of b e t t e r t h a n
1 % c a n be o b t a i n e d from - 175 C t o 725 C.
2. Melting
Processes
and Equilibrium
Properties
It is difficult if n o t impossible t o g r o w p o l y m e r
crystals of sufficient size t h a t e x p e r i m e n t a l equi
librium p a r a m e t e r s c a n be o b t a i n e d b y direct
measurement. Thus, extrapolation techniques have
been developed t o give e q u i l i b r i u m d a t a from
m e a s u r e m e n t s o n small, m e t a s t a b l e crystals o r o n
equilibrium crystals of small molecules. A p p l i c a t i o n
of these m e t h o d s t o o b t a i n t h e e q u i l i b r i u m t h e r m o
d y n a m i c p r o p e r t i e s of polyethylene is described below
since its melting b e h a v i o r h a s been studied m o r e t h a n
t h a t of a n y o t h e r m a c r o m o l e c u l e .
T h e melting of b u l k crystallized p o l y m e r s usually
occurs over a b r o a d t e m p e r a t u r e r a n g e d u e t o a
d i s t r i b u t i o n of crystal sizes a n d defects. A linear
polyethylene s a m p l e w h i c h w a s c o o l e d slowly from
the melt before t h e s t a r t of t h e h e a t c a p a c i t y d e t e r m i
n a t i o n is s h o w n in Fig. 2 (solid line). Cp rises s h a r p l y
over a t e m p e r a t u r e r a n g e of 2 0 - 2 5 C t o a m a x i m u m
at 133 C, t h e n d r o p s a b r u p t l y a n d levels off. I n
c o n t r a s t t o this b e h a v i o r , t h e Cp of p o l y e t h y l e n e single
crystals p r e p a r e d from diluted h e x a d e c a n e s o l u t i o n is
p l o t t e d against t e m p e r a t u r e ( d a s h e d line, Fig. 2).
N e a r l y 90 % of t h e single crystals melt within a
372
100
120
Temperature
(C)
Figure 2
Melting curves of linear polyethylene:
bulk crystallized;
, solution crystallized
, annealed,
n a r r o w t w o - d e g r e e ( 1 2 6 - 1 2 8 C) interval. O n l y a trace
of m e l t i n g o c c u r s b e y o n d 128 C ( S o u t h e r n et al.
1972). T h i s n a r r o w m e l t i n g p e a k is a t t r i b u t e d t o
crystals with u n i f o r m thickness ( ~ 1 5 . 4 n m ) a n d t h e
a b s e n c e of a n y lamellar r e o r g a n i z a t i o n . T h e latter
process leads t o a n increase in t h e chain-folded lamel
lar thickness. U n d e r similar m e l t i n g c o n d i t i o n s crys
tals t h i n n e r t h a n 1 5 n m will thicken a n d exhibit
multiple m e l t i n g p e a k s . Bair et al. (1967) h a v e s h o w n
that radiation-induced
crosslinking c a n
retard
lamellar t h i c k e n i n g . T h e latter t e c h n i q u e c a n allow
m e a s u r e m e n t of a single m e l t i n g t e m p e r a t u r e w i t h o u t
reorganization.
A n a l t e r n a t i v e a p p r o a c h t o melting m e t a s t a b l e
p o l y m e r crystals w i t h o u t r e o r g a n i z a t i o n d u r i n g
fusion is t o seek a c o n s t a n t m e l t i n g t e m p e r a t u r e as
h e a t i n g rates a r e increased. T h i s process is referred t o
as t h e z e r o - e n t r o p y m e l t i n g m e t h o d ( W u n d e r l i c h
1980). U n f o r t u n a t e l y , in s o m e cases, h e a t i n g rates in
-1
excess of 1000 C m i n
m a y b e necessary t o arrest
r e o r g a n i z a t i o n a l effects.
T h e e q u i l i b r i u m m e l t i n g t e m p e r a t u r e Tm of a
p o l y m e r m a y be calculated from t h e T h o m s o n - G i b b s
e q u a t i o n b y s u b s t i t u t i n g t h e e x p e r i m e n t a l l y deter
m i n e d m e l t i n g t e m p e r a t u r e s Tm of small crystals
w h o s e lamellar thickness / h a s been d e t e r m i n e d from
low-angle x-ray p h o t o g r a p h s :
Polymers:
Properties
= ( / ? / A / / f) [ ^ ( K 1- ^ . v ) ]
(7)
w h e r e a n d Vl a r e t h e m o l a r v o l u m e s of t h e r e p e a t
u n i t a n d diluent, a n d v, is t h e v o l u m e fraction diluent.
T h e h e a t of fusion is o b t a i n e d from t h e intercept a t
zero v o l u m e fraction diluent of a p l o t of ( 1 / 7 ^ - 1 / 7 ^ ) /
v, versus v,. Q u i n n a n d M a n d e l k e r n (1958) h a v e
1
r e p o r t e d AH{ values of 277, 2 7 8 , 295 a n d 289 J g " for
p o l y e t h y l e n e using four different solvents. Similar
e s t i m a t e s of AH{ for p o l y e t h y l e n e c a n be m a d e from a
detailed l o o k a t t h e c h a n g e of h e a t of fusion with
c h a i n length.
04
06
1000//
O.i
3. Glass
(nm )
Figure 3
Melting temperatures of polyethylene single crystals as a
function of reciprocal lamellar thickness: , crystal from
xylene solution; , crystal from hexadecane solution
Tm =
Tm[\-(2oJlAH()]
Transition
A t t h e glass-transition t e m p e r a t u r e Tg t h e h e a t c a p a
city of a c o m p l e t e l y a m o r p h o u s p o l y m e r increases b y
(6)
w h e r e ae is t h e crystal's t o p a n d b o t t o m specific
surface free energy a n d AHf t h e b u l k h e a t of fusion
per cubic centimeter.
A p p l i c a t i o n o f this t e c h n i q u e t o m e l t i n g o f lightly
crosslinked p o l y e t h y l e n e crystals, g r o w n from solu
tion, is s h o w n in F i g . 3. T h e intercept in F i g . 3
coincides well with t h e 7 ^ of 145 C e s t i m a t e d b y
F l o r y et al. (1963) a n d B r o a d h u r s t (1966). I n t h e latter
case a n a l t e r n a t i v e a p p r o a c h w a s used for finding t h e
melting t e m p e r a t u r e of l o w - m o l e c u l a r - w e i g h t h o m o logs of polyethylene, a n d t h e d a t a e x t r a p o l a t e d t o
infinite m o l e c u l a r weight.
T h e r e a r e n o a b s o l u t e values of t h e e n t h a l p y of
a m o r p h o u s o r crystalline p o l y m e r s . E v a l u a t i o n o f t h e
e q u i l i b r i u m h e a t of fusion is b y o n e of three e x t r a p o
lation techniques. T h e s e m e t h o d s involve t h e deter
m i n a t i o n of t h e h e a t o f fusion AH{ a s a function
of crystallinity, t h e m e a s u r e m e n t of m e l t i n g t e m
p e r a t u r e s in diluent m i x t u r e s a s a function of c o n
c e n t r a t i o n , o r t h e d e t e r m i n a t i o n of h e a t s of fusion of
low-molecular-weight a n a l o g s .
Integration of the area above the heat capacity
baseline ( d a s h e d line, F i g . 2) yields t h e a p p a r e n t h e a t
of fusion AQ{. A p l o t of AQf a g a i n s t specific v o l u m e
or reciprocal lamellar thickness for p o l y e t h y l e n e
Temperature
(b)
I
1
/ ^ ^ ^ ^
Temperature
Figure 4
Schematic diagrams of the specific heat (a) and enthalpy
(b) versus temperature for the quenched glass 1 and the
annealed glass 2
373
Polymers:
Tests for
Thermal
Properties
a b o u t 11 J k m o l of m o b i l e u n i t s ( W u n d e r l i c h 1960).
T h e r e is n o h e a t o f t r a n s i t i o n associated with this
p h e n o m e n o n . H o w e v e r , Petrie (1972) h a s s h o w n t h a t
m o l e c u l a r r e l a x a t i o n c a n o c c u r resulting in a n e n d o t h e r m s u p e r i m p o s e d u p o n this increase in Cp. T h e s e
e n d o t h e r m s c a n be related t o t h e p r i o r t h e r m o m e c h a nical history of t h e p o l y m e r .
I n o r d e r t o e v a l u a t e t h e e n t h a l p y difference AH
b e t w e e n t w o glassy states with different t h e r m a l his
tories, the net difference in t h e a r e a s u n d e r t h e C
versus curves s h o u l d b e d e t e r m i n e d ( M a t s u o k a a n d
Bair 1977). T h i s is schematically illustrated in F i g . 4.
First, a reference s a m p l e of t h e s a m e m a t e r i a l is m a d e
which c a n be b r o u g h t t o a certain glassy state r e p e a t
edly a n d r e p r o d u c i b l y . N o r m a l l y , this is d o n e b y
cooling t h e s a m p l e r a p i d l y from t h e liquid state a t t h e
s a m e r a t e t h a t will b e e m p l o y e d in all s u b s e q u e n t
- 1
h e a t i n g r u n s (a typical r a t e is 20 m i n , w h i c h p r o
d u c e s glass 1 in F i g . 4). G l a s s 2 c a n b e f o r m e d b y
simply h o l d i n g glass 1 below its glass-transition t e m
p e r a t u r e ( r g l) .
This annealing process occurs m o r e rapidly the
closer t h e a n n e a l i n g t e m p e r a t u r e is t o Tgl. T h e glass-
3.0
t r a n s i t i o n t e m p e r a t u r e of glass 1 s h o u l d be higher
t h a n t h a t of t h e l o w e r - e n t h a l p y glass 2, b u t b e c a u s e of
t h e longer r e l a x a t i o n time of t h e latter, t h e glassy state
persists t o t h e higher t e m p e r a t u r e T g 3, if t h e h e a t i n g
rates a r e t h e s a m e . I n o r d e r t o r e a c h t h e e q u i l i b r i u m
r u b b e r state a b o v e Tg3, a delayed b u t s u d d e n j u m p in
e n t h a l p y t a k e s place, a n d a p e a k in t h e specific h e a t Cp
is o b s e r v e d . T h e difference in t h e initial values of
e n t h a l p y for glass 1 a n d glass 2 s h o u l d be o b t a i n e d by
s u b t r a c t i n g a r e a A from a r e a B. T h i s o b v i o u s aspect
h a s often b e e n neglected, a n d only t h e p e a k a r e a h a s
been t a k e n as t h e difference in e n t h a l p y . T h i s p r o c e d
u r e results in o v e r e s t i m a t i n g t h e e n t h a l p y decrease
with time. A n e x a m p l e w h e r e specific h e a t versus
t e m p e r a t u r e d a t a h a v e been carefully collected follow
ing t h e a f o r e m e n t i o n e d c o n s i d e r a t i o n s is s h o w n in
F i g . 5 for p o l y s t y r e n e s a m p l e s .
T h e limiting e n t h a l p y difference b e t w e e n t h e
q u e n c h e d s a m p l e (glass 1) a n d t h e e q u i l i b r i u m glassy
s t r u c t u r e (glass 3) a t a n n e a l i n g t e m p e r a t u r e T* is
r e a c h e d after l o n g times. T h u s , m a y be o b t a i n e d by
p l o t t i n g at SL given a n n e a l i n g t e m p e r a t u r e against
t h e log of time. T h e limiting e n t h a l p y is t a k e n a t t h e
b r e a k in t h e c u r v e w h e r e is i n d e p e n d e n t of time. A n
a l t e r n a t i v e a p p r o a c h h a s b e e n a d v a n c e d b y Prest et al.
(1981) w h i c h utilizes t h e Active t e m p e r a t u r e defined
by t h e intersection of t h e e x t r a p o l a t e d liquid a n d
glassy e n t h a l p i e s .
See also: Polymers: Thermal Analysis
Bibliography
2.0
350
360
370
380
Temperature
390
400
410
(K)
Figure 5
Specific heat versus temperature for polystyrene samples
with different thermal histories
374
Polymers:
1. DSC
Measurements
on
Polyblends
1.1 Compatibility
of Polymer
Blends
Binary p o l y m e r b l e n d s s e l d o m f o r m h o m o g e n e o u s ,
o n e - p h a s e systems since t h e e n t r o p y of m i x i n g ASmix
in the free energy of m i x i n g expression
AGmix
= AHmix-TASmix
(1)
1001
02
04
06
Thermal
1
08
Analysis
.
10
Figure 1
Phase diagram for a blend of /?-chlorostyrene/
o-chlorostyrene copolymer with PPO as a function of
weight fraction PPO (after Karasz and MacKnight 1977)
is usually t o o small t o o v e r c o m e t h e n o r m a l l y positive
h e a t of m i x i n g AHmix t h a t w o u l d p r o d u c e a negative
free energy of m i x i n g A G m i x. T h e latter is a necessary
c o n d i t i o n for p o l y m e r c o m p a t i b i l i t y . E x p e r i m e n t a l l y
t h e least a m b i g u o u s criterion of p o l y m e r c o m p a t i
bility is t h e detection of a single glass-transition
t e m p e r a t u r e Tg w h i c h is i n t e r m e d i a t e between those
c o r r e s p o n d i n g t o the t w o c o m p o n e n t p o l y m e r s . P h a s e
s e p a r a t i o n is j u d g e d by t h e existence of t w o distinct
glass t r a n s i t i o n t e m p e r a t u r e s ( K r a u s e 1978).
Below p h a s e s e p a r a t i o n is m e a s u r e d from the
h e a t s of s o l u t i o n of t h e p o l y m e r s a n d their blends by
Tian-Calvert
microcalorimetry.
Application
of
H e s s ' s law t o these values yields AHm[x ( R y a n et al.
1980). Positive levels of AHmix a r e a sufficient c o n
d i t i o n for p h a s e d e m i x i n g .
O n e of t h e best d o c u m e n t e d cases of c o m p a t i b l e
p o l y m e r b l e n d s is t h a t of p o l y s t y r e n e (PS) a n d
poly(2, 6 - m e t h y l - l , 4 - p h e n y l e n e oxide) ( P P O ) . A
single Tg h a s been detected for all b l e n d c o m p o s i t i o n s
by n u m e r o u s t h e r m a l t e c h n i q u e s . T h e effect of c h e m
ical modification of P P O a n d P S a n d their related
c o p o l y m e r s o n miscibility h a s been m u c h investigated
( M a c K n i g h t et al. 1978). K a r a s z a n d M a c K n i g h t
(1977) h a v e r e p o r t e d t h e p h a s e d i a g r a m for a blend of
/ 7 - c h l o r o s t y r e n e / o - c h l o r o s t y r e n e c o p o l y m e r with P P O
as a function of P P O c o n c e n t r a t i o n ( F i g . l ) . T h u s , if
t h e p h a s e b o u n d a r i e s a r e k n o w n , t h e processing c o n
d i t i o n s c a n be c o n t r o l l e d t o yield either a h o m o
geneous polyblend at r o o m temperature or a mixture
c o n t a i n i n g t w o discrete p h a s e s . A d d i t i o n a l tests m u s t
be c a r r i e d o u t t o d e t e r m i n e the m o s t desirable physi
cal state.
1.2 Quantitative
Analysis
M u l t i c o m p o n e n t p o l y m e r b l e n d s w h i c h c a n n o t be
a n a l y z e d by c o n v e n t i o n a l spectroscopic t e c h n i q u e s
d u e t o o v e r l a p p i n g a b s o r p t i o n b a n d s o r the screening
effects of additives c a n often be assayed b y D S C
375
Polymers:
Thermal
Analysis
indicates t h e a c t u a l c o n c e n t r a t i o n of r u b b e r w h i c h is
effective in m o d i f y i n g t h e d e f o r m a t i o n a l b e h a v i o r of
the S A N matrix.
2500k
2. Application
of DSC
to the Curing
of
Thermosets
All t h e r m o s e t t i n g resins liberate h e a t d u r i n g cure:
reactants
Temperature (C)
Figure 2
Specific heat capacity versus temperature for a commercial
ABS resin (after Bair 1974 Polym. Eng. Sci. 14: 202-5)
w i t h o u t r e s o r t i n g t o e x t r a c t i o n p r o c e d u r e s . If a
p o l y m e r o r a l o w - m o l e c u l a r - w e i g h t a d d i t i v e is i n c o m
patible with t h e b a s e resin, it c a n be detected in a
s e p a r a t e crystalline o r glassy p h a s e by either its melt
ing p o i n t Tm o r a n d m e a s u r e d q u a n t i t a t i v e l y from
heat of fusion AHf d e t e r m i n a t i o n s a t Tm o r i n c r e m e n
tal c h a n g e in h e a t c a p a c i t y AC m e a s u r e m e n t s a t Tg.
Conversely, in miscible a m o r p h o u s b l e n d s , t h e c o m
p o s i t i o n c a n b e e s t i m a t e d from Tg versus c o m p o s i t i o n
plots m e a s u r e d for t h a t system. Likewise, w h e n a n
additive is soluble in a p o l y m e r its c o n c e n t r a t i o n c a n
be e s t i m a t e d from shifts in t h e Tm o r Tg of t h e resin
(Bair 1981, S h a l a b y a n d Bair 1981).
T h e typical Cp b e h a v i o r of a c o m m e r c i a l a c r y l o n i t r i l e - b u t a d i e n e - s t y r e n e ( A B S ) resin is s h o w n in F i g .
2. A B S is a r u b b e r - t o u g h e n e d plastic w h e r e a brittle
c o p o l y m e r of s t y r e n e - a c r y l o n i t r i l e ( S A N ) is b l e n d e d
o r chemically b o n d e d t o s u b m i c r o n spheres of p o l y
b u t a d i e n e ( B D ) . In t h e l o w - t e m p e r a t u r e insert, t h e
discontinuity in Cp (ACp) n e a r - 9 0 C is identified
with B D in t h e c o m p o s i t e . T h e weight fraction of B D
(0.13) is e s t i m a t e d from t h e r a t i o of t h e o b s e r v e d ACp
t o the ACp m e a s u r e d in a s e p a r a t e e x p e r i m e n t o n
the u n b l e n d e d h o m o p o l y m e r . In t h e high t e m p e r a
t u r e r a n g e , t h e Tg n e a r 104 C is d u e t o t h e S A N
c o p o l y m e r ( 7 6 w t % ) while t h e t w o first-order t r a n s i
tions n e a r 70 C a n d 1 5 0 C a r e a t t r i b u t e d t o t h e
melting of 0.24 w t % fatty acid residue a n d 3.6 w t % of
a mold lubricant.
R e c e n t D S C studies h a v e s h o w n t h a t t h e m a g
n i t u d e of ACp at Tg for t h e B D p h a s e of a n A B S
c o m p o s i t e w a s r e d u c e d n o n l i n e a r l y as t h e r a t i o of
S A N grafted t o B D w a s increased (Bair et al. 1981).
T h e a t t e n u a t i o n s of ACp with increasing graft levels
a p p e a r t o be c a u s e d by t h e r e d u c e d n u m b e r of config u r a t i o n a l c h a n g e s t h a t c a n o c c u r in t h e grafted B D
molecules at Tg. T h u s , at high graft levels c a l o r i m e t r i c
d e t e r m i n a t i o n of t h e r u b b e r c o n t e n t of a n A B S resin
d o e s n o t give a m e a s u r e of the t o t a l r u b b e r b u t
376
products
(2)
w h e r e AHRXN is t h e e x o t h e r m i c h e a t p e r m o l e of
r e a c t i n g g r o u p s . Since t h e D S C m e a s u r e s h e a t flow
(dH/dt) directly it is ideally suited t o m e a s u r e n o t o n l y
t h e h e a t of r e a c t i o n b u t also t h e r a t e of h e a t e v o l u t i o n .
If t h e c u r e r e a c t i o n is t h e only t h e r m a l event in t h e
c u r i n g p r o c e s s , t h e r e a c t i o n r a t e do/L/dt is directly
p r o p o r t i o n a l t o dH/dt:
da/dt = (dH/dt)/AHRXN
(3)
D u r i n g i s o t h e r m a l D S C r u n s , t h e degree of c o n v e r
sion is:
, = # , / / /
(4)
w h e r e a, is t h e e x t e n t of r e a c t i o n a n d AHt t h e h e a t
evolved u p t o t i m e t ( P r i m e 1981).
A n e x a m p l e of t h e D S C m e t h o d for following t h e
c u r i n g of a n e p o x y resin is s h o w n in F i g . 3. If t h e
i s o t h e r m a l c u r e is c a r r i e d o u t a t c o m p a r a t i v e l y low
t e m p e r a t u r e s , t h e r e a c t i o n will be r e t a r d e d severely
w h e n r g, w h i c h increases as increases, reaches t h e
c u r e t e m p e r a t u r e . A t this p o i n t t h e r e a c t i o n b e c o m e s
diffusion c o n t r o l l e d . T h e residual h e a t of r e a c t i o n
AHifes a s s o c i a t e d with t h e h e a t liberated d u r i n g c o m
p l e t i o n of t h e cross-linking c a n be m e a s u r e d in a
d y n a m i c r u n a b o v e Tg.
W h e n Tg exceeds t h e c u r e t e m p e r a t u r e t h e g e n e r a
tion of t i m e - t e m p e r a t u r e - d e g r e e of c o n v e r s i o n curves
c a n b e a t t e m p t e d by residual h e a t .
20^
Time (min)
Figure 3
Isothermal DSC methods for curing epoxy 1 at 170C
Polymers:
3. Thermal
Analysis
of Water
in a
of Diffusion
in Polymers
by
Thermobalance
Ol
Time (h)
Figure 5
Typical desorption curve for water from high-density
polyethylene at 23 C (C 0 = 36 ppm) (after McCall et al.
1984)
50
Analysis
i.o?
Polymer
All p o l y m e r s c a n a b s o r b w a t e r from t h e a t m o s p h e r e
a n d its presence in a p o l y m e r c a n lead t o m a r k e d
changes in t h e m a t e r i a l ' s physical p r o p e r t i e s a n d , in
s o m e cases, its chemical state. T h e influence of w a t e r
o n the of poly(vinyl acetate), P V A c , as m e a s u r e d
by D S C is s h o w n in F i g . 4. N o t e the plastizing effect
of w a t e r a b s o r b e d a t 23 C until a c o n c e n t r a t i o n of
a b o u t 4 w t % is r e a c h e d . All a d d i t i o n a l w a t e r is f o u n d
to be in a freezable state. T h e difference b e t w e e n t h e
total w a t e r WT m e a s u r e d c o u l o m e t r i c a l l y a n d the
a m o u n t of freezable w a t e r WF e q u a l s t h e c o n c e n t r a
tion of b o u n d w a t e r WB in this system. WF c a n be
m e a s u r e d by D S C d o w n t o a b o u t 20 p p m . I n this
technique, the s a m p l e is c o o l e d t o a b o u t 70 C a n d
then h e a t e d t o r o o m t e m p e r a t u r e . T h e o b s e r v e d h e a t
of t r a n s i t i o n for the melting ice crystals is divided by
w a t e r ' s h e a t of fusion t o yield t h e fraction of WF (Bair
et al. 1978).
This freezing followed by fusion t e c h n i q u e c a n b e
used t o s t u d y t h e a t t a c k of w a t e r a t a resin-filler
interface. U s u a l l y a c o m p o s i t e is placed in w a t e r a t
t e m p e r a t u r e s below Tg w h e r e freezable w a t e r will n o t
form in the p u r e resin b u t will slowly a c c u m u l a t e in
the glass-filled m a t e r i a l . A n y freezable w a t e r is p r e
s u m e d t o be f o r m e d a t the resin-glass interface (Bair
a n d M i n e r 1982).
4. Measurements
Thermal
4
6
Concentration of water (wt %)
Figure 4
The influence of water on the glass transition1 temperature
of PVAc as measured by DSC at 20 C mm (after Bair
1981 Polym. Eng. Sci. 21: 930-5)
Z) = 0 . 0 4 9 2 ( / / / 1 / 2)
Conversely, from a p l o t of C 0 -CJC0
( C r a n k a n d P a r k 1968):
2 2
D = nl S /\6
(5)
against
(6)
A n a u t o m a t i c null-type e l e c t r o b a l a n c e is ideally
suited t o following the escape of a volatile liquid from
a solid with a m a s s sensitivity of 0.1 p p m . A typical
e x a m p l e of the d e s o r p t i o n of w a t e r from a 1.27 m m
thick slab of high-density polyethylene a t 23 C is
s h o w n in F i g . 5. C 0 is e q u a l t o t h e t o t a l weight loss
from / = 0 until the s a m p l e ' s weight is c o n s t a n t
( M c C a l l et al. 1984).
In a n interesting v a r i a t i o n of this T G t e c h n i q u e for
s t u d y i n g diffusion it h a s been s h o w n t h a t C 0 a n d D
c a n b e m e a s u r e d s i m u l t a n e o u s l y for a nonvolatile
a n t i o x i d a n t molecule in a p o l y m e r ( R o e et al. 1974).
T h i s m e t h o d is b a s e d o n a n a l y z i n g the c o n c e n t r a t i o n
profile a c r o s s a stack of p o l y e t h y l e n e sheets which the
a n t i o x i d a n t h a s been forced t o diffuse t h r o u g h . T h e
level of a n t i o x i d a n t in a p o l y m e r sheet is d e t e r m i n e d
by T G b a s e d u p o n a p l o t of oxidative i n d u c t i o n times
as a function of a n t i o x i d a n t c o n c e n t r a t i o n .
See also: Polymers: Tests for Thermal Properties; Thermal
Analysis: An Overview; Thermal Analysis: Recent Develop
ments
377
Polymers:
Thermal
Analysis
Bibliography
Bair 1981 Thermal analysis of additives in polymers. In:
Turi 1981, pp. 845-906
Bair , Johnson G E, Merriweather R 1978 Water
sorption of polycarbonate and its effect on the polymer's
dielectric behaviour J. Appl. Phys. 49: 4976-84
Bair , Miner R J 1982 The effect of water on the impact
strength of glass filled polyphenylene sulfide. Soc. last.
Eng. Tech. Pap. 28: 105
Bair , Shepherd L, Boyle D J 1981 The effective
butadiene content in a rubber toughened plastic as
measured by DSC. In: Turi 1981, pp. 114-23
Crank J, Park G S (eds.) 1968 Diffusion in Polymers.
Academic Press, New York
Karasz F E, MacKnight W J 1977 Problems in compatibility
studies. Contemp. Top. Polym. Sci 2: 143-56
Krause S 1978 Polymer-polymer compatibility. In: Paul D
R, Newman S (eds.) 1978 Polymer Blends, Vol. 1. Aca
demic Press, New York, pp. 16-106
McCall D W 1957 Diffusion in ethylene polymers. J. Polym.
Sci. 26: 151-69
McCall D W, Douglass D C, Blyler L L Jr, Johnson G
Jelinski L W, Bair 1984 Solubility and diffusion of
water in low-density polyethylene. Macromol. 17: 1644-9
MacKnight W J, Karasz F E, Fried J R 1978 Solid state
transition behaviour of blends. In: Paul D R, Newman S
(eds.) 1978 Polymer Blends, Vol. 1. Academic Press, New
York, pp. 186-238
Prime R 1981 Thermosets. In: Turi 1981, pp. 435-563
Roe R J, Bair , Gieniewski C 1974 Solubility and
diffusion coefficient of antioxidants in polyethylene.
J.Appl. Polym. Sci. 18: 843-56
Ryan C L, Karasz F E, MacKnight W J 1980 Thermal
analysis of miscible and immiscible blends of and
fluorostyrene copolymers. Proc. 16th AT AS Conf. 1:
15-18
Shalaby S W, Bair 1981 Block copolymers and polyblends. In: Turi 1981, pp. 365-434
Turi (ed.) 1981 Thermal Characterization of Polymeric
Materials. Academic Press, New York
. E. Bair
[ A T & T Bell L a b o r a t o r i e s , M u r r a y Hill,
N e w Jersey, U S A ]
(a) Continuous
( b ) Discrete
Isotropic
(c)
Arced
(d)2-point
(e)4-point
Oriented
Figure 1
Representative SAXS patterns of polymers. For the
oriented patterns, the orientation axis is vertical
1. Experimental
378
Aspects
Polymers:
T h e p a t t e r n s a r e r e c o r d e d either o n p h o t o g r a p h i c
film o r by t h e use of electronic d e t e c t o r s . Q u a n t i t a t i v e
w o r k w i t h film d e t e c t i o n requires t h e use of a m i c r o d e n s i t o m e t e r t o o b t a i n t h e angle d e p e n d e n c e of t h e
scattered intensity. T h e d e v e l o p m e n t of p o s i t i o n sensitive p r o p o r t i o n a l c o u n t e r s h a s p r o v e d a b o o n for
S A X S e x p e r i m e n t s . P a r t i c u l a r l y significant a r e t w o dimensional detectors, which permit anisotropic pat
terns t o be r e c o r d e d quickly a n d a c c u r a t e l y . High-flux
s y n c h r o t r o n r a d i a t i o n sources a r e b e c o m i n g avail
able; these p e r m i t e x p e r i m e n t s w h i c h were previously
impractical b e c a u s e of t i m e c o n s t r a i n t s o r sample-size
r e q u i r e m e n t s . A review of these a n d o t h e r d e v e l o p
m e n t s is given by Schelten a n d H e n d r i c k s (1978).
Analysis of S A X S p a t t e r n s falls i n t o t w o categories:
those involving line s h a p e (or t h e intensity d i s t r i b u
tion), a n d t h o s e w h i c h utilize i n t e g r a t e d intensities.
T h e latter a r e frequently p u t o n a n a b s o l u t e basis b y
c o m p a r i s o n w i t h a s t a n d a r d s a m p l e of k n o w n scatter
ing p o w e r . F o r this m a n i p u l a t i o n , a n d also for t h e
s u b t r a c t i o n of p a r a s i t i c scattering, t h e linear a b s o r p
tion coefficient of t h e s a m p l e is r e q u i r e d . T h e s a m p l e
-1
for
s h o u l d be p r e p a r e d w i t h a thickness t
m a x i m u m intensity; this c o r r e s p o n d s t o a thickness of
a few t e n t h s of a millimeter for m o s t p o l y m e r s .
2. Structure
of Amorphous
Polymers
A l t h o u g h t h e r e h a s been m u c h interest in t h e q u e s t i o n
of s t r u c t u r e within n o n c r y s t a l l i n e h o m o p o l y m e r s ,
evidence by scattering t e c h n i q u e s h a s b e e n lacking.
A n a l m o s t a n g l e - i n d e p e n d e n t b a c k g r o u n d intensity
d u e t o t h e r m a l l y i n d u c e d density fluctuations is n o r
mally o b s e r v e d . T h i s c a n b e expressed as
m = plW
(1)
3. Structure
of Semicrystalline
X-Ray
Scattering
Polymers
w h e r e 2 0 * is t h e angle of t h e scattering m a x i m u m a n d
is t h e w a v e l e n g t h of t h e r a d i a t i o n . 2 0 * is observed
directly in well-oriented p a t t e r n s (Figs. I d , e), t h o u g h
a radial Lorentz correction must be applied to isotro
pic o r a r c e d p a t t e r n s (Figs, l b , c). T h e c o r r e c t e d
intensity function IC is o b t a i n e d from t h e e x p e r i m e n t a l
profile / o bs a c c o r d i n g t o
2
/ C ( 2 0 ) = 0 / O b (s 2 0 )
(3)
A s t h e b r e a d t h of t h e p e a k is a p p r e c i a b l e , this c o r r e c
tion decreases t h e a p p a r e n t L b y 2 0 % o r m o r e .
It is usually o b s e r v e d t h a t L increases a n d t h e
b r e a d t h of t h e scattered p e a k decreases with m o r e
careful crystallization. N e v e r t h e l e s s , only o n e o r per
h a p s t w o reflection o r d e r s a r e n o r m a l l y o b s e r v e d ,
m a k i n g m o r e detailed analyses of t h e p a t t e r n very
u n c e r t a i n . T h e a p p a r e n t lack of l o n g - r a n g e o r d e r h a s
led t o t h e use of p a r a c r y s t a l l i n e t h e o r y t o describe
imperfect s t a c k s of lamellar crystals. T w o e q u i v a l e n t
m o d e l l i n g a p p r o a c h e s a r e used: o n e involves calcu
lated intensities of t h e t y p e
I{s) = CF\s)Z(s)
(4)
a n d t h e o t h e r utilizes t h e o n e - d i m e n s i o n a l c o r r e l a t i o n
function
I(s)cos(2nsx)
ds
(5)
Q = (p2-pl) ^2-3z/L)
(6)
379
Polymers:
X-Ray
Scattering
Deformation
Transformations
Crystallization
and
melting
of
semicrystalline
p o l y m e r s h a v e a n u m b e r of features which a r e p r o
ductively studied by S A X S . T h e d e v e l o p m e n t of t h e
S A X S p a t t e r n with time d u r i n g i s o t h e r m a l crystalliza
tion of polyethylene h a s been a n a l y z e d (Schultz et al.
1978); the c o n t i n u o u s scattering from effectively iso
lated lamellar crystals or a m o r p h o u s g a p s is replaced
by a discrete p a t t e r n as t h e lamellar stacks g r o w .
C o p o l y m e r s h a v e very b r o a d reversible melting
ranges which a r e n o w u n d e r s t o o d from t h e s t u d y of
Strobl et al. (1980). It w a s s h o w n t h a t thin lamellae
a r e selectively melted a t t h e lowest t e m p e r a t u r e s ;
these thin crystals p r e s u m a b l y c o n t a i n a n excess of
c o m o n o m e r which restricts t h e crystal size.
T h e glass t r a n s i t i o n in a m o r p h o u s p o l y m e r s is
manifested by a c h a n g e in t h e t e m p e r a t u r e d e p e n
dence of the fluctuation scattering in E q n . (1) ( W e n -
380
Porosity:
1. Structural
Parameters
T h r e e p a r a m e t e r s a r e used t o c h a r a c t e r i z e t h e s t r u c
t u r e of a p o r o u s m a t e r i a l ; these describe (a) t h e e x t e n t
of the p o r e space, (b) t h e d i s t r i b u t i o n of t h e p o r e
v o l u m e a c c o r d i n g t o p o r e size a n d (c) t h e extent of t h e
Characterization
and
Investigation
(1)
w h e r e dV is t h e fractional v o l u m e of p o r e s h a v i n g
radii b e t w e e n r a n d r + dr. T h e d i s t r i b u t i o n m a y be
r e p r e s e n t e d either as a c o n t i n u o u s function o r as a
h i s t o g r a m ; it m a y be b r o a d o r n a r r o w , a n d s h o w o n e
p e a k o r m o r e , a c c o r d i n g t o t h e c o m p l e x i t y of the p o r e
structure concerned.
T h i s definition of p o r e size d i s t r i b u t i o n a p p e a r s t o
p r e s u p p o s e t h a t t h e p o r e s a r e of such a s h a p e (cylin
drical, for instance) t h a t they h a v e identifiable radii;
familiarity with c o m m o n p o r o u s m a t e r i a l s s h o w s ,
h o w e v e r , t h a t this is practically never t h e case. In
deed, m o s t p o r e s t r u c t u r e s a r e of such e x t r e m e irregu
larity t h a t it is impossible, at t h e m i c r o s c o p i c level, t o
define a n y e l e m e n t of t h e p o r e space as c o n s t i t u t i n g a
single " p o r e , " let a l o n e t o specify its " r a d i u s " in t e r m s
of its real d i m e n s i o n s . W a y s in which this p r o b l e m is
resolved will be described later.
Specific surface s is t h e e x p o s e d a r e a of solid surface
in u n i t m a s s of m a t e r i a l . W h e t h e r o r n o t this includes
t h e surface of closed p o r e s d e p e n d s o n t h e m e t h o d of
m e a s u r e m e n t . M o r e rarely t h e specific surface m a y be
referred t o as u n i t v o l u m e of m a t e r i a l , a n d given the
s y m b o l . T h e r e l a t i o n s h i p b e t w e e n a n d s is
381
Porosity:
Characterization
and
= ( 1 -
Investigation
(2)
w h e r e ps is t h e density of t h e solid m a t r i x .
T h e three m a i n s t r u c t u r a l p a r a m e t e r s a r e related,
since specific surface is p r o p o r t i o n a l t o p o r o s i t y a n d
inversely p r o p o r t i o n a l t o p o r e size. T h e p r o p o r t i o n a
lity coefficient d e p e n d s o n t h e p o r e s h a p e . F o r ex
a m p l e , if t h e p o r e s a r e all e q u a l cylinders of r a d i u s r,
then
= 2e/r
(3)
(4)
382
Figure 1
Pore size and specific surface of some common porous
materials
a r e c o r r e s p o n d i n g l y n u m e r o u s . W h e r e a s direct m e t h
ods, w h e n p r o p e r l y a p p l i e d , m a y yield results of high
a b s o l u t e a c c u r a c y , their i n t e r p r e t a t i o n in t e r m s of t h e
practical p e r f o r m a n c e of m a t e r i a l s is often u n c e r t a i n .
Indirect m e t h o d s , o n t h e o t h e r h a n d , give results t h a t
a r e strongly m o d e l - d e p e n d e n t b u t m a y nevertheless
yield i n f o r m a t i o n of m o r e i m m e d i a t e practical value.
Indirect m e t h o d s a r e therefore m o r e widely used.
It s h o u l d be m e n t i o n e d t h a t reference samples of
c a l i b r a t e d s t a n d a r d surface a r e a m a t e r i a l s a r e avail
able, as a result of a n i n t e r l a b o r a t o r y c o l l a b o r a t i v e
project (Everett et al. 1974). T h e four m a t e r i a l s avail
2
1
able cover t h e r a n g e 10-300 m g " as d e t e r m i n e d b y
t h e B r u n a u e r - E m m e t t - T e l l e r ( B E T ) t e c h n i q u e using
n i t r o g e n (see below). S a m p l e s of lower specific surface
a n d m a t e r i a l s of c a l i b r a t e d s t a n d a r d p o r e size a r e also
being studied as p o t e n t i a l reference m a t e r i a l s .
2. Direct Methods
Characterization
of Pore
Structural
A p l a n e section t h r o u g h a p o r o u s m a t e r i a l , w h e n
e x a m i n e d b y a suitable optical- o r electronm i c r o s c o p e t e c h n i q u e , reveals the intersections of t h e
s a m p l i n g p l a n e with t h e b o u n d a r i e s b e t w e e n solid
matrix and pores. Contrast between pore a n d matrix
m a y be e n h a n c e d b y p r i o r i m p r e g n a t i o n of t h e p o r e s
by resin; this m a y also r e d u c e t h e possibility of
accidental d a m a g e t o t h e p o r e s t r u c t u r e d u r i n g
specimen p r e p a r a t i o n . T h e r e c o n s t r u c t i o n of t h r e e dimensional information a b o u t the pore structure
Porosity:
Characterization
and
Investigation
s=
Figure 2
Stereological quantities revealed by a plane section
through a porous solid: (a) areal analysis; (b) lineal
analysis; (c) point counting; (d) intersect analysis
(O = termination, = intersection)
from o b s e r v a t i o n s in t w o , o n e o r z e r o d i m e n s i o n s is
c o n d u c t e d b y t h e m e t h o d s of stereology.
T h e definition of p o r o s i t y c a n b e e x t e n d e d i n t o
lower dimensionalities:
e=Vp/(Vp+Vs)
= Ap/(Ap
As)
( 2 D : areal analysis)
= L p/ ( L p + L s)
( I D : lineal analysis)
= Np/(Np
(OD: p o i n t c o u n t i n g )
+ Ns)
(5)
4eXpJ(l-s)psXTp
(6a)
I n p r a c t i c e , such m e a s u r e m e n t s a r e m a d e o n a suit
ably magnified i m a g e of t h e p l a n e section a n d the
a c t u a l length of t h e test line m u s t b e divided b y the
magnification factor t o o b t a i n t h e a p p r o p r i a t e value
of .
Stereological d e t e r m i n a t i o n of p o r e size is m u c h
m o r e difficult, n o t only b e c a u s e of t h e e x t r e m e irregu
larity of p o r e s h a p e , b u t also b e c a u s e t h e cross section
of a given p o r e as revealed by sectioning d e p e n d s o n
t h e o r i e n t a t i o n of t h e p o r e axis relative t o t h e s a m
pling p l a n e . F o r e x a m p l e , a n elliptical outline m a y
indicate a n elliptical p o r e o r a n o b l i q u e section of a
cylinder. T h e d i s t a n c e b e t w e e n t w o parallel t a n g e n t s
t o a p o r e o u t l i n e m a y be t a k e n as a m e a s u r e of the
p o r e size, t h o u g h this will d e p e n d o n t h e o r i e n t a t i o n
of t h e t a n g e n t s . If t h e m a x i m u m a n d m i n i m u m of
such lengths c a n be m e a s u r e d , their m e a n m a y be a
b e t t e r m e a s u r e of d i a m e t e r , t h o u g h there m a y be
a m b i g u i t y if t h e p o r e h a s a r e e n t r a n t outline. Diffi
culties arise, h o w e v e r , w h e n this projected d i a m e t e r in
t h e s a m p l i n g p l a n e m u s t be related t o a t r u e p o r e size.
A m e a n p o r e size c a n b e defined in t e r m s of
h y d r a u l i c r a d i u s r h. F o r a p o r e of a r b i t r a r y s h a p e this
is defined a s twice t h e r a t i o of t h e p e r i m e t e r of a given
cross section t o its a r e a . I n t e r m s of q u a n t i t i e s a l r e a d y
defined, this leads t o
rh = 2s/L
=
(7)
/2
ps
(8)
383
Porosity:
3. Indirect
Characterization
Methods
and
of Pore
Investigation
Structural
Characterization
M o s t m a c r o s c o p i c p r o p e r t i e s of p o r o u s m e d i a d e p e n d
strongly o n the p o r e s t r u c t u r e , a n d in a n u m b e r of
instances the influence of p o r e s t r u c t u r e o n a given
p r o p e r t y is described q u a n t i t a t i v e l y by theories in
which the real, c o m p l e x s t r u c t u r e is replaced by a
simple m o d e l . S t r u c t u r a l p a r a m e t e r s for t h e m o d e l a r e
then derived from e x p e r i m e n t a l m e a s u r e m e n t s of the
p r o p e r t i e s of t h e real m a t e r i a l a n d a p p l i c a t i o n of the
a p p r o p r i a t e t h e o r y . T h e r e l a t i o n s h i p (if a n y ) b e t w e e n
m o d e l a n d real structures is often o b s c u r e , a n d varies
from case t o case; this p r o b l e m is considered further
in Sect. 4.
M a t e r i a l p r o p e r t i e s c o m m o n l y used for indirect
p o r e s t r u c t u r a l c h a r a c t e r i z a t i o n include density, per
meability t o fluids, a d s o r p t i v e c a p a c i t y for gases a n d
v a p o u r s , a n d capillary b e h a v i o u r t o w a r d s liquids.
3.1 Density
T h e density of a p o r o u s m a t e r i a l m a y be expressed
either as ph, t h e b u l k density (i.e., the m a s s of u n i t
v o l u m e of m a t e r i a l including all p o r e s ) , o r as ps, t h e
solid density (i.e., t h e m a s s of u n i t v o l u m e of the solid
m a t r i x ) . If closed p o r e s a r e present, a further c o n c e p t
is p's, the a p p a r e n t solid density, which is the m a s s of
unit v o l u m e of m a t r i x including its closed p o r e s . It
then follows t h a t the p o r o s i t y is given by
e=\-ph/ps
(9)
9a
-PblP's
()
ec = Pb(Ps-p's)/PsPs
(9b)
and
384
(10)
T h e p r o p o r t i o n a l i t y c o n s t a n t k is k n o w n as t h e
specific p e r m e a b i l i t y coefficient, o r m o r e briefly t h e
permeability.
All the q u a n t i t i e s in D a r c y ' s law a r e directly m e a
surable, except for k. T h u s , by m e a s u r i n g t h e v o l u m e
flow r a t e of a liquid of k n o w n viscosity u n d e r a
k n o w n pressure t h r o u g h a s a t u r a t e d s a m p l e of a
p o r o u s m a t e r i a l of regular s h a p e a n d k n o w n d i m e n
sions, k m a y be d e t e r m i n e d experimentally. P r o v i d e d
t h a t t h e liquid is N e w t o n i a n , t h e flow r a t e s h o u l d b e
directly p r o p o r t i o n a l t o t h e applied p r e s s u r e a n d k
s h o u l d be i n d e p e n d e n t of flow r a t e . E x c e p t i o n s m a y
be e n c o u n t e r e d
(a)
(b)
(c)
P e r m e a b i l i t y h a s d i m e n s i o n s of [length ]. A c o m
m o n practical u n i t of p e r m e a b i l i t y is t h e d a r c y , which
1 3
2
in SI units h a s t h e value 9.8 1 0 " m . A p o r o u s
m a t e r i a l h a s a permeability of o n e d a r c y w h e n a
p r e s s u r e difference of 1 a t m p r o d u c e s a flow of
3
1
1 c m s " of a fluid with viscosity 1 M P a s t h r o u g h a
c u b e of 1 c m edge. T h e p e r m e a b i l i t y is t h u s a m e a s u r e
of t h e ease of fluid flow t h r o u g h a p o r o u s solid a n d is
evidently p r o p o r t i o n a l b o t h t o the p o r o s i t y a n d t o
s o m e function of p o r e size (since smaller p o r e s , h a v
ing a g r e a t e r s u r f a c e - v o l u m e r a t i o , offer m o r e resis
t a n c e t o flow). A simple a p p l i c a t i o n of Poiseuille's law
Porosity:
k = er /S
(11)
: = /2(1
s) sYs
(12)
k n o w n as t h e K o z e n y e q u a t i o n .
E q u a t i o n (12) is b a s e d o n t h e a s s u m p t i o n t h a t t h e
pores a r e u n i f o r m cylinders aligned in t h e direction of
flow. It h a s been modified t o t a k e a c c o u n t of t h e fact
t h a t t h e p o r e cross section m a y b e noncylindrical a n d
t h a t flow m a y p u r s u e a m o r e t o r t u o u s p a t h t h r o u g h
the p o r o u s m e d i u m , t h u s s p r e a d i n g t h e p r e s s u r e d r o p
over a length greater t h a n L. T h e r e s u l t a n t K o z e n y Carman equation
k =
2 2 2
s /2(\-s) s p sTf
(12a)
c o n t a i n s t w o dimensionless empirical q u a n t i t i e s ,
(the t o r t u o s i t y factor) a n d / (the p o r e s h a p e factor),
which c a n n o t b e e v a l u a t e d a priori. F r o m e x p e r i m e n t s
with m a t e r i a l s of s u p p o s e d l y k n o w n p o r e g e o m e t r y ,
C a r m a n f o u n d t h a t t h e p r o d u c t Tf w a s a p p r o x i m a t e l y
equal t o 2.5. T h e K o z e n y - C a r m a n e q u a t i o n is often
used with this value of Tf t o e v a l u a t e t h e specific
surface of m a t e r i a l s from e x p e r i m e n t a l m e a s u r e m e n t s
of k, a n d ps
T h e flow of gases in p o r o u s m e d i a follows b r o a d l y
similar principles a n d t h e e q u a t i o n s given a b o v e c a n
easily be modified t o include t h e effects of c o m p r e s s i
bility, a s s u m i n g ideal-gas b e h a v i o u r . G a s t r a n s p o r t
b e c o m e s m o r e c o m p l i c a t e d in fine p o r e s (or a t low
pressures) w h e n t h e m e a n free p a t h of t h e g a s m o l
ecules is n o longer small c o m p a r e d with t h e d i a m e t e r
of t h e p o r e s . T h e i n t e r p r e t a t i o n m a y b e further c o m
plicated b y a d s o r p t i o n o n t h e p o r e walls o r even
capillary c o n d e n s a t i o n of c o n d e n s a b l e v a p o u r s (see
Sects. 3.3 a n d 3.5). Electrokinetic effects a r e , h o w e v e r ,
absent in t h e case of g a s flow.
E x p e r i m e n t a l t e c h n i q u e s for d e t e r m i n i n g t h e speci
fic permeability from either liquid o r gas flow a r e
relatively simple a n d several c o m m e r c i a l i n s t r u m e n t s
are available. T h e r e q u i r e m e n t is merely t o b e able t o
m e a s u r e t h e fluid flow r a t e across a s a m p l e of k n o w n
d i m e n s i o n s u n d e r a given i m p o s e d pressure; it is
possible either t o establish a c o n s t a n t flow r a t e b y
m e a n s of a p u m p a n d t o m e a s u r e t h e r e s u l t a n t p r e s
sure d r o p , o r conversely t o establish a c o n s t a n t p r e s
sure d r o p a n d t o m e a s u r e t h e flow. Alternatively, a
falling-head device m a y be used, in which t h e p r e s s u r e
decays as flow p r o c e e d s : this gives d a t a c o v e r i n g a
range of flow rates, from which t h e c o n s t a n c y of k
m a y b e tested.
F o r c o m p r e h e n s i v e discussions of t h e t h e o r y of
fluid flow in p o r o u s m e d i a , see Scheidegger (1974) a n d
Dullien (1979), a n d for useful e x p e r i m e n t a l details,
Characterization
and
Investigation
Vmcx
(l-*)[l + (c-l)x]
(13)
V(\-x)
Vmc
Vmc
(13a)
a n d t h e e x p e r i m e n t a l d a t a (V as a function of x) c a n
be p l o t t e d as x/ V( 1 x) a g a i n s t x. T h e slope a n d
intercept of t h e r e s u l t a n t straight line c a n t h e n be
solved t o give Vm a n d c. In practice, r e a s o n a b l e
linearity is often f o u n d in t h e r a n g e 0.05 < < 0.30,
with t h e m o n o l a y e r being c o m p l e t e d (V= Vm) a t
= 0.12 0.04. T h e m o n o l a y e r c a p a c i t y is c o n v e r t e d
to a n u m b e r of molecules b y m u l t i p l i c a t i o n b y
19
3
2.687 x 1 0 (the n u m b e r of molecules in 1 c m of ideal
gas a t S T P ) . M u l t i p l i c a t i o n b y t h e a r e a p e r molecule
t h e n gives t h e specific surface of t h e solid.
T h e B E T e q u a t i o n is based o n a simplified m o d e l of
t h e a d s o r p t i o n process; for a detailed criticism see, for
e x a m p l e , A d a m s o n (1982). A l t e r n a t i v e m o d e l s yield
o t h e r e q u a t i o n s which c a n also be used t o e v a l u a t e t h e
m o n o l a y e r capacity. Since, h o w e v e r , such m o d e l s
often c o n t a i n adjustable p a r a m e t e r s , w h o s e values a r e
c o n v e n t i o n a l l y c h o s e n t o yield a g r e e m e n t with the
B E T Vm, there is little a d v a n t a g e in using t h e m , a n d
they a r e n o t discussed here.
385
Porosity:
Characterization
and
Investigation
Table 1
Some typical adsorbates suitable for specific surface
determination at different temperatures
Adsorbate
Working
temperature
CQ
Saturation vapor
pressure (torr)
Molecular2
area (nm )
Nitrogen
w-Butane
Benzene
Water
- 195.8
0
25
25
760
774.5
95.18
23.756
0.162
0.444
0.430
0.125
A key p a r a m e t e r in d e t e r m i n i n g s from Vm is t h e
a r e a assigned t o a single a d s o r b e d molecule. A selec
tion of c o n v e n t i o n a l l y accepted values is given in
T a b l e 1. T h e s e values h a v e b e e n allocated principally
o n the basis of their ability t o p r o v i d e self-consistency
between values of s d e t e r m i n e d from t h e a d s o r p t i o n
of different v a p o r s . H o w e v e r , there is evidence t h a t
the effective m o l e c u l a r a r e a of a given a d s o r b a t e m a y
d e p e n d o n t h e n a t u r e of t h e solid surface; this, c o m
bined with t h e simplifying a s s u m p t i o n s of t h e B E T
m o d e l , m e a n s t h a t specific surface a r e a s e s t i m a t e d
from gas a d s o r p t i o n h a v e a r a t h e r limited claim t o
a b s o l u t e accuracy.
T h e r e a r e three general m e t h o d s available for
e x p e r i m e n t a l m e a s u r e m e n t of gas a d s o r p t i o n iso
t h e r m s . T h e basic r e q u i r e m e n t is t o m e a s u r e t h e
q u a n t i t y a d s o r b e d p e r g r a m of solid, a t s o m e fixed
t e m p e r a t u r e , as a function of relative v a p o r p r e s s u r e .
T h e t e m p e r a t u r e c h o s e n is usually below t h e critical
t e m p e r a t u r e of t h e gas c o n c e r n e d a n d s h o u l d be o n e
at which the v a p o r pressures a r e conveniently m e a s u r
able; the t e m p e r a t u r e s given in T a b l e 1 a r e often used.
Before t h e m e a s u r e m e n t , t h e s a m p l e m u s t b e freed of
foreign a d s o r b e d m a t e r i a l ( " o u t g a s s e d " ) , usually b y
e x p o s u r e t o high v a c u u m a t elevated t e m p e r a t u r e .
T h e choice of o u t g a s s i n g t e m p e r a t u r e m a y be difficult
for t h e r m a l l y sensitive m a t e r i a l s .
Gravimetric methods depend on estimating the
q u a n t i t y a d s o r b e d from t h e c h a n g e in m a s s of t h e
s a m p l e as it is e x p o s e d t o successively higher relative
v a p o r pressures. B u o y a n c y c o r r e c t i o n s a r e significant
with m a t e r i a l s of low specific surface. C o m m e r c i a l l y
available v a c u u m m i c r o b a l a n c e s h a v e sensitivities of
6
1
1 0 " g g~ o r better, which is a d e q u a t e for such w o r k .
2
( F o r e x a m p l e , a m o n o l a y e r of w a t e r o n 1 m of
surface h a s a m a s s of 0.277 m g . )
V o l u m e t r i c m e t h o d s e m p l o y a gas b u r e t t e t o esti
m a t e t h e n u m b e r of m o l e s of a gas from m e a s u r e
m e n t s of p r e s s u r e , v o l u m e a n d t e m p e r a t u r e . Similar
m e a s u r e m e n t s after e x p o s u r e t o t h e s a m p l e give a
r e d u c e d n u m b e r of m o l e s , t h e difference being t h e
a m o u n t a d s o r b e d . T h e effective v o l u m e of t h e s a m p l e
c h a m b e r is r e d u c e d by t h e v o l u m e o c c u p i e d b y t h e
s a m p l e ; m a k i n g a c c u r a t e a l l o w a n c e for this ( " d e a d s p a c e " c o r r e c t i o n ) b e c o m e s increasingly i m p o r t a n t
386
from
Solution
A d s o r p t i o n forces also o p e r a t e a t t h e s o l i d - l i q u i d
interface a n d m a y c a u s e local c h a n g e s in t h e c o m p o s i
tion of a s o l u t i o n close t o a solid surface. A c c u m u l a
tion of solute a t t h e surface will c a u s e a c o r r e s p o n d i n g
d e p l e t i o n in t h e b u l k s o l u t i o n , from w h i c h t h e q u a n
tity a d s o r b e d m a y t h e n b e e s t i m a t e d . F o r e x a m p l e ,
t h e d y e m e t h y l e n e b l u e is s t r o n g l y a d s o r b e d from
dilute a q u e o u s s o l u t i o n b y m a n y solids a n d t h e q u a n
tity a d s o r b e d c a n b e d e d u c e d from c o l o r i m e t r i c a n a l y
sis of t h e s o l u t i o n before a n d after a d s o r p t i o n .
A d s o r p t i o n of this k i n d m a y s o m e t i m e s follow t h e
Langmuir equation
n/nm = bc/(l+bc)
(14)
w h e r e is t h e n u m b e r of m o l e s of a d s o r b e d m a t e r i a l
p e r g r a m of solid, in e q u i l i b r i u m w i t h a s o l u t i o n
of m o l a r c o n c e n t r a t i o n c, a n d b is a t e m p e r a t u r e d e p e n d e n t c o n s t a n t loosely related t o t h e s t r e n g t h of
a d s o r p t i o n . T h e m o n o l a y e r c a p a c i t y nm (in similar
u n i t s t o t h o s e of n) c a n b e d e t e r m i n e d from experi
m e n t a l d a t a p l o t t e d in t h e linearized form:
c/n = c/nm+l/nmb
(14a)
Porosity:
Characterization
and
Table 2
Hydrostatic pressure difference and relative vapor pressure
p/p0 as a function of meniscus radius of curvature r0 for
mercury and water at 25 C
Vapor
Mercury
Solid
r0 ()
Figure 3
Definition of the contact angle
Equilibrium
Investigation
- 2 / r 0 = - ( 2 cos 0)/r
(15)
w h e r e r 0 is t h e r a d i u s o f c u r v a t u r e of t h e (spherical)
meniscus. ( D i s t o r t i o n b y gravity is negligible in p o r e s
small e n o u g h t o b e of p r a c t i c a l interest.) T h e interfa
cial m e a n c u r v a t u r e C c a n b e d e t e r m i n e d e x p e r i m e n
tally in a n u m b e r of w a y s , w h i c h therefore afford
indirect r o u t e s t o t h e p o r e size r.
100
10
1
0.1
0.05
0.01
0.005
0.002
AP
(MPa)
0.0096
0.096
0.96
9.6
19.2
96
192
480
Water
PlPo
1.000
1.001
1.006
1.059
1.121
1.772
3.14
17.5
(MPa)
0.00144
0.0144
0.144
1.44
2.88
14.4
28.8
72.0
PlPo
1.000
1.000
0.999
0.990
0.979
0.901
0.811
0.593
First, t h e m e c h a n i c a l e q u i l i b r i u m c o n d i t i o n for a
c u r v e d fluid interface w i t h surface t e n s i o n is given
by t h e L a p l a c e e q u a t i o n :
AP = aC
(16)
w h e r e AP is a h y d r o s t a t i c p r e s s u r e difference across
t h e interface. F r o m E q n . (15), C is negative for a
w e t t i n g liquid a n d t h e p r e s s u r e in t h e liquid is less
t h a n t h a t in t h e v a p o r . T h u s , in o r d e r t o w i t h d r a w a
w e t t i n g liquid from a p o r e , a suction m u s t b e applied,
with m a g n i t u d e inversely p r o p o r t i o n a l t o t h e p o r e
size. F o r a n o n w e t t i n g liquid (such a s m e r c u r y against
m o s t solids) C is positive a n d t h e p r e s s u r e in t h e liquid
exceeds t h a t in t h e v a p o r . H e r e , a n excess pressure
m u s t b e a p p l i e d t o force liquid i n t o t h e p o r e , a g a i n
inversely p r o p o r t i o n a l t o p o r e size.
S e c o n d , t h e c o n d i t i o n of diffusional e q u i l i b r i u m
a t t h e s a m e c u r v e d fluid interface is given b y t h e
Kelvin e q u a t i o n (also k n o w n a s t h e G i b b s - T h o m s o n Freundlich equation):
(RT/V^lnp/p^aC
Figure 4
Relationship between radius r of a cylindrical pore and
radius of curvature r0 of the meniscus
- AP
(17)
w h e r e R is t h e gas c o n s t a n t , t h e a b s o l u t e t e m p e r a
t u r e , Vx t h e m o l a r v o l u m e of t h e liquid a n d p/p0 its
relative v a p o r p r e s s u r e ( c o m p a r e E q n . (13)). T h u s ,
w h e n C is negative, a s for a w e t t i n g liquid, < p0 a n d
s u c h a liquid c o n d e n s e d in a p o r e exerts a r e d u c e d
v a p o r p r e s s u r e . T h e relative m a g n i t u d e s of these t w o
effects a r e c o m p a r e d , for w a t e r a n d m e r c u r y , in T a b l e
2. (Kelvin effects for m e r c u r y a r e usually i g n o r e d
b e c a u s e of its low a b s o l u t e v a p o r p r e s s u r e a t r o o m
temperature.)
A t least three indirect m e t h o d s of s t r u c t u r a l e x a m i
n a t i o n a r e b a s e d o n these effects. I n m e r c u r y p o r o s i m e t r y ( v a n B r a k e l 1981), a n e v a c u a t e d weighed
s a m p l e o f a p o r o u s m a t e r i a l is i m m e r s e d in m e r c u r y in
a d i l a t o m e t e r h a v i n g a capillary stem a n d is subjected
t o progressively increasing p r e s s u r e . A s m e r c u r y is
forced i n t o smaller a n d smaller p o r e s , t h e v o l u m e of
p o r e space i n t r u d e d is d e t e r m i n e d from t h e m o v e m e n t
387
Porosity:
Characterization
and
Investigation
388
Applied pressure
Suction
Relative vapor
pressure
Figure 5
Hysteresis in capillary equilibria: (a) mercury intrusion;
(b) capillary suction; (c) capillary condensation. In (a) and
(b) the first cycle (single arrow) differs from subsequent
ones
a k i n t o m u l t i l a y e r a d s o r p t i o n , w i t h o u t f o r m a t i o n of a
m e n i s c u s . Special m e t h o d s a r e n e e d e d for the s t u d y of
m i c r o p o r e s ( G r e g g a n d Sing 1982).
A c o m p l i c a t i o n in p o r e size analysis by capillary
c o n d e n s a t i o n arises from t h e fact t h a t while smaller
p o r e s a r e filling by c o n d e n s a t i o n , n o r m a l multilayer
a d s o r p t i o n is p r o c e e d i n g i n d e p e n d e n t l y o n the walls
of larger p o r e s , as yet unfilled. A l t h o u g h m e t h o d s for
s e p a r a t i n g t h e t w o effects h a v e b e e n p r o p o s e d , they
r e m a i n o p e n t o theoretical objection. T h e y also i n t r o
d u c e s o m e a r i t h m e t i c a l c o m p l e x i t y i n t o t h e analysis of
t h e d a t a , preferably h a n d l e d by c o m p u t e r . A p p a r a t u s
suitable for such m e a s u r e m e n t s is similar t o t h a t
described in Sect. 3.3.
T h e three m e t h o d s discussed in this section all rely
heavily o n t h e cylindrical-pore m o d e l o n which E q n .
(15) is b a s e d . O t h e r simple geometrical m o d e l s h a v e
been p r o p o s e d , such as parallel-sided slot-shaped
p o r e s , b u t it is o b v i o u s t h a t t h e c o m p l e x p o r e s h a p e s
f o u n d in reality c a n n o t be described in a n y t r a c t a b l e
w a y . T h e q u e s t i o n of m o d e l d e p e n d e n c e is referred t o
a g a i n in Sect. 4.
A n o t h e r p r o b l e m arises from t h e hysteresis which is
a l m o s t i n v a r i a b l y associated with all three m e t h o d s : a
m e r c u r y i n t r u s i o n c u r v e is n o t r e t r a c e d w h e n t h e
applied p r e s s u r e is slowly r e d u c e d (Fig. 5a), n o r is a
w a t e r d r a i n a g e c u r v e w h e n t h e suction is relaxed (Fig.
5b), a n d t h e d e s o r p t i o n c u r v e is always displaced t o
lower relative pressures t h a n t h e a d s o r p t i o n curve in
the capillary c o n d e n s a t i o n region (Fig. 5c). T h e p r i n
cipal r e a s o n for this is t h e t h e r m o d y n a m i c a l l y irrever
sible m a n n e r in which l i q u i d - v a p o r menisci m o v e
t h r o u g h the p o r e space: dissipative processes o c c u r
b o t h a t t h e m i c r o s c o p i c level within single p o r e s a n d
o n a scale involving c o o p e r a t i v e effects in m u c h larger
g r o u p s of p o r e s . T h e s e s p o n t a n e o u s m e n i s c u s m o v e
m e n t s (which a r e k n o w n as " H a i n e s j u m p s " after the
British physicist w h o first o b s e r v e d t h e m in 1924)
p r e s e n t yet a n o t h e r obstacle t o t h e i n t e r p r e t a t i o n of
p o r e size d i s t r i b u t i o n s o b t a i n e d b y these m e t h o d s .
Porosity:
Imbibition
W h e n a p o r o u s solid is placed in c o n t a c t w i t h a
wetting liquid, t h e liquid is d r a w n i n t o t h e p o r e s b y
capillary a c t i o n . T h i s familiar p h e n o m e n o n is of g r e a t
practical i m p o r t a n c e in m a n y a p p l i c a t i o n s of p o r o u s
m a t e r i a l s . Since t h e i m b i b i t i o n r a t e is related t o t h e
p o r e size, it affords a n o t h e r indirect m e t h o d of s t r u c
tural characterization.
C o n s i d e r a t i o n h e r e is limited t o o n e - d i m e n s i o n a l
flow. T h e driving force for i m b i b i t i o n is given b y E q n .
(16) a n d is inversely p r o p o r t i o n a l t o p o r e size. Viscous
resistance t o flow is given b y t h e Poiseuille e q u a t i o n
a n d increases as t h e flowing liquid p e n e t r a t e s further
a l o n g t h e p o r e s . C o m b i n i n g these t w o e q u a t i o n s
yields t h e W a s h b u r n e q u a t i o n giving t h e d i s t a n c e
p e n e t r a t e d JC as a function of t i m e t:
x = k wt
0 5
(18)
T h e W a s h b u r n c o n s t a n t fcw is given b y
fcw = ( < 7 r / 2 / / )
05
(18a)
w h e r e r is t h e p o r e r a d i u s a n d a n d a r e , respect
ively, t h e surface tension a n d viscosity of t h e i m b i b i n g
liquid. I n this simple t r e a t m e n t , t h e p o r e s a r e t r e a t e d
as u n i f o r m cylinders a n d t h e c o n t a c t angle is a s s u m e d
t o b e zero. It is also a s s u m e d t h a t t h e w e t t i n g front is
s h a r p , o r a t least t h a t it d o e s n o t b e c o m e m o r e diffuse
as i m b i b i t i o n p r o c e e d s .
T h u s , b y m e a s u r i n g as a function of t i m e in a
linear i m b i b i t i o n e x p e r i m e n t , & w c a n b e e v a l u a t e d ,
a n d t h e n c e t h e p o r e size r. Since t h e p o r e s a r e unlikely
t o resemble u n i f o r m cylinders, t h e value o b t a i n e d will
be t h e r a d i u s of a n " e q u i v a l e n t cylindrical p o r e . "
4. Interpretation
of Indirect
Measurements
In all indirect m e t h o d s of p o r e s t r u c t u r a l c h a r a c t e r i
z a t i o n , simplifying a s s u m p t i o n s a r e m a d e . V a r i o u s
m o d e l s a r e i n t r o d u c e d , b o t h of physical processes
Characterization
and
Investigation
389
Porosity:
Characterization
and
Investigation
p o r e s t r u c t u r e of p a p e r b y capillary action; t h e c o n
trolling factors a r e t h e p o r o s i t y a n d p o r e size of t h e
p a p e r . (In practice, t h e process is c o m p l i c a t e d b y
v a r i a t i o n s in p o r e s t r u c t u r e a c r o s s t h e thickness of
clay-coated p a p e r a n d by t h e n o n - N e w t o n i a n viscos
ity of inks a t high s h e a r rates.) T h e p o r e size of a
p a p e r m i g h t be m e a s u r e d directly by m i c r o s c o p i c
e x a m i n a t i o n o r indirectly by a variety of m e t h o d s
such as m e r c u r y i n t r u s i o n o r p e r m e a m e t r y , o r via t h e
W a s h b u r n c o n s t a n t . Very p r o b a b l y , all these m e t h o d s
will give different results a n d only the m i c r o s c o p i c
d a t a will be in a n y w a y related t o the real physical
p o r e structure. It w o u l d be impossible, h o w e v e r , t o
use the m i c r o s c o p i c d a t a t o calculate the capillary
effects o p e r a t i n g in p o r e s of such irregular s h a p e . By
c o n t r a s t , the single " p o r e size" o b t a i n e d from t h e
W a s h b u r n c o n s t a n t , even t h o u g h totally fictitious,
m a y completely describe t h e effect of p o r e s t r u c t u r e
o n the p a p e r ' s p e r f o r m a n c e in t h e p r i n t i n g process.
T h e w i d e s p r e a d practical uses of p o r o u s m a t e r i a l s
ensure t h a t efforts will be c o n t i n u e d t o d e v e l o p a n d
i m p r o v e m e t h o d s of c h a r a c t e r i z i n g their s t r u c t u r e a n d
to u n d e r s t a n d t h e influence of t h a t s t r u c t u r e o n their
p e r f o r m a n c e . In p a r t i c u l a r , there is a need for n o n d e s
tructive test m e t h o d s t h a t c a n be applied in situ.
H o w e v e r , k n o w l e d g e of p o r e s t r u c t u r a l p a r a m e t e r s is
likely t o r e m a i n m o r e empirical t h a n a b s o l u t e .
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pore properties of constructional and other materials: a
collection of 12 papers. Mater. Constr. (Paris) 6: 169-250
Modry S, Svata (eds.) 1973-4 Proc. Int. Symp. RILEMj
IUPAC: Pore Structure and Properties of Materials. Academia, Prague
Scheidegger A 1974 The Physics of Flow Through Porous
Media, 3rd edn. University of Toronto Press, Toronto,
Canada
Underwood 1970 Quantitative Stereology. AddisonWesley, Reading, MA
van Brakel J (ed.) 1981 Issue devoted to mercury porosimetry. Powder Technol. 29: 1-208
Young D M, Crowell A D 1962 Physical Adsorption of
Gases. Butterworth, London
J. M . H a y n e s
[University of Bristol, Bristol, U K ]
Positron
Annihilation
Spectroscopy
of Defects
in
Metals
as o c c u r s d u r i n g p o s t i r r a d i a t i o n a n n e a l i n g . V a c a n c y
f o r m a t i o n , u n d e r c o n d i t i o n s of t h e r m o d y n a m i c equi
librium, h a s been widely a n d successfully studied in
m e t a l s u s i n g P A S m e a s u r e m e n t s as a function of
t e m p e r a t u r e . T h e s e m e a s u r e m e n t s h a v e yielded either
t h e m o s t precise o r t h e o n l y values for t h e m o n o
v a c a n c y f o r m a t i o n e n t h a l p y H u in a large n u m b e r
of m e t a l s . T h e s e values, w h e n s u b t r a c t e d from the
respective l o w - t e m p e r a t u r e a c t i v a t i o n e n t h a l p i e s for
self-diffusion in m e t a l s , Qx = H\y + / / f j , h a v e in a d d i
tion yielded values for t h e a c t i v a t i o n e n t h a l p y for
monovacancy migration, / / f j . Vacancy migration
during postirradiation and postquenching annealing
e x p e r i m e n t s h a s also been investigated by P A S . F r o m
these high- a n d l o w - t e m p e r a t u r e (equilibrium a n d
n o n e q u i l i b r i u m ) m e a s u r e m e n t s of v a c a n c y mobility, a
generally consistent p i c t u r e h a s e m e r g e d . V a c a n c y
f o r m a t i o n in dilute a n d c o n c e n t r a t e d alloys h a s been
studied with P A S , b u t often w i t h s o m e w h a t less
q u a n t i t a t i v e success t h a n in p u r e m e t a l s , o w i n g t o a
p r e s e n t lack of detailed u n d e r s t a n d i n g of t h e w a y in
w h i c h t h e p o s i t r o n interacts w i t h t h e alloy system.
A t o m i c - d e f e c t recovery in m e t a l s after energeticparticle i r r a d i a t i o n , q u e n c h i n g a n d d e f o r m a t i o n h a s
b e e n extensively studied b y P A S . T h e s e studies h a v e
clearly elucidated the temperature range during post
i r r a d i a t i o n a n n e a l i n g (usually d e s i g n a t e d as stage III)
in w h i c h vacancies a r e m o b i l e a n d cluster in a variety
of m e t a l s . Defect-recovery investigations in dilute
alloys h a v e yielded q u a l i t a t i v e i n f o r m a t i o n r e g a r d i n g
t h e i n t e r a c t i o n of v a c a n c y defects with solute a t o m s ,
p a r t i c u l a r l y t h o s e n o r m a l l y in interstitial s o l u t i o n .
E x p e r i m e n t s o n d e f o r m e d m e t a l s h a v e generally suf
fered from a lack of u n d e r s t a n d i n g of the relative
i m p o r t a n c e of t h e variety of d e f e c t - t r a p p e d p o s i t r o n
states t h a t result from d e f o r m a t i o n . T h e clustering of
vacancies t o f o r m voids in electron- a n d n e u t r o n i r r a d i a t e d m e t a l s h a s b e e n studied by P A S , a n d
a t t e m p t s h a v e been m a d e t o c o r r e l a t e t h e o b s e r v e d
p o s i t r o n lifetimes in these clusters with t h e n u m b e r of
vacancies s t o r e d therein. T h e ability of t h e p o s i t r o n t o
detect c o n t a m i n a t i o n of s u c h v o i d s b y g a s e o u s i m p u r
ities h a s also been d e m o n s t r a t e d . T h e s e a p p l i c a t i o n s
of P A S t o m o r e c o m p l e x defect-related p h e n o m e n a
a r e e x p a n d i n g rapidly, as a r e a t t e m p t s a t using t h e full
electron m o m e n t u m i n f o r m a t i o n available from P A S
t o s t u d y t h e detailed a t o m i c a n d electronic s t r u c t u r e s
of defects in m e t a l s .
G e n e r a l reviews of p o s i t r o n a n n i h i l a t i o n in solids
a r e given b y H a u t o j a r v i (1979) a n d , in a m o r e c o n
d e n s e d f o r m for m e t a l s , b y Siegel (1980). T h e applica
tion of P A S t o t h e s t u d y a n d c h a r a c t e r i z a t i o n of
defects in m e t a l s h a s b e e n reviewed b y Siegel (1982).
A variety of a p p l i c a t i o n s of t h e P A S t e c h n i q u e s t o
defects a n d o t h e r p r o b l e m s in m a t e r i a l s science a r e
briefly reviewed a n d described in t h e v o l u m e s edited
b y H a s i g u t i a n d F u j i w a r a (1979) a n d C o l e m a n et al.
(1982).
391
Positron
Annihilation
Spectroscopy
of Defects
in
Metals
cknowledgement
T h e a u t h o r a c k n o w l e d g e s financial s u p p o r t from t h e
U S D e p a r t m e n t of E n e r g y u n d e r C o n t r a c t N o . W - 3 1 109-ENG-38.
See also: Electron Microscope Analysis of Defect Clusters,
Voids and Bubbles; Field-Ion Microscopy: Observation of
Radiation Effects
Bibliography
Coleman G, Sharma S C, Diana L (eds.) 1982 Proc. 6th
Int. Conf. Positron Annihilation. North-Holland, Amster
dam
Hasiguti R R, Fujiwara (eds.) 1979 Positron Annihilation.
Japan Institute of Metals, Sendai, Japan
Hautojarvi (ed.) 1979 Positrons in Solids. Springer, Berlin
Siegel R W 1980 Positron annihilation spectroscopy. Annu.
Rev. Mater. Sci. 10: 393^25
Siegel R W 1982 The characterization of defects in metals by
positron annihilation spectroscopy. In: Wiffen F W,
Spitznagel J A (eds.) 1982 Advanced Techniques for Char
acterizing Microstructures. The Metallurgical Society
(AIME), Warrendale, PA, pp. 4 1 3 ^ 2
R. W . Siegel
[Argonne National Laboratory,
A r g o n n e , Illinois, U S A ]
Powder Characterization
T h o r o u g h c h a r a c t e r i z a t i o n of a p o w d e r requires suffi
cient analyses o n representative s a m p l e s t o d e t e r m i n e
the d i s t r i b u t i o n of particle sizes, a n e s t i m a t e of typical
particle s h a p e s , the surface a r e a of t h e particles p e r
unit m a s s o r v o l u m e , particle m i c r o s t r u c t u r e a n d
chemical c o m p o s i t i o n (bulk a n d particle surface). T o
a great extent, these characteristics d e t e r m i n e t h e b u l k
p r o p e r t i e s of t h e p o w d e r such as its m a s s p e r u n i t
v o l u m e ( a p p a r e n t density), its ability t o flow freely
(flowability), its r e s p o n s e t o c o m p a c t i o n forces ( c o m
pressibility) a n d the p r o p e r t i e s of c o m p a c t e d a n d
sintered bodies which m a y be c o n s o l i d a t e d from t h e
powder.
r = [2g(p-p*)/9vtf '
1. Particle
Distribution
392
(1)
w h e r e r is t h e r a d i u s a n d is the density of t h e
particle, g is t h e g r a v i t a t i o n a l acceleration, a n d is t h e
t e r m i n a l settling velocity of t h e particle in a fluid of
density p* a n d viscosity . T h e e q u a t i o n a s s u m e s t h a t
viscous d r a g is t h e only r e s t r a i n i n g force o n t h e
particles. W h e n particle s h a p e s o t h e r t h a n spheres a r e
tested a n d e v a l u a t e d o n t h e basis of t h e S t o k e s
e q u a t i o n , t h e particle-size d i s t r i b u t i o n is calculated in
t e r m s of e q u i v a l e n t radii a n d m a y be significantly
different from t h e a p p a r e n t d i s t r i b u t i o n d e t e r m i n e d
by o t h e r m e t h o d s . S e d i m e n t a t i o n t e c h n i q u e s m a y be
Powder
(2)
Characterization
ir^L_n
2
2
( 3 )
/> L ( l - < p ) 5 a J
w h e r e is t h e p o w d e r m a t e r i a l density expressed in
3
2
_1
a n d in
g e m " . Sw is typically expressed in c m g
2
c m . T h e p e r m e a b i l i t y t o l a m i n a r flow is d e t e r m i n e d
from t h e v o l u m e t r i c flow r a t e of t h e fluid p e r u n i t b e d
cross section Q, t h e p r e s s u r e g r a d i e n t a n d t h e fluid
viscosity u s i n g t h e D a r c y e q u a t i o n :
= ////>
(4)
61pd
(5)
T h e m a g n i t u d e of Sw o b t a i n e d from t h e p e r m e a b i l i t y
is c h a r a c t e r i s t i c only of t h e surface a r e a within the
p o w d e r b e d o v e r w h i c h t h e fluid flows (i.e., t h e
friction surface). Since a particle a r r a y m a y c o n t a i n
surfaces such as i n t r a p a r t i c l e p o r e s a n d d e a d - e n d
c h a n n e l s (which a r e n o t involved in t h e d y n a m i c s of
t h e fluid flow), Sw will t e n d t o b e u n d e r e s t i m a t e d
c o m p a r e d t o t h e v a l u e o b t a i n e d from a t e c h n i q u e
such as gas a d s o r p t i o n w h i c h senses virtually all of t h e
i n t e r c o n n e c t e d surface of t h e bed.
T h e g a s - a d s o r p t i o n m e t h o d for d e t e r m i n i n g t h e
specific surface a r e a of a p o w d e r relies u p o n a
m e a s u r e m e n t of t h e a m o u n t of a specific gas a d s o r b e d
o n t h e particle surfaces a s s u m i n g a n a d s o r b e d layer of
m o n o m o l e c u l a r thickness a n d s o m e effective areal
c o v e r a g e p e r gas molecule. T h e t e c h n i q u e w a s p i o
neered b y B r u n a u e r , E m m e t t a n d Teller (1938) a n d
b e a r s t h e a c r o n y m i c n a m e B E T (Lowell a n d Shields
1984). G a s a d s o r p t i o n by t h e p o w d e r m a y be either
physical (van d e r W a a l s forces) o r chemical in n a t u r e .
T h e a d s o r p t i o n m e t h o d , in principle, detects all of the
i n t e r c o n n e c t e d surface a r e a in t h e p o w d e r s a m p l e . A s
such, t h e t e c h n i q u e typically results in specific surface
a r e a m e a s u r e m e n t s w h i c h a r e s o m e w h a t larger t h a n
t h o s e o b t a i n e d from p e r m e a b i l i t y m e a s u r e m e n t s . T h i s
difference m a y b e q u i t e significant, d e p e n d i n g p r i m a r
ily u p o n t h e i n t e r n a l s t r u c t u r e a n d surface t o p o g
r a p h y of t h e particles.
393
Powder
Characterization
Table 1
Particle size and specific surface area measurement methods
Approximate
particle size
range ()
Method
Typical equipment
Sieving
Microscopy
Elutriation
Sedimentation
Turbidimetry
Electrolyte resistance
Permeametry
Gas adsorption
Laser scattering
>45
10-50
0.5-100
0.001-5
2-50
2-100
>0.1
0.5-100
0.1-100
>0.5
0.5^0
0.01-25
2-200
ASTM/ANSI
standard
Ell, B214
B293
B430
B330
2. Particle
Shape
acicularneedle s h a p e d ,
(b)
a n g u l a r r o u g h l y p o l y h e d r a l s h a p e with s h a r p
edges,
(c)
d e n d r i t i c o f b r a n c h e d crystalline s h a p e ,
(d)
(e)
fibrousregularly
o r irregularly t h r e a d l i k e ,
flakyplatelike,
(f)
equidi-
(g)
(h)
n o d u l a r o f r o u n d e d irregular s h a p e , a n d
(i)
s p h e r o i d a l n o m i n a l l y spherical.
T h e s e general particle m o r p h o l o g i e s a r e s h o w n in F i g .
1. Particle s h a p e s will be d i c t a t e d p r i m a r i l y b y t h e
c o m p o s i t i o n of t h e p a r t i c u l a t e m a t e r i a l a n d t h e m a n u
facturing p r o c e s s used t o p r o d u c e t h e p o w d e r .
394
T h e q u a n t i t a t i v e c h a r a c t e r i z a t i o n of real particle
s h a p e s c a n b e very c o m p l e x a n d often involves t h e
d e t e r m i n a t i o n of o n e o r m o r e s h a p e factors from
analyses of magnified projected particle images. Bedd o w a n d M e l o y (1980) c o n t a i n s several t h o r o u g h
discussions of s h a p e c h a r a c t e r i z a t i o n t e c h n i q u e s a n d
analysis.
P a r t i c l e - s h a p e factors c o m m o n l y p r o v i d e s o m e
m e a s u r e of t h e d e v i a t i o n from a n idealized g e o m e t r y
such as a s p h e r e o r c u b e . F o r e x a m p l e , w h e n three
m u t u a l l y p e r p e n d i c u l a r particle d i m e n s i o n s c a n b e
ascertained, it is possible t o e s t i m a t e b o t h a particle
flatness o r flakiness, a n d t h e m a x i m u m axial aspect
r a t i o . A l t h o u g h nonspecific with respect t o particle
surface t o p o g r a p h y , these p a r a m e t e r s afford a q u a n t i
tative i n d i c a t i o n of t h e d e v i a t i o n of t h e particle from
a n e q u i a x e d m o r p h o l o g y . T w o s h a p e factors w h i c h
c a n b e e v a l u a t e d from projected particle images a r e
illustrated in Fig. 2.
Stereological m e t h o d s c a n be useful in particle
s h a p e c h a r a c t e r i z a t i o n . C o n c e r n e d largely with t h e
a p p l i c a t i o n of g e o m e t r i c a l p r o b a b i l i t i e s t o infer threed i m e n s i o n a l m a t e r i a l s t r u c t u r e s from t h e s t u d y of
p l a n a r sections, stereology c a n p r o v i d e specific q u a n
tities w h i c h m a y be q u i t e useful in particle-shape
c h a r a c t e r i z a t i o n . S u c h p a r a m e t e r s as m e a n surface
c u r v a t u r e , particle p e r i m e t e r a n d m e a n particle
a r e a c a n be d e t e r m i n e d b y established stereological
m e t h o d s using either m a n u a l o r a u t o m a t e d i m a g i n g
equipment.
3. Bulk Powder
Properties
A l t h o u g h t h e characteristics of t h e individual p a r t i
cles c o m p r i s i n g a p o w d e r a r e t h e principal d e t e r m i
n a n t s of t h e b u l k b e h a v i o r of t h a t p o w d e r , it is often
Powder
Characterization
Figure 1
Particle morphologies of powders: (a) acicular, (b) angular, (c) dendritic, (d) fibrous, (e) flaky, (f) granular, (g) irregular,
(h) nodular and (i) spheroidal
for m a n y m e t a l , c e r a m i c a n d m i n e r a l p o w d e r s , includ
ing p h a r m a c e u t i c a l s .
T h e m a s s p e r u n i t v o l u m e of a loose p o w d e r , as
m e a s u r e d u n d e r specific test c o n d i t i o n s , is called its
a p p a r e n t density. F o r free-flowing m e t a l p o w d e r s , the
test involves filling a 25 c m 3 c u p with the p o w d e r
falling t h r o u g h t h e 0.25 c m d i a m e t e r orifice of a
funnel (called t h e H a l l funnel) from a fixed height.
T h e a p p a r a t u s is illustrated in Fig. 3. T h e filled,
levelled c u p is weighed a n d t h e a p p a r e n t density of the
395
Powder
Characterization
Table 2
Tests for bulk properties of metal powders
Property
Figure 2
Particle shape factors derived from projected particle
image dimensions. Both
the elongation E( = a/b) and the
2
surface area 5 ( = C /12.6 A) are unity for a sphere
Apparent density
free-flowing
powders
non-free-flowing
powders
refractory-metal
powders
Flowability (flow
time)
Compressibility
Green strength
p o w d e r d e t e r m i n e d in g e m . T h e a p p a r e n t density
of a non-free-flowing p o w d e r is d e t e r m i n e d in a
similar m a n n e r except t h a t a 0.51 c m funnel orifice
( C a r n e y funnel) is e m p l o y e d .
T h e flowability of a m e t a l p o w d e r is d e t e r m i n e d
using t h e H a l l flow m e t e r a p p a r a t u s described p r e
viously. T h e t i m e r e q u i r e d for 50 g of t h e p o w d e r t o
flow t h r o u g h t h e orifice of t h e H a l l funnel, suitably
corrected for n o n s t a n d a r d test c o n d i t i o n s , is r e p o r t e d
as t h e flowability of t h e p o w d e r .
It is o b v i o u s t h a t b o t h t h e flowability a n d a p p a r e n t
density of a p o w d e r will b e influenced significantly b y
t h e theoretical density of its p a r t i c u l a t e m a t e r i a l . F o r
a given b a s e m a t e r i a l , these b u l k p r o p e r t i e s will b e
d e p e n d e n t u p o n particle-size d i s t r i b u t i o n , particle
s h a p e a n d i n t e r n a l particle s t r u c t u r e (e.g., p r e s e n c e of
voids). I n general, s p h e r o i d a l p o w d e r s , such as t h o s e
p r o d u c e d by inert gas a t o m i z a t i o n , will exhibit t h e
Hall
funnel
Test apparatus
ASTM/ANSI
standard
Hall flowmeter
B212
Carney funnel
B417
Scott volumeter
B329
Hall flowmeter
B213
B331
B312
Bibliography
Figure 3
Hall flowmeter apparatus
396
Powder
Irani R R, Callis C F 1963 Particle Size: Measurement
Interpretation and Application. Wiley, New York
Lenel F V 1980 Powder Metallurgy: Principles and Applica
tions. Metal Powder Industries Federation, Princeton, NJ
Lowell S, Shields J 1984 Powder Surface Area and Porosity.
Chapman and Hall, London
Orr C, Dallavalle J 1959 Fine Particle Measurement.
Macmillan, New York
Poster A R (ed.) 1966 Handbook of Metal Powders. Reinhold, New York
Weiss L, Frock 1976 Rapid analysis of particle size
distributions by laser light scattering. Powder Technol. 14:
287-93
Cubic
Mechanics
Orthorhombic
D . W. Smith
[ M i c h i g a n T e c h n o l o g i c a l University,
Houghton, Michigan, USA]
T e t r a g o n a l - sphenoidal
Powder Mechanics
T h e b e h a v i o r of p o w d e r s c a n n o t be fully described b y
t h e o r y a t present, yet it is of g r e a t i m p o r t a n c e in t h e
practical use of soils, s a n d s , c e m e n t s , ceramics,
p o w d e r m e t a l s , p i g m e n t s , catalysts, p h a r m a c e u t i c a l s
a n d m a n y o t h e r g r a n u l a r solids. A l m o s t all e v e r y d a y
objects g o t h r o u g h a p o w d e r stage a t s o m e p o i n t in
their m a n u f a c t u r e a n d m o r e k n o w l e d g e is needed t o
optimize p o w d e r processing.
M u c h of t h e difficulty in describing p o w d e r m e c h a
nics stems from the r a n g e of s t r u c t u r e s t h a t c a n exist
in a g r a n u l a r m e d i u m (Deresiewicz 1958). F o r ex
a m p l e , a highly c o m p a c t e d pellet m a d e b y pressing
p o w d e r i n t o a m o l d b e h a v e s as a H o o k e a n solid; it is
largely elastic, exhibits a linear stress-strain c u r v e ,
t r a n s m i t s v i b r a t i o n s , displays brittle fracture in ten
sion a n d d e f o r m s plastically w h e n i n d e n t e d . A p h a r
maceutical tablet is a n e x a m p l e of this type. By
contrast, a composition m a d e by mixing powder into
a liquid c a n b e h a v e as a solid gel if t h e particles
c o n n e c t t o form a c o n t i n u o u s s t r u c t u r e with t h e liquid
in t h e interstices, o r c a n b e h a v e as a liquid, flowing
like water, if the particles r e m a i n s e p a r a t e . E m u l s i o n
p a i n t , designed t o c h a n g e from a solid t o a liquid
o n stirring t o b r e a k d o w n t h e particle s t r u c t u r e , is a
g o o d illustration of this. W h e n dispersed in a gas, a
fine p o w d e r c a n b e h a v e as a gas itself, d i s p l a y i n g
B r o w n i a n m o t i o n , diffusion a n d flow. Alternatively, a
bed of p o w d e r fluidized b y p a s s i n g a gas t h r o u g h it
m a y b e h a v e like a boiling liquid, f o r m i n g b u b b l e s of
gas which mix t h e b e d a n d efficiently transfer h e a t .
T h e objective of p o w d e r m e c h a n i c s is t o describe
these p h e n o m e n a theoretically. O n e m a y resolve this
description i n t o three p a r t s :
(a)
(b)
Rhombohedra I
Figure 1
The four dense regular packings of equal rigid spheres
(c)
t h e q u e s t i o n of i n t e r a c t i o n of t h e g r a n u l a r m a t e r
ial with t h e s u r r o u n d i n g s , w i t h stress fields, with
v i b r a t i o n , o r with flowing fluids, for e x a m p l e .
7. Structure
of Powder
Masses
T h e simplest m o d e l of a p o w d e r is a h e a p of rigid
s m o o t h spheres all t h e s a m e size. Since sphere m o d e l s
h a v e b e e n used t o explain t h e s t r u c t u r e of crystals
( B a r l o w 1883) a n d h a v e also been e m p l o y e d t o simu
late t h e s t r u c t u r e of liquids (Bernal 1964) it is h a r d l y
surprising t h a t p o w d e r s exhibit s o m e solid a n d s o m e
liquid c h a r a c t e r . E x p e r i m e n t s using dispersions of
p o l y m e r spheres in a liquid of t h e s a m e refractive
index h a v e s h o w n t h a t t h e s p h e r e s a r e in a d i s o r d e r e d
liquidlike state a t low c o n c e n t r a t i o n s , b u t form
o r d e r e d a r r a y s a t ~ 5 0 % solids, b e c o m i n g d i s o r d e r e d
a n d glasslike a t c o n c e n t r a t i o n s n e a r 6 0 % (Pusey a n d
v a n M e g e n 1986).
Solid p o w d e r s t r u c t u r e s m a y b e m o d e l l e d by the
four r e g u l a r d e n s e p a c k i n g s of spheres s h o w n in Fig.
1. T h e s e give p a c k i n g v o l u m e fractions ( v o l u m e of
s p h e r e s / v o l u m e of assembly), porosities a n d c o o r d i
n a t i o n n u m b e r s ( p o i n t s of c o n t a c t p e r sphere) as
s h o w n in T a b l e 1. T h e t o p layer of particles is
i n d i c a t e d in F i g . 1 b y t h e full line a n d t h e second layer
by b r o k e n lines. E x c e p t for (simple) cubic stacking,
t h e layering c a n b e varied t o give further complexity,
as e x p l a i n e d b y C u m b e r l a n d a n d C r a w f o r d (1987).
T h e m o s t stable p a c k i n g is t h e densest, t h a t is, the
r h o m b o h e d r a l s t r u c t u r e with a p a c k i n g v o l u m e frac
tion of 0.7405. S u c h p a c k i n g s h a v e been achieved b y
individually placing balls in a regular a r r a y . Slow
397
Powder
Mechanics
Table 1
Properties of the four dense regular packings of equal rigid
spheres
Packing
Porosity
Coordination
Cubic
Orthorhombic
0.5236
0.4764
6
0.6046
0.3954
8
Tetragonalsphenoidal Rhombohedral
0.6981
0.3019
10
0.7405
0.2595
12
398
0.2
0.4
Fine
0.6
0.8
fraction
Figure 2
Increase in packing density achieved by filling the gaps
between large spheres with smaller spheres, for
comparison with experimental results
r a n d o m p a c k i n g , t h e n p o u r i n g fine s h o t t h r o u g h the
interstices a n d v i b r a t i n g again. A r a t i o of d i a m e t e r s of
20/1 is r e q u i r e d t o a p p r o a c h t h e theoretical level. If
t h e s a m e p o w d e r s a r e mixed in a fluid, t h e p a c k i n g
rarely rises a b o v e 0.8 because the fine particles i n t r u d e
b e t w e e n t h e c o a r s e spheres a n d e x p a n d t h e assembly.
A decrease in p a c k i n g is generally o b s e r v e d w h e n
the particles a r e m a d e n o n s p h e r i c a l . F i b r o u s o r p l a t e
like particles c a n form gel s t r u c t u r e s a t v o l u m e frac
tions as low as 0.05. T o explain these effects is
impossible by o r d i n a r y g e o m e t r y . R e c e n t a d v a n c e s in
p a c k i n g t h e o r y h a v e e m e r g e d from c o m p u t e r simula
tion. Particles of a r b i t r a r y s h a p e a r e d e p o s i t e d
a c c o r d i n g t o m a t h e m a t i c a l rules, allowing p a c k i n g
density t o be e v a l u a t e d (Cargill 1984).
2. Problem
of
Contact
Powder
Mechanics
=[ -^f]"
deformation
3<l
H e also c o m p u t e d t h e relative d i s p l a c e m e n t o f t h e
s p h e r e centers a s t h e particles were p u s h e d together:
Figure 3
Two elastic spheres, pushed into contact by a force F, and
attracted by a work of adhesion , deform elastically to
give a contact circle of diameter d
tion t o w a r d s n e i g h b o r i n g g r a i n s . If this a t t r a c t i o n is
repulsed b y electrical d o u b l e - l a y e r forces o r b y thick
a d s o r b e d p o l y m e r layers, t h e n t h e particles c a n n o t
achieve full c o n t a c t , b u t r e m a i n s e p a r a t e , c a u s i n g t h e
m i x t u r e t o b e h a v e a s a liquid. S u c h colloidally stable
suspensions c a n b e p o u r a b l e a t high v o l u m e l o a d i n g s
of solids, g r e a t e r t h a n 0.5. O n t h e o t h e r h a n d , w h e n
there is n o l o n g - r a n g e r e p u l s i o n b e t w e e n t h e particles,
the grains c o m e i n t o m o l e c u l a r c o n t a c t a n d c a n form
a s t r u c t u r e t h a t b e h a v e s a s a solid, even t h o u g h t h e
solid p a c k i n g m a y b e a s l o w a s 0.05. T h e force
i m p o s e d o n t h e particles a t t h e c o n t a c t regions m a y b e
considerable, c a u s i n g elastic a n d even plastic defor
m a t i o n w h e n t h e particles a r e sufficiently small.
T h e solution t o t h e p r o b l e m o f elastic c o n t a c t for
t w o e q u a l s m o o t h spheres o f d i a m e t e r Z>, Y o u n g ' s
modulus a n d Poisson's ratio pushed together by
a n external force F a n d pulled i n t o c o n t a c t b y surface
a t t r a c t i o n s defined b y w o r k of a d h e s i o n (the energy
required t o s e p a r a t e u n i t a r e a of interface) w a s given
by J o h n s o n et al. (1971). T h e d i a m e t e r d of t h e c o n t a c t
circle (Fig. 3) is defined b y t h e e q u a t i o n
3
</ = 3(l -
9 ( 1
v 2 ) 2
13 /
^J
( 4 )
'-d^-)]"'
v )^{F+inTD
2 l/2
+ [lnrDF+(irD) ] }
(1)
F=\nYD
(2)
,= r J ^ l T
2
3
( 6 )
Ll6(l - v ) J
w h i c h s h o w s t h a t cohesive p o w d e r s a r e H o o k e a n a t
low stresses.
C o h e s i v e p o w d e r s m a y b e m a d e less so b y reducing
t h e w o r k of a d h e s i o n b e t w e e n t h e particles. T h i s is
i m p o r t a n t in p h a r m a c e u t i c a l , m e t a l a n d c e r a m i c p r o
cessing w h e r e g o o d flow o f fine p o w d e r s is beneficial.
Surface active a g e n t s such a s stearates, polyethyleneoxide o r silanes m a y b e a d d e d . D i s p e r s i o n in
fluids c a n also r e d u c e if t h e wetting angle is low.
S u r f a c t a n t o r p o l y m e r solutions also p r o m o t e flow
by p r e v e n t i n g m o l e c u l a r c o n t a c t b e t w e e n particle
surfaces.
S o m e t i m e s it is necessary t o m a k e n o n c o h e s i v e
p o w d e r s m o r e cohesive, for e x a m p l e , w h e n stabilizing
399
Powder
Mechanics
l o a d a n d a n increasing m o d u l u s a t higher l o a d s . F o r a
cubic s t a c k i n g of u n i f o r m spheres t h e elastic m o d u l u s
is calculated from E q n s . (3) a n d (4) t o be
3
E* = ^ = [
volume
fraction,
Figure 4
Calculated elastic moduli for regular particle assemblies
plotted against the packing
volume fraction to show the
4,
near dependence on
soils. T h i s m a y be achieved by c e m e n t i n g t h e grains a t
the c o n t a c t p o i n t s using b i n d e r s . Alternatively, t h e
p o w d e r s m a y be c o a t e d with t a c k y b i n d e r s o r r u b b e r y
layers which increase substantially.
3. Interaction
with
Surroundings
T h e m a i n p u r p o s e of p o w d e r m e c h a n i c s is t o p r e d i c t
the response of p o w d e r masses t o external fields such
as stress fields, electrical fields, v i b r a t i o n s o r fluid
flow.
C o n s i d e r first t h e r e s p o n s e t o m e c h a n i c a l stress.
Cohesive p o w d e r s b e h a v e in the simplest w a y b e c a u s e
they give linear, H o o k e a n s t r e s s - s t r a i n curves as
indicated in E q n . (6). F o r a cubic p a c k i n g of spheres
2
the m e a n stress o n e a c h particle is F/D a n d t h e strain
is /D. T h e r e f o r e , Y o u n g ' s m o d u l u s c a n be defined
for this assembly as
.
stress Z=
=
strain
DS
/3
L\6D(\ - v ) J
E*=\7A
/ E T\
<P {^)
4
1/3
/ 3
(9)
K)
T h e d e p e n d e n c e of elastic p r o p e r t i e s o n t h e applied
l o a d F for n o n c o h e s i v e p o w d e r s is relevant t o t h e
p a s s a g e of s o u n d waves t h r o u g h the m a s s . W h e r e a s
cohesive p o w d e r s give n o c h a n g e in w a v e speed as t h e
1 6
l o a d is increased n o n c o h e s i v e assemblies s h o w a n F '
d e p e n d e n c e of c o m p r e s s i o n a l w a v e velocity, b e c a u s e
1/2
w a v e velocity d e p e n d s o n m o d u l u s . T h i s relation
ship h a s been verified experimentally for s a n d .
F u r t h e r extensions of this t h e o r y h a v e been useful for
m e a s u r i n g the fluid c o n t e n t of oil-bearing o r w a t e r
bearing sands.
Deresiewicz (1958) also c o n s i d e r e d t h e stress
r e q u i r e d t o s h e a r a cubic a r r a y of n o n a d h e s i v e spheres
h a v i n g a friction coefficient . T h e cubic stack w a s
originally c o m p r e s s e d isotropically u n d e r a stress 0,
t h e n a n e x t r a stress w a s applied parallel t o o n e of the
c u b e face d i a g o n a l s .
Deresiewicz f o u n d t h a t the angle of failure w a s
given by
t a n 2 = \/
(10)
a n d t h e m i n i m u m failure stress w a s
= 20(
+ (\-
1 2
(11)
(8)
T
max = c +
400
L z) (i-v ) J
Dds
Packing
fE
(12)
Powder
15.6/r/(Dc)
1 /2
(13)
where is t h e p a c k i n g v o l u m e fraction, is t h e w o r k
of a d h e s i o n , D is t h e particle d i a m e t e r a n d c is t h e
n o t c h length. It is clear from this e q u a t i o n t h a t
p o w d e r c o m p a c t s c a n a t t a i n high s t r e n g t h s if t h e
grains a r e small a n d t h e r e a r e n o flaws bigger t h a n t h e
particles themselves. F o r e x a m p l e , a t i t a n i u m dioxide
p o w d e r c o m p a c t c o u l d give a s t r e n g t h of 168 P a a t
0.2 d i a m e t e r . I n reality, all t h e c o m p a c t s e x a m i n e d
c o n t a i n e d flaws m u c h larger t h a n t h e grain size. T h e s e
flaws were often a g g l o m e r a t e s in t h e original p o w d e r ,
too strong to be broken down by the compaction
Mechanics
Bibliography
Barlow W 1883 Probable nature of the internal symmetry of
crystals. Nature (London) 29: 186-8, 205-7
Bernal J D 1964 The structure of liquids. Proc. R. Soc.
London, Ser. A 280: 299-322
Cargill G S 1984 Radial distribution functions and microgeometry of dense random packings of hard spheres. In:
Johnson D L, Sen (eds.) 1984 Physics and Chemistry
of Porous Media, Conference Proceedings Vol. 107. Am
erican Institute of Physics, New York, pp. 20-36
Cumberland D J, Crawford R J 1987 The Packing of
Particles. Elsevier, Amsterdam
Deresiewicz 1958 Mechanics of granular matter. Adv.
Appl. Mech. 5: 233-306
Finney J L 1970 Random packings and the structure of
simple liquids. I. The geometry of random close packing.
Proc. R. Soc. London, Ser. 319: 479-93
Finney J L 1983 Modelling the atomic structure. In:
Luborsky F (ed.) 1983 Amorphous Metallic Alloys.
Butterworth, London, pp. 42-57
Hill R 1950 The Mathematical Theory of Plasticity. Claren
don, Oxford
Johnson L, Kendall K, Roberts A D 1971 Surface energy
and the contact of elastic solids. Proc. R. Soc. London,
Ser. A 324: 301-13
Keedwell J 1984 Rheology and Soil Mechanics. Elsevier
Applied Science, London
Kendall 1986 Inadequacy of Coulomb's friction law for
particle assemblies. Nature (London) 319: 203-5
Kendall K, Alford McN, Birchall J D 1987 Elasticity of
particle assemblies as a measure of the surface energy of
solids. Proc. R. Soc. London, Ser. A 412: 269-83
Pusey , van Megen W 1986 Phase behaviour of concen
trated suspensions of nearly hard colloidal spheres.
Nature (London) 320: 340-2
Reynolds 1885 On the dilatancy of media composed of
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Sutherland D N, Hutchinson 1965 An open-structured
random solid. Nature (London) 206: 1036-7
K. Kendall
[ICI, R u n c o r n , U K ]
401
R
Raman Spectroscopy
R a m a n s p e c t r o s c o p y is a n analytical t e c h n i q u e t h a t
yields i n f o r m a t i o n a b o u t t h e m o l e c u l a r s t r u c t u r e of
s a m p l e m a t e r i a l s b a s e d o n o b s e r v a t i o n of scattered
light spectra. T h e t e c h n i q u e , as well as t h e p h e n o m e
n o n o n which it is b a s e d , is n a m e d after t h e I n d i a n
physicist, C . V. R a m a n , w h o s e w o r k w a s inspired by
curiosity a b o u t t h e distinct b l u e c o l o r of t h e M e d i t e r
r a n e a n Sea. In 1928, after m o r e t h a n seven years of
studying t h e effects of scattered light, R a m a n r e p o r t e d
his discovery of frequency-shifted lines in t h e scat
tered light spectra of t r a n s p a r e n t s u b s t a n c e s . T h e
shifted lines, R a m a n a n n o u n c e d , were i n d e p e n d e n t of
the exciting r a d i a t i o n a n d characteristic of t h e s a m p l e
itself. F u r t h e r research efforts established t h e univer
sality of t h e p h e n o m e n o n a n d t h e r e l a t i o n s h i p of t h e
R a m a n s p e c t r u m of a m o l e c u l e t o its v i b r a t i o n a l a n d
r o t a t i o n a l frequencies. A l t h o u g h t h e i m p o r t a n c e of
the R a m a n scattering m e t h o d for t h e s t u d y of m o l e c u
lar s t r u c t u r e w a s recognized by t h e scientific c o m
m u n i t y , a lack of suitable i n s t r u m e n t a t i o n i m p e d e d its
early d e v e l o p m e n t as a n analytical t e c h n i q u e . H o w
ever, t h e c o n t r i b u t i o n of R a m a n s p e c t r o s c o p y t o a
wide r a n g e of m o d e r n a p p l i c a t i o n s , including m a t e r
ials science, h a s been e n s u r e d by t h e d e v e l o p m e n t
of t h e laser, which p r o v i d e s a c o n v e n i e n t s o u r c e
of intense m o n o c h r o m a t i c light, a n d of p h o t o e l e c
tric r e c o r d i n g devices, w h i c h offer sensitive signal
detection.
1.
Theory
Light, which is a f o r m of e l e c t r o m a g n e t i c r a d i a t i o n ,
c a n interact with m a t t e r in a n u m b e r of different
ways, s o m e of w h i c h involve t h e transfer of energy
between p h o t o n s a n d molecules. Since differences in
e l e c t r o m a g n e t i c energy c a n b e o b s e r v e d as differences
in wavelength, t h e result of a n energy transfer c a n be
m e a s u r e d with spectroscopic m e t h o d s .
T h e i n t e r a c t i o n of light of a given w a v e l e n g t h with
a p a r t i c u l a r object d e p e n d s o n t h e m o l e c u l a r s t r u c t u r e
of t h e object. I n c i d e n t light m a y be t r a n s m i t t e d ,
reflected, a b s o r b e d o r scattered b y t h e molecules.
Reflection o r t r a n s m i s s i o n o c c u r s with little o r n o
c h a n g e in t h e r a d i a n t energy, so light is reflected o r
t r a n s m i t t e d a t t h e s a m e w a v e l e n g t h as t h e incident
r a d i a t i o n . Light is a b s o r b e d a t w a v e l e n g t h s c o r r e s
p o n d i n g t o energy differences b e t w e e n t w o electron
states of t h e molecule.
M o s t light scattering o c c u r s w i t h o u t gain o r loss of
energy a n d is referred t o as Rayleigh scattering.
H o w e v e r , as R a m a n discovered, a small fraction of
vnm)
w h e r e h is P l a n c k ' s c o n s t a n t , v 0 t h e frequency of t h e
incident r a d i a t i o n a n d vnm t h e frequency of t h e R a m a n
b a n d (i.e., t h e frequency of t h e v i b r a t i o n t h a t results
from t h e t r a n s i t i o n b e t w e e n energy levels a n d m).
F o r a n a n t i - S t o k e s s p e c t r u m , t h e frequency t e r m is
T h e intensity of a given v i b r a t i o n is p r o p o r t i o n a l t o
t h e f o u r t h p o w e r of t h e a b s o l u t e frequency of t h e
v i b r a t i o n ; t h a t is, t h e intensity of t h e signal increases
geometrically with t h e difference b e t w e e n incident
a n d v i b r a t i o n a l frequencies. Intensity is also directly
related t o t h e polarizability o r i n d u c e d dipole of t h e
molecule. F o r e x a m p l e , highly p o l a r i z a b l e molecules
like b e n z e n e o r c a r b o n disulfide p r o d u c e s t r o n g e r
signals t h a n w a t e r .
2. Information
Obtained
R a m a n s p e c t r o s c o p y c a n p r o v i d e qualitative, q u a n t i
tative a n d s t r u c t u r a l i n f o r m a t i o n a b o u t a variety of
m a t e r i a l s . M o s t significantly, t h e R a m a n s p e c t r u m
yields i n f o r m a t i o n a b o u t t h e m o l e c u l a r , r a t h e r t h a n
elemental, s t r u c t u r e of t h e s a m p l e .
Because t h e presence of p a r t i c u l a r a t o m i c g r o u p s
a n d chemical b o n d s is indicated by characteristic
frequencies in t h e R a m a n s p e c t r u m , t h e chemical
functional g r o u p s in a c o m p o u n d c a n be identified by
these g r o u p frequencies. T h e further a p p l i c a t i o n of
chemical i n t u i t i o n often leads t o t h e identity of t h e
c o m p o u n d itself.
403
Raman
Spectroscopy
T h e intensities of the b a n d s in a R a m a n s p e c t r u m
c a n be used t o d e t e r m i n e t h e c o n c e n t r a t i o n of a
c o m p o u n d of interest even in t h e presence of o t h e r
c o m p o u n d s . C o n c e n t r a t i o n s t o a few w t % a r e easily
achieved with a n y of several c a l i b r a t i o n t e c h n i q u e s ,
including c o m p a r i s o n with a n e x t e r n a l c a l i b r a t i o n
curve, a p p l i c a t i o n of the s t a n d a r d a d d i t i o n m e t h o d , in
which a k n o w n c o n c e n t r a t i o n of t h e c o m p o u n d is
a d d e d t o the m i x t u r e , o r use of a b a n d c o m m o n t o all
c o m p o n e n t s of t h e m i x t u r e as a n i n t e r n a l s t a n d a r d .
A w e a l t h of s t r u c t u r a l i n f o r m a t i o n a b o u t a c o m
p o u n d c a n be supplied b y R a m a n s p e c t r o s c o p y . F o r
e x a m p l e , it c a n be used t o differentiate a m o n g v a r i o u s
geometric forms of a c o m p o u n d , define t h e c o n f o r m a
tion a n d s y m m e t r y of a p o l y m e r o r d e t e r m i n e t h e
degree of crystallinity of a s u b s t a n c e .
T h e n u m b e r of R a m a n v i b r a t i o n s expected for a
given g e o m e t r y c a n be predicted by g r o u p theoretical
m e t h o d s . By c o m p a r i n g the o b s e r v e d R a m a n spec
t r u m with theoretical values, it is possible t o differen
tiate between g e o m e t r i c forms such as t e t r a h e d r a l a n d
s q u a r e p l a n a r c o o r d i n a t i o n . In several cases R a m a n
spectroscopy h a s p r o v i d e d t h e first evidence t h a t a n
i n o r g a n i c c o m p o u n d exists in o n e g e o m e t r y r a t h e r
than another.
T h e s h a r p n e s s a n d p o s i t i o n of t h e R a m a n b a n d s
are related t o t h e degree of crystallinity of t h e scatter
ing m e d i u m : the m o r e crystalline a m a t e r i a l , t h e
s h a r p e r the R a m a n b a n d s . E l e m e n t a l silicon, used
widely in the s e m i c o n d u c t o r i n d u s t r y , h a s a s t r o n g ,
1
s h a r p b a n d b e t w e e n 520 a n d 525 A c m " in t h e crystal
line state. In the a m o r p h o u s form this b a n d m o v e s t o
- 1
a lower R a m a n shift, as low as 480 A c m , a n d
becomes m u c h b r o a d e r a n d w e a k e r .
T h e R a m a n s p e c t r u m of a p o l y m e r reveals detailed
i n f o r m a t i o n a b o u t its s t r u c t u r e . It is possible t o define
the c o n f o r m a t i o n o r s e c o n d a r y s t r u c t u r e of p o l y m e r s
from the frequency p o s i t i o n s of certain sensitive
b a n d s in the R a m a n s p e c t r u m . I n b i o p o l y m e r s , for
e x a m p l e , t h e a m i d e b e n d i n g m o d e s in t h e 1 2 0 0 1
1700 A c m " region a r e used as m a r k e r s to c h a r a c t e r
ize w h e t h e r the molecule is in a helical, r a n d o m o r
folded-sheet s t r u c t u r e .
T h e degree of s t r u c t u r a l s y m m e t r y of a s u b s t a n c e is
indicated by t h e a m o u n t of v a r i a t i o n in t h e p o l a r i z a
tion characteristics of the R a m a n b a n d s . In a highly
o r d e r e d p o l y m e r , there is a m i x t u r e of b o t h p o l a r i z e d
a n d depolarized b a n d s , while in a d i s o r d e r e d p o l y m e r ,
all the R a m a n active b a n d s a r e polarized. T h e distinc
tion b e t w e e n t h e t w o is evidenced b y t h e intensity of
the b a n d s as viewed t h r o u g h a n a n a l y z e r o r i e n t e d
n o r m a l t o the p o l a r i z a t i o n of the scattered r a d i a t i o n :
the intensity of the p o l a r i z e d b a n d s a p p r o a c h e s z e r o ,
while t h a t of the d e p o l a r i z e d b a n d s is n o n z e r o .
T h e m o l e c u l a r c h a i n length of p o l y m e r s is indicated
by a
special class of low-frequency
bands
- 1
( < 100 A c m ) in t h e R a m a n s p e c t r u m . F o r these
b a n d s , k n o w n as l o n g i t u d i n a l a c o u s t i c m o d e s
( L A M s ) , p o s i t i o n is inversely related t o c h a i n length;
404
5.
Instrumentation
Raman
4. Comparison
with Infrared
Other
Techniques
Spectroscopy
and
R a m a n s p e c t r o s c o p y a n d infrared a b s o r p t i o n spec
t r o s c o p y a r e c o m p l e m e n t a r y analytical t e c h n i q u e s .
Both provide vibrational information about the mol
ecule, b u t different d a t a a r e c o n v e y e d in t h e scattering
a n d a b s o r p t i o n s p e c t r a a n a l y z e d , respectively, b y
R a m a n a n d infrared s p e c t r o s c o p y (see Infrared Spec
troscopy). B o t h R a m a n a n d infrared d a t a a r e r e q u i r e d
to characterize fully t h e v i b r a t i o n a l s p e c t r u m of a n
Spectroscopy
u n k n o w n c o m p o u n d , p a r t i c u l a r l y o n e with highly
symmetric geometry.
T h e c o m p l e m e n t a r y n a t u r e of t h e techniques is
exemplified b y their selection rules: a v i b r a t i o n is
R a m a n - a c t i v e if there is a c h a n g e in t h e i n d u c e d
dipole o r polarizability of t h e molecule; it is infraredactive if there is a c h a n g e in t h e p e r m a n e n t dipole.
I o n i c species, such as s o d i u m c h l o r i d e , a r e a m o n g t h e
few types of c o m p o u n d which d o n o t h a v e a R a m a n
s p e c t r u m . A h o m o n u c l e a r d i a t o m i c molecule like
n i t r o g e n d o e s n o t h a v e a n infrared s p e c t r u m , b u t
sodium chloride does.
A p a r t i c u l a r m o l e c u l a r v i b r a t i o n m a y b e observ
able in b o t h spectra, b u t different in intensity. T h e
lower t h e s y m m e t r y of a molecule, t h e greater t h e
o v e r l a p of its R a m a n - a c t i v e a n d infrared-active vibra
tions. I n m o s t real-world s a m p l e s , a high degree of
o v e r l a p p e r m i t s selection of R a m a n o r infrared spec
t r o s c o p y as t h e preferred analytical t e c h n i q u e . In
general, n o n p o l a r c o m p o u n d s a n d s y m m e t r i c vibra
tions a r e m o r e readily o b s e r v e d in R a m a n spectros
c o p y , w h e r e a s infrared s p e c t r o s c o p y favors p o l a r
compounds and asymmetric vibrations.
T a b l e s 1-3 illustrate differences in s a m p l e h a n d l i n g ,
i n s t r u m e n t a t i o n a n d t y p e of i n f o r m a t i o n o b t a i n e d for
the R a m a n a n d infrared t e c h n i q u e s . A s indicated in
the tables, R a m a n s p e c t r o s c o p y offers a n u m b e r of
a d v a n t a g e s over infrared s p e c t r o s c o p y . A p r i m a r y
a d v a n t a g e of R a m a n is t h a t it c a n b e p e r f o r m e d in t h e
visible region of t h e s p e c t r u m , w h e r e sources a r e m o r e
intense a n d d e t e c t o r s a r e m u c h m o r e sensitive t h a n in
t h e infrared. A n o t h e r a d v a n t a g e is t h e spectral r a n g e
of R a m a n i n s t r u m e n t a t i o n . T h e entire s p e c t r u m , from
1
10 t o 4000 c m , c a n be r e c o r d e d in a single scan with
t h e s a m e R a m a n i n s t r u m e n t . I n infrared spectros
c o p y , t h e scan r a n g e is m o r e limited: a different
Spectrograph stage
Focal plane
7 5 mm
outside housing
Turret with
3 kinematic
^-
!--_-0
Slot
(EK-V
Slit
gratings
Filter stage
- -
Subtractive
dispersion
Entrance I
slit
Figure 1
Optical schematic of a typical Raman system
405
Raman
Spectroscopy
Table 1
Comparison of sampling handling in Raman and infrared
3
spectroscopy
Raman
General applicability 95
(%)
Unsuitable materials fluorescent and
colored samples
Sample preparation
liquids
powders
single crystals
polymers
single fibers
gases and vapors
Cells
Micro work
mass ^g)
size ()
Trace work
High and low
temperature
Limits of detection
very simple
very simple
very simple
very simple
very simple (but see
unsuitable
materials)
moderately simple
with microscope
moderately simple
very simple (glass)
good
<1
1
sometimes
moderately simple
good
Infrared
99
single crystals,
metals,
aqueous
solutions
variable
very simple
more difficult
very difficult
more difficult
moderate
laser
Detector
1
Resolution ( c m )
Principal limitation
Wave number
range
1
(Acm )
Purge requirement
Photometry
simple
more complex
(alkali halide)
good
<1
20
sometimes
moderately
simple
very good
406
Infrared
slightly greater
blackbody or
diode laser
photomultiplier tube thermal,
pyroelectric,
bolometers
-0.15
-0.05
energy
energy
10-4000
18(M000 (one
instrument)
10-400
(second
instrument or
alternative
beam splitter,
source and
detector)
no
yes
scattering single
absorption
beam
double beam
Infrared
excellent
symmetric
excellent
excellent
excellent
fair
excellent
asymmetric
very good
excellent
very difficult
good
excellent
difficult
fair
excellent
difficult
Table 2
Comparison 8of instrumentation for Raman and infrared
spectroscopy
Complexity
Source
Fingerprinting
Best vibrations
Structural
Group frequencies
Aqueous solutions
Quantitative
analysis
Low-frequency
modes
Libraries
Raman
Raman
Table 3
Comparison of quality of 8information provided by Raman
and infrared spectroscopy
i n s t r u m e n t , o r at least a c h a n g e of b e a m splitter a n d
1
d e t e c t o r , is r e q u i r e d below 180 c m .
R a m a n also offers a n a d v a n t a g e in s a m p l e p r e p a r a
tion. Typically, there is little o r n o s a m p l e p r e p a r a t i o n
required for R a m a n t e c h n i q u e s , while ir s p e c t r o s c o p y
requires t h e s a m p l e t o be pressed i n t o a pellet with a
K B r m a t r i x o r g r o u n d i n t o a m u l l with m i n e r a l oil.
A q u e o u s s o l u t i o n s , which p o s e serious difficulties for
infrared s p e c t r o s c o p y , p r e s e n t n o p r o b l e m s for
R a m a n , p r i m a r i l y b e c a u s e w a t e r is a p o o r R a m a n
scatterer b u t a s t r o n g ir a b s o r b e r . T h e s a m p l e cells
also c o n t r i b u t e t o t h e difference: glass, which is used
in R a m a n cells, is easy t o h a n d l e , b u t ir cells, typically
m a d e of a n alkali halide o r s o m e o t h e r highly h y g r o
scopic salt, a r e m u c h m o r e delicate.
A n analytical a d v a n t a g e of infrared over R a m a n
s p e c t r o s c o p y is t h e g r e a t e r availability of d o c u m e n t e d
spectra. Extensive spectral libraries facilitate t h e iden
tification of u n k n o w n c o m p o u n d s .
T h e m o l e c u l a r n a t u r e of t h e i n f o r m a t i o n o b t a i n e d
with R a m a n s p e c t r o s c o p y gives it a distinct a d v a n t a g e
over electron t e c h n i q u e s such as electron spectros
c o p y for chemical analysis ( E S C A ) , A u g e r spectros
c o p y a n d electron m i c r o p r o b e s , which yield only
elemental i n f o r m a t i o n . F o r e x a m p l e , R a m a n c a n dis
tinguish b e t w e e n styrene a n d 1,4-butadiene in a s a m
ple, w h e r e a s E S C A c a n d e t e r m i n e only t h a t there is
c a r b o n p r e s e n t (see Electron Spectroscopy for Chem
ical Analysis). T h e R a m a n capability for in situ a n a l y
sis is also a n a d v a n t a g e for m a n y a p p l i c a t i o n s .
F l u o r e s c e n c e interference is a m a j o r d i s a d v a n t a g e
in R a m a n s p e c t r o s c o p y . Because fluorescence is a
m u c h s t r o n g e r effect, it c a n completely o v e r w h e l m t h e
R a m a n s p e c t r u m . W h e n impurities a r e t h e s o u r c e of
t h e fluorescence, t h e p r o b l e m m a y be c o r r e c t e d b y
purifying t h e s a m p l e , for e x a m p l e by recrystallization
o r simply by filtering it t h r o u g h activated c h a r c o a l o r
a l u m i n a . O t h e r a p p r o a c h e s include selecting a n exci
t a t i o n frequency a w a y from t h e fluorescence excita
tion o r q u e n c h i n g t h e fluorescence. A p e r i o d of laser
Raman
Monitor
TV
camera
Rotating
Spectroscopy
Photomultiplier
tube
prism
Optional
viewing port
S p a t i a l filter
,
Collimated
light
Beam
'splitters
HHH)
Reflection
illuminator
- g
>
U*
Objective
~ T s t a g e
Transmission
illuminator
Figure 2
Optical schematic of a triple spectrograph designed for multichannel detectors
5. Important
Developments
in
Raman
Spectroscopy
T h e m u l t i c h a n n e l optical d e t e c t o r , o r a r r a y d e t e c t o r ,
h a s b e c o m e increasingly i m p o r t a n t in R a m a n spec
t r o s c o p y . T h i s device e m p l o y s 512 o r 1024 s e p a r a t e
d e t e c t o r elements for s i m u l t a n e o u s o b s e r v a t i o n of a
large s e g m e n t of a s p e c t r u m . Because a m u l t i c h a n n e l
d e t e c t o r eliminates t h e need for p o i n t - b y - p o i n t inte
g r a t i o n of t h e s p e c t r u m , it p e r m i t s m u c h faster d a t a
acquisition. S h o r t e r a c q u i s i t i o n times a r e critical in
t h e investigation of p h a s e c h a n g e s , excited states o r
t r a n s i e n t species such as r e a c t i o n i n t e r m e d i a t e s . T h e
resulting decrease in i r r a d i a t i o n t i m e is also i m p o r t a n t
for u n s t a b l e s a m p l e s .
A d a p t a t i o n s of t h e R a m a n system s p e c t r o m e t e r a r e
necessary t o m a k e it c o m p a t i b l e with a m u l t i c h a n n e l
d e t e c t o r . H i g h dispersion is a p r o b l e m , because it
limits t h e spectral c o v e r a g e , b u t it is still necessary t o
reject t h e n o n - R a m a n scatter. O n e s o l u t i o n is t h e use
of a triple s p e c t r o g r a p h such as t h a t s h o w n in Fig. 2.
A s i n d i c a t e d in t h e d i a g r a m , a short-focal-length,
z e r o - d i s p e r s i o n d o u b l e m o n o c h r o m a t o r acts as a
n o t c h filter t o isolate t h e R a m a n scatter from the
u n w a n t e d r a d i a t i o n . A s p e c t r o g r a p h t h e n disperses it
with a n u n v i g n e t t e d , flat focus across t h e d e t e c t o r
face. T h e triple s p e c t r o g r a p h c a n b e used with either
macrosample or microsample modules.
A t e c h n i q u e w h i c h h a s p r o v e d very effective for
thin films is t h e c o u p l i n g of i n t e g r a t e d optics with the
n o r m a l R a m a n collection optics. T h i s p e r m i t s the
laser t o b e m u l t i p a s s e d t h r o u g h the film several
407
Raman
Spectroscopy
6.
Applications
T h e diverse a p p l i c a t i o n s of R a m a n s p e c t r o s c o p y in
clude m a t e r i a l s analysis of s e m i c o n d u c t o r s , p o l y m e r s ,
p i g m e n t s a n d catalysts, a n d investigations in t h e fields
of physics, g e o c h e m i s t r y a n d b i o c h e m i s t r y . F o r ex
a m p l e , R a m a n s p e c t r o s c o p y h a s been used t o m o n i t o r
impurities d u r i n g the processing of silicon crystals
a n d t o detect toxic m o n o m e r s in c o n t a c t lenses.
H i g h - p u r i t y crystalline silicon is used extensively in
408
Raman
shift
(cm )
Figure 3
Raman spectra of silicon wafers containing interstitial
oxygen (upper trace) and oxygen-free (lower trace).
(Micro-Raman spectrometer with 514.5 nm 0.02 W argon
ion laser source)
t h e m a n u f a c t u r e of s e m i c o n d u c t o r s a n d solar cells.
T h e m o s t c o m m o n m e t h o d for g r o w i n g silicon, the
C z o c h r a l s k i m e t h o d , i n t r o d u c e s interstitial oxygen
a n d s u b s t i t u e n t c a r b o n impurities i n t o t h e silicon
crystal. A l t h o u g h a t low levels these impurities serve
beneficial roles, excluding o t h e r impurities a n d
t h e r e b y p r e v e n t i n g l e a k a g e c u r r e n t s in t h e e n d device,
at higher c o n c e n t r a t i o n s they c a u s e w a r p i n g of t h e
silicon wafer. M o r e o v e r , h e a t m a y c a u s e p r e c i p i t a t i o n
of t h e interstitial oxygen t o f o r m S i 0 2 . R a m a n spec
t r o s c o p y offers a n o n d e s t r u c t i v e t e c h n i q u e for m o n i
t o r i n g i m p u r i t y levels, w h i c h m a y b e altered d u r i n g
t h e m a n u f a c t u r i n g process.
F i g u r e 3 s h o w s m i c r o - R a m a n spectra for t w o sili
c o n wafers, o n e m a n u f a c t u r e d b y t h e C z o c h r a l s k i
m e t h o d ( u p p e r trace), t h e o t h e r g r o w n b y a n a l t e r n a t
ive p r o c e s s t h a t d o e s n o t i n t r o d u c e interstitial oxygen.
B o t h spectra exhibit a p h o n o n b a n d of crystalline
1
silicon a t 525 A c m " . T h e w e a k , b r o a d feature a t
-1
~1000 Acm
is a n o v e r t o n e s p e c t r u m of t h e
-1
525 A c m
p e a k . T h e s p e c t r u m for t h e C z o c h r a l s k i
- 1
wafer clearly s h o w s a b a n d a t 510 Acm , which is d u e
to t h e interstitial oxygen, while t h e lower s p e c t r u m
s h o w s only t h e crystalline silicon b a n d s .
P o l y ( m e t h y l m e t h a c r y l a t e ) ( P M M A ) is a p o l y m e r
used for b o t h c o n t a c t lenses a n d i m p l a n t lenses. T h e
p r o d u c t i o n of P M M A involves b r e a k i n g the d o u b l e
b o n d b e t w e e n c a r b o n a t o m s in t h e m o n o m e r m e t h y l
m e t h a c r y l a t e . A l t h o u g h P M M A c a n be safely i n t r o
d u c e d i n t o t h e b o d y e n v i r o n m e n t , r e p o r t s indicate
t h a t t h e m o n o m e r from w h i c h it is f o r m e d m a y be
toxic. R a m a n s p e c t r o s c o p y c a n b e used t o d e t e r m i n e
t h e residual q u a n t i t y of m o n o m e r in t h e P M M A lens
material.
F i g u r e 4 s h o w s a R a m a n s p e c t r u m for a P M M A
s a m p l e w i t h ~ 1 % m o n o m e r . T h e d e t e r m i n a t i o n is
Reflection
Electron
Microscopy
I I 0
F . Purcell
[Spex I n d u s t r i e s , E d i s o n ,
N e w Jersey, U S A ]
I
0
1550
2000
Raman shift
(cm)
Figure 4
Raman spectrum of poly(methyl methacrylate) with ~ 1 %
residual monomer. (Raman spectrometer with 488.0 nm
0.125 W argon ion laser source)
7. Future
Prospects
Interest in R a m a n s p e c t r o s c o p y , which h a s g r o w n
steadily since t h e 1960s, is likely t o receive further
i m p e t u s from c o n t i n u e d d e v e l o p m e n t s in b o t h tech
niques a n d i n s t r u m e n t a t i o n . A d v a n c e s in c o n t i n u o u s wave ultraviolet lasers will e x t e n d t h e applicability of
r e s o n a n c e R a m a n s p e c t r o s c o p y . I m p r o v e m e n t s in
m u l t i c h a n n e l d e t e c t o r s will increase t h e speed a n d
convenience of R a m a n investigations. D e v e l o p m e n t
of surface-enhanced R a m a n s p e c t r o s c o p y will lead t o
new analytical m e t h o d s for s t u d y i n g surface p h e n o
m e n a . W i d e r availability of c o m p u t e r i z e d systems
will e n a b l e m o r e sophisticated e x p e r i m e n t s a n d d a t a
h a n d l i n g . Extensive spectral libraries a n d c o m p u t e r
ized searches will a d d c o n v e n i e n c e a n d efficiency t o
R a m a n analyses. T h e future of R a m a n s p e c t r o s c o p y
a p p e a r s bright, with p r o m i s e s of faster acquisition
times, better a n d m o r e flexible sources a n d completely
a u t o m a t e d systems.
See also: Infrared Spectroscopy; Polymers: Raman Spec
troscopy
Bibliography
Clark R J H, Hester R (eds.) 1976-84 Advances in Infrared
and Raman Spectroscopy, Vols. 1-11. Wiley, New York
7. Imaging
and Image
Interpretation
F o r R E M i m a g i n g in a c o n v e n t i o n a l t r a n s m i s s i o n
electron m i c r o s c o p e , t h e s a m p l e m u s t be flat a n d
crystalline. T o achieve surface sensitivity the electrons
s h o u l d n o t p e n e t r a t e far b e l o w t h e surface a n d this is
achieved b y h a v i n g t h e incident parallel b e a m of
electrons i m p i n g i n g o n t h e surface at a glancing angle.
W i t h this g e o m e t r y t h e electrons reflected from the
surface give rise t o a reflection high-energy electron
diffraction ( R H E E D ) p a t t e r n (see Fig. 1) in the b a c k
focal p l a n e of t h e objective lens. I n o r d e r t o p r o d u c e a
409
Reflection
Electron
Microscopy
Sample
Figure 1
REM image formation
C h a n g e s of t h e diffraction c o n d i t i o n across t h e s a m
ple will result in c h a n g e s of intensity across t h e i m a g e .
F o r a specimen o r i e n t e d t o t h e B r a g g c o n d i t i o n t h e
d i s t o r t i o n of a t o m i c p l a n e s a r o u n d a defect will
a p p e a r d a r k in t h e i m a g e . T h i s d i s t o r t i o n is d u e t o t h e
strain field a r o u n d t h e e m e r g e n c e of a screw disloca
tion o r a l o n g a step. T h e c o n t r a s t from a screw
dislocation in a s a m p l e t h a t is n o t exactly a t t h e B r a g g
c o n d i t i o n c a n be w o r k e d o u t in a similar w a y , with
o n e of t h e wings a r o u n d t h e d i s l o c a t i o n being closer
t o t h e B r a g g c o n d i t i o n a n d therefore b r i g h t e r a n d the
o t h e r being further from t h e B r a g g c o n d i t i o n a n d
consequently darker. These arguments are based on
t h e c o l u m n a p p r o x i m a t i o n , w h e r e t h e intensity of a n y
region is c o n s i d e r e d t o be e q u a l t o t h a t from a perfect
surface w h o s e o r i e n t a t i o n is t h e s a m e as t h e region
u n d e r c o n s i d e r a t i o n . T h i s intensity i n f o r m a t i o n c a n
b e o b t a i n e d from a r o c k i n g c u r v e calculated for a
perfect crystal a n d , in general, t h e full w i d t h s a t half
m a x i m u m of t h e B r a g g p e a k s a r e in t h e r a n g e 1 0 ~ 3 1 0 " 4 r a d so t h a t surface d i s t o r t i o n s as small as
1 0 " 4 r a d c a n b e detected. Diffraction c o n t r a s t c a n also
s h o w d o m a i n s of surface r e c o n s t r u c t i o n o r a d s o r p
tion in cases w h e r e t h e different d o m a i n s c o n t r i b u t e
different intensities t o certain diffraction s p o t s .
M o s t of a n R E M i m a g e is o u t of focus a n d so
electrons, h a v i n g different optical p a t h lengths d u e t o
d i s t o r t i o n s a r o u n d defects, c a n interfere c o n s t r u c
tively o r destructively giving rise t o d a r k - b r i g h t
fringes a r o u n d steps a n d screw dislocations a n d this
p h a s e c o n t r a s t is often d o m i n a n t in R E M i m a g e s . If
t w o diffraction s p o t s t h a t a r e parallel t o t h e edge of
t h e s a m p l e a r e allowed t h r o u g h t h e objective a p e r t u r e
they c a n interfere t o give lattice fringes t h a t a r e useful
Figure 2
Monatomic steps terminate at the points where screw
dislocations emerge at the surface. At A the dislocation is
in focus and at the Bragg condition, at the dislocation is
slightly off the Bragg condition and at C the black-white
fringe is due to phase contrast from an out-of-focus
dislocation
Reflection
2.
Observations
O n e of t h e first uses of R E M w a s t o s t u d y t h e p h a s e
c h a n g e o n a silicon (111) surface from 1 1 t o 7 x 7.
H e r e it w a s noticed t h a t n u c l e a t i o n o c c u r s preferen
tially o n t h e t o p side of t h e steps. W h e n gold is
deposited o n t h e silicon (111) 7 x 7 s t r u c t u r e t h e
nucleation of t h e a d s o r b a t e s t r u c t u r e occurs o n t h e
t o p of t h e steps b u t w h e n gold is d e p o s i t e d o n a
p l a t i n u m (111) m o n o l a y e r islands of gold nucleate a t
t h e b o t t o m o f t h e steps. I n t h e l a t t e r case t h e g r o w t h
r a t e d e p e n d s o n t h e w i d t h of t h e lower terraces
indicating t h a t t h e a d a t o m s d o n o t "fall d o w n " t h e
steps. Results like these o b t a i n e d b y R E M s h o w
clearly t h a t w h e n t h e t e r r a c e w i d t h is n a r r o w e r t h a n
the diffusion distance t h e surface d y n a m i c processes
are c o n t r o l l e d b y t h e steps. T h e s e facts s h o u l d b e
b o r n e in m i n d b y all surface scientists since even a
sample c u t t o within | of a low-index p l a n e will h a v e
steps a p p r o x i m a t e l y every 25 n m a n d this is w i t h o u t
allowing for small u n d u l a t i o n s t h a t o c c u r d u r i n g
preparation!
T h e c o n t r o l l e d o x i d a t i o n of surfaces is a n o t h e r a r e a
of research t h a t c a n b e e x a m i n e d b y R E M very
effectively. W h e n a silicon (111) 7 x 7 surface is
oxidized a t 920 it is n o t e d t h a t t h e steps m o v e b a c k
a n d between t h e steps small h o l l o w s a p p e a r . T h e s e
topographic changes are caused by the formation a n d
diffusion of vacancies. T h e vacancies a r e c r e a t e d b y
the s u b l i m a t i o n of SiO. (Similar l o o k i n g h o l l o w s h a v e
also been o b s e r v e d o n n o b l e m e t a l surfaces t h a t h a v e
been p r e p a r e d b y h i g h - t e m p e r a t u r e a n n e a l i n g . )
T h e n u c l e a t i o n a n d g r o w t h of t h r e e - d i m e n s i o n a l
islands o f C u 2 0 o n c o p p e r is also affected b y t h e
presence of steps a n d , conversely, t h e presence of
these islands c a n affect t h e m o v e m e n t of t h e steps.
3. Scanning
Analyses
R E M c a n also b e p e r f o r m e d using a s c a n n i n g t r a n s
mission electron m i c r o s c o p e ( S T E M ) a n d d u e t o t h e
reciprocity t h e o r e m similar surface i m a g e s a r e
o b t a i n e d (see Electron Microscopy,
Analytical).
The
d i s a d v a n t a g e o f S T E M is t h e l o w e r signal s o t h a t
larger a p e r t u r e s a r e r e q u i r e d . L a r g e r a p e r t u r e s t e n d t o
Electron
Microscopy
4. Future
Developments
Bibliography
Cowley J 1986 Electron microscopy of surface structure.
Prog. Surf. Sci. 21: 209-50
411
Reflection
Electron
Microscopy
Monochromator
Figure 1
The principles of strain measurement, showing the
definition of gauge volume sampled and the direction of
strain measured
412
1.
Principles
Residual
w h e r e a s a large s a m p l e m a y b e m o v e d t h r o u g h t h e
gauge v o l u m e in o r d e r t o o b t a i n a profile o f a
p r o p e r t y such a s strain.
Polycrystalline m a t e r i a l s give rise t o c o n e s of dif
fracted n e u t r o n s a t angles q>hkl = 26hkl a b o u t t h e inci
d e n t b e a m o n t h e s a m p l e . T h e s e angles a r e given b y
Bragg's law:
2 ^ / S i n ^
(1)
w h e r e dm is t h e lattice s p a c i n g of p l a n e s w i t h Miller
indices hkl. T h e c o n e of scattering arises from t h e
subset of crystallites o r g r a i n s in t h e s a m p l e w h i c h
satisfy B r a g g ' s l a w a n d w h i c h a r e o r i e n t e d s o t h a t t h e
planes a r e a t a n angle t o t h e incident b e a m . I t is
usual t o define a scattering v e c t o r Q = k{ - k(, w h e r e
k{ a n d k{ a r e t h e incident a n d scattered n e u t r o n w a v e
vector of m a g n i t u d e \k\ = 2/, a s s h o w n in F i g . 1.
F o r B r a g g reflection, Q is n o r m a l t o t h e p l a n e s giving
the diffracted b e a m a n d of m a g n i t u d e e q u a l t o t h a t of
the reciprocal lattice vector r of t h e p l a n e s : \Q\ = \rhkl\
(Kittel 1986).
T h e d e t e c t o r is s c a n n e d t h r o u g h <phkl t o d e t e r m i n e
the p e a k - c o u n t angle w h i c h , in t h e case of a large
sample, c o r r e s p o n d s t o t h e a v e r a g e dm of t h e g r a i n s in
the g a u g e v o l u m e s a m p l e d . U s u a l l y a fitting r o u t i n e
using least-squares m i n i m i z a t i o n is used t o d e t e r m i n e
the angle a n d a n g u l a r w i d t h of t h e p e a k . T h e a v e r a g e
lattice m a c r o s t r a i n in t h e v o l u m e s a m p l e d is t h e n
given b y
e
hki
(dhkl
dohjcl)/dohkl
= - (cot eohkl)(q>hkl_
(p0hkl)/2
(2)
Stresses:
Measurement
Using Neutron
Diffraction
m a y hit t h e s p e c t r o m e t e r h a r d w a r e , o r p a t h lengths of
t h e b e a m in t h e s a m p l e m a y b e c o m e excessive, p r e
venting some orientations. It should be noted that the
v o l u m e s a m p l e d is i n d e p e n d e n t of t h e vertical height
of t h e a p e r t u r e in t h e scattered b e a m , so in o r d e r t o
increase intensity this c a n b e m a d e a s large a s possible
consistent w i t h t h e r e q u i r e d definition in t h e direction
of e. A vertical d e t e c t o r c a n b e used with a d v a n t a g e .
A t = 90 t h e c o n e b e c o m e s a p l a n e of scattering a n d
this is also t h e o p t i m u m scattering angle for definition
of t h e g a u g e v o l u m e . A l t h o u g h t h e r e s o l u t i o n in strain
increases with a n d is best a t ~ 180, using <p~90
scattering a t b o t h m o n o c h r o m a t o r a n d s a m p l e is
often a g o o d c o m p r o m i s e . H o w e v e r , a n angle of
90 m a y h a v e t h e a d v a n t a g e t h a t it c a n p r o v i d e
m o r e r e a d y access t o t h e p o i n t in t h e s a m p l e a t which
t h e strain is t o b e m e a s u r e d . T h e g a u g e v o l u m e s h a p e
a n d size m u s t b e c h o s e n w i t h d u e c o n s i d e r a t i o n t o
t h e direction a n d m a g n i t u d e o f t h e strain g r a d i e n t ,
t h e intensity of scattering a n d c o n s e q u e n t m e a s u r e
m e n t time, a n d t h e size o f t h e grains in t h e s a m p l e .
3
Typically, g a u g e v o l u m e s a r e b e t w e e n 1 m m a n d
3
27 m m .
T h e u s e o f a h o r i z o n t a l position-sensitive d e t e c t o r
( P S D ) c a n speed u p d a t a collection b y effectively
p e r f o r m i n g t h e scan of a t o n e setting. H o w e v e r , t h e
definition of t h e g a u g e v o l u m e b e c o m e s difficult a s
m a s k s m u s t b e placed very close t o t h e s a m p l e a n d
these m a y p r e v e n t r o t a t i o n o f t h e s a m p l e t o give
s t r a i n s in different d i r e c t i o n s . I t s h o u l d b e n o t e d t h a t ,
in c o n t r a s t with n o r m a l p o w d e r diffraction, higher
w a v e l e n g t h o r d e r s (A/2, A/3, etc.) from t h e m o n o c h r o
m a t o r c a n often b e u s e d w i t h a d v a n t a g e in strain
m e a s u r e m e n t . I n o r d e r t o o b t a i n diffraction angles of
0
0?~9O , n e u t r o n w a v e l e n g t h s in t h e region A = 0 . 1 5 0.25 n m m u s t usually b e used.
A n a l t e r n a t i v e t o a s t e a d y r e a c t o r s o u r c e of n e u
t r o n s is t h e p u l s e d w h i t e b e a m o f n e u t r o n s given b y a
s p a l l a t i o n s o u r c e . I n this case polycrystalline diffrac
tion is o b s e r v e d a t a fixed . O n m o s t s t a n d a r d
p o w d e r diffraction i n s t r u m e n t s is usually a r o u n d
150 t o 180 t o give very g o o d r e s o l u t i o n a n d t i m e
of flight t is used t o scan t h e different lattice p l a n e s .
T h e strain is n o w given b y e = At/t = /, w h e r e t =
L/v = (hrn\K)L is time t a k e n for a n e u t r o n with m a s s m
a n d velocity t o travel a p a t h length L , a n d h is
P l a n c k ' s c o n s t a n t . T h e a d v a n t a g e of this m e t h o d is
t h a t strains m a y b e m e a s u r e d from m a n y lattice
p l a n e s {hkl} a t o n c e . H o w e v e r , Q is nearly a l o n g k{ in
t h e b a c k - s c a t t e r i n g a r r a n g e m e n t . A s for t h e r e a c t o r
i n s t r u m e n t , c o u n t e r s a t 90 m u s t b e used t o give
m e a s u r e m e n t of t h e full strain t e n s o r a n d such instru
m e n t s a r e u n d e r d e v e l o p m e n t . T h e p o s i t i o n i n g of t h e
s a m p l e is even m o r e critical h e r e a s it m a y affect L a n d
h e n c e t.
I n m o s t cases, t h e strain a n d stress a r e triaxial a n d
c a n b e r e p r e s e n t e d b y a strain t e n s o r a n d a stress
t e n s o r . If o n e defines axes Oxyz within t h e s a m p l e
a n d a t a p o i n t with respect t o these axes, t h e n t h e
413
Residual
Stresses:
Measurement
Using Neutron
Diffraction
= l'\x
+ m'hyy
+ 2m'n'eyz
+ n'\
2\'m'exy
+ 2'
(3)
+ v ) ] # + {vE/[(\
+ * ? r + zz)>
- 2v)(l + v)]}(er
i = *,Y,Z
(4)
of Strain
and Stress
Field
Measurement
A selection of examples of measurements is briefly given
to illustrate the range of application of the technique.
Full details can be found in the references given.
2.1 Stress in
Weldments
Stress in Railroad
Rails
Residual
Stresses:
Measurement
Using Neutron
Diffraction
after PWHT
-5
-10
-15
-20
Depth f r o m t o e , z ( m m )
Figure 2
Variation of strain ex through the plate beneath the toe of
the weld in a T-butt weldment (inset) before and after
postweld heat treatment (PWHT). The direction of strain
measured is perpendicular to the weld line (after Allen et
al. 1988) (the arrow indicates zero-strain angle)
P S D for r a p i d d a t a collection. A n e x a m p l e of t h e
detailed p a t t e r n of t h e t r a n s v e r s e c o m p o n e n t of resi
d u a l stress f o u n d a c r o s s t h e h e a d of a used rail is
s h o w n in Fig. 3. T h e a s s y m e t r y in t h e p a t t e r n arises
from the fact t h a t t h e r u n n i n g line of wheel c o n t a c t is
offset by + 6 m m from t h e rail c e n t r e .
2.3 Stress During Fatigue Cycling of a Compact
Tension Specimen
T h e m a x i m u m triaxial stress levels a l o n g t h e line of
c r a c k i n g of a small (31.5 m m 49.6 m m 13.1 m m )
c o m p a c t tension specimen of BS 4360 steel h a v e b e e n
m e a s u r e d b y b o l t i n g t h e specimen a t t h e p e a k stress
level ( H u t c h i n g s et al. 1990). T h e specimen h a d b e e n
subjected t o 20 000 cycles of fatigue l o a d i n g , w i t h
a stress intensity level v a r y i n g b e t w e e n a m i n i m u m
of
= 3 M P a ram"2 a n d
a
maximum
of
K= 34 M P a m m 1 / 2, in o r d e r t o p r o d u c e a small c r a c k
of 3.6 m m in length. T h e d a t a w e r e t a k e n with a g a u g e
v o l u m e of 1 m m 3 a n d a r e s h o w n in Fig. 4. T h e stress
field w a s f o u n d t o be n e i t h e r p l a n e strain n o r p l a n e
Figure 3
Transverse residual stress contour levels found from a
series of scans of the gauge volume across the head of a
section of used railroad rail (after Webster et al. 1990)
15
20
25
Distance f r o m s a m p l e c e n t e r ,
(mm)
Figure 4
Triaxial stress variation with position JC (y = = 0) in a
cracked fatigue test specimen bolted in the maximum
crack-tip stress configuration. The arrow denotes the
position of the crack tip on the specimen center line and
the shaded line the outer edge of the specimen (after
Hutchings et al. 1990)
stress, states often a s s u m e d in theoretical calculations,
a n d t h e p e a k stress levels were spatially b r o a d e r a n d
smaller in m a g n i t u d e t h a n expected from t h e o r y
a s s u m i n g p l a n e strain. I n s t r u m e n t a l g a u g e v o l u m e
r e s o l u t i o n c o u l d h a v e c o n t r i b u t e d t o this r e d u c t i o n .
O n r e m o v a l of t h e b o l t t o give the m i n i m u m l o a d
s i t u a t i o n , it w a s f o u n d t h a t t h e p e a k level m o v e d a w a y
from t h e c r a c k tip, with c o n s e q u e n c e s for h y d r o g e n o r
sulfur e m b r i t t l e m e n t .
2.4 Residual
Autofrettaged
Stress Distribution
Tubing
in
Cracked
Residual
Stresses:
Measurement
uncracked
cracked
Using Neutron
Diffraction
Q_
oSiC
alumina
<024>
alumina
<006>
(C)
Radial position ( m m )
Figure 5
Comparison of residual hoop stress along a radius in the
cracked and uncracked sides of an autofrettaged, fatigued
ring. The crack tip is estimated to be at R ^ 15 mm (after
Bourke et al. 1992)
surface is plastically d e f o r m e d by b o m b a r d m e n t with
fine shot. It is used t o p r o d u c e compressive stress a t
the surface layer of c o m p o n e n t s in o r d e r t o inhibit t h e
p r o p a g a t i o n of surface c r a c k s . T h e c o m p o n e n t s of
residual stress as a function of d e p t h b e n e a t h t h e
surface of a heavily p e e n e d block of nickel-based
superalloy h a v e been m e a s u r e d b y Ezeilo et al. (1992)
using a g a u g e v o l u m e of a p p r o x i m a t e d i m e n s i o n
0.5 m m p e r p e n d i c u l a r t o t h e surface. T h e results a r e
s h o w n in Fig. 6. T h e compressive surface stress
rapidly diminishes a n d a significant tensile region is
observed between d e p t h s of 0.6 m m a n d 2 m m . T h e
n a t u r e of this tensile region w a s first revealed b y such
n e u t r o n diffraction m e a s u r e m e n t s .
2.6 Residual Stress in Composite
Materials
T h e stress in each c o m p o n e n t of a c o m p o s i t e m a t e r i a l
c a n be m e a s u r e d separately from its distinct B r a g g
Figure 6
Residual stress components as a function of depth from
the surface of a shot-peened nickel superalloy block. The
and axes lie in the surface plane of the block (after
Ezeilo et al. 1992)
416
Figure 7
Measured (symbols) and predicted (solid line) residual
average hydrostatic strain as a function of temperature for
whiskers and matrix of a ceramic composite of SiC
whiskers in A1 20 3 (after Majumdar et al. 1991)
reflections. In m o s t studies t o d a t e it is the m e a n
microstress levels in t h e c o m p o n e n t s w h i c h h a v e been
m e a s u r e d , b u t t h e profile of stress as a function of
p o s i t i o n c a n also b e d e t e r m i n e d as in single-phase
m a t e r i a l s . A n e x a m p l e of t h e p o w e r of the t e c h n i q u e
is t h e m e a s u r e m e n t of t h e h y d r o s t a t i c strain as a
function of t e m p e r a t u r e for b o t h t h e SiC whisker a n d
t h e a l u m i n a m a t r i x of a c e r a m i c m a t r i x c o m p o s i t e of
1 5 w t % SiC in A 1 2 0 3 ( M a j u m d a r et al. 1991). T h e
results a r e s h o w n in F i g . 7. B o t h t h e relatively large
c o m p r e s s i v e stress in t h e whiskers a n d t h e smaller
tensile stress in t h e A 1 2 0 3 m a t r i x a r e relieved as t h e
c o m p o s i t e is h e a t e d t o w a r d s t h e fabrication t e m p e r a
t u r e . T h e e x t r a p o l a t e d z e r o strain p o i n t is 1400 C,
s o m e 300 C b e l o w t h e fabrication t e m p e r a t u r e , sug
gesting t h a t d u r i n g t h e initial t e m p e r a t u r e d r o p from
1700 C t o 1400 C t h e m a t e r i a l is relaxing by creep
a n d is n o t b u i l d i n g u p residual stress.
3. Future
Developments
N e u t r o n diffraction p r o v i d e s a u n i q u e , n o n d e s t r u c
tive, a n d a b s o l u t e m e t h o d of residual stress m e a s u r e
m e n t a t d e p t h s of u p t o a p p r o x i m a t e l y 2.5 c m in steel
a n d a p p r o x i m a t e l y 7 c m in a l u m i n u m . H o w e v e r , a
high-flux n e u t r o n s o u r c e m u s t b e used p r e c l u d i n g its
use for in situ m e a s u r e m e n t s o n p l a n t a n d s t r u c t u r e s .
It c a n b e used for p o r t a b l e s a m p l e s of less t h a n 1 m
typical size a n d for t h e v a l i d a t i o n a n d c a l i b r a t i o n of
o t h e r t e c h n i q u e s w h i c h c a n be used in t h e field b u t
w h i c h a r e usually limited in a p p l i c a t i o n . U n f o r t u n
ately, p o r t a b l e n e u t r o n sources of sufficient intensity
for general use in t h e field a r e unlikely t o b e c o m e
available in t h e foreseeable future.
T h e n e u t r o n m e t h o d is also b e c o m i n g increasingly
v a l u a b l e in t h e f u n d a m e n t a l m a t e r i a l s science field, in
t h e u n d e r s t a n d i n g of t h e stress d i s t r i b u t i o n in n e w
m a t e r i a l s t o be used b y engineers such as m e t a l m a t r i x
c o m p o s i t e s a n d in s h e d d i n g light o n t h e strain re-
Residual
cknowledgement
This w o r k w a s c o m p l e t e d while t h e a u t h o r w a s
e m p l o y e d by the U n i t e d K i n g d o m A t o m i c E n e r g y
A u t h o r i t y w h o r e t a i n possession of the c o p y r i g h t of
the article. P u b l i s h e d with p e r m i s s i o n .
See also: Residual Stresses: Nondestructive Evaluation;
Stress Distribution: Analysis Using Thermoelastic Effect
Nondestructive
Evaluation
Bibliography
Allen A J, Andreani C, Hutchings , Windsor C G 1981
Measurement of internal stress within bulk materials
using neutron diffraction. NDT Int. October 249-54.
Allen A J, Bourke M, David W I F, Dawes S, Hutchings
, Krawitz A D, Windsor C G 1989 Effects of elastic
anisotropy on the lattice strains in polycrystalline metals
and composites measured by neutron diffraction. In: Beck
G, Denis S, Simon A (eds) 1989 Int. Conf. Residual Stress
ICRS2. Elsevier, London, pp. 78-83.
Allen A J, Hutchings , Rainey V S 1988 Measurement
of through-thickness residual stress in T-butt weldments
of offshore steel by high resolution neutron diffraction.
In: Farley J M, Nicols R W (eds.) 1988 Non-Destructive
Testing. Pergamon, Oxford, pp. 1808-17
Allen A J, Hutchings , Windsor C G, Andreani C 1985
Neutron diffraction methods for the study of residual
stress fields. Adv. Phys. 34: 445-73
Bourke M A M , MacGillivray J, Webster G A, Webster J
1992 Residual stress distribution in cracked autofrettaged
tubing. In: Hutchings and Krawitz 1992, pp. 481-92
Ezeilo A N, Webster S, Webster G A, Webster J 1992
Development of the neutron diffraction technique for the
determination of near surface residual stress in critical gas
turbine components. In: Hutchings and Krawitz 1992, pp.
535-43
Hutchings , Hipplsey C, Rainey V 1990 Neutron
diffraction measurement of the stress field during fatigue
cycling of a cracked test specimen. Mater. Res. Soc.
Symp. Proc. 166: 317-21
Hutchings , Krawitz A D (eds.) 1992 Measurement of
Residual and Applied Stress Using Neutron Diffraction.
Kluwer, Dordrecht, The Netherlands
Kittel C 1986 Introduction to Solid State Physics, 6th edn.
Wiley, New York
Krawitz A D, Brune J E, Schmank J 1982 Measurement
of stress in the interior of solids with neutrons. In: Kula E,
Weiss V (eds.) 1982 Residual Stress and Stress Relaxation.
Plenum, New York, pp. 139-55
Leffers 1981 Microstructures and mechanisms of polycrystal deformation at low temperatures. In: Hansen N,
Horsewell A, Leffers T, Lilholt (eds.) 1981 Deformation
Stresses:
1. General
Considerations
417
Residual
Stresses:
Nondestructive
Evaluation
2. X-Ray
Diffraction
M o s t n o n d e s t r u c t i v e m e a s u r e m e n t s of residual stress
are m a d e by x-ray diffraction t e c h n i q u e s (see X-Ray
Powder Diffraction), w h e r e b y x-ray b e a m s a r e used t o
m e a s u r e selected c r y s t a l l o g r a p h i c lattice spacings in
the m a t e r i a l t h r o u g h B r a g g ' s law. It is a s s u m e d t h a t
t h e u n i t c h a n g e in lattice spacing is e q u a l t o t h e elastic
strain in t h e c o n t i n u u m a t t h e p o i n t of m e a s u r e m e n t
a n d in a direction p e r p e n d i c u l a r t o t h e lattice p l a n e s .
T h a t is, if d is t h e spacing between lattice p l a n e s
t h a t a r e o r i e n t e d p e r p e n d i c u l a r t o s o m e direction ,
a n d if t h e u n s t r a i n e d lattice spacing is d0, t h e n the
elastic strain in direction is
Figure 1
Rectangular coordinate system at the surface of a
material. Direction y is perpendicular to the page; plane
xy is coincident with the surface of the material; plane xz
is the diffraction plane; and direction is in the
diffraction plane, inclined to by angle
M o n o c h r o m a t i c r a y s , such as t h o s e used in c o n v e n
t i o n a l x-ray diffraction w o r k , p e n e t r a t e crystalline
m a t e r i a l s t o a d e p t h of only a few m i c r o m e t e r s , so t h e
m e t h o d applies only t o t h e n o n d e s t r u c t i v e m e a s u r e
m e n t of surface stresses. A t a free surface (Fig. 1) t h e
n o r m a l stress a n d t h e s h e a r stresses a n d xyz a r e
z e r o a n d h e n c e , b y H o o k e ' s law, t h e n o r m a l stress in
t h e surface in t h e direction is
YT~v^ ~
x
z)
( 2 )
- c o s
.
sin
a n d s u b s t i t u t i n g i n t o E q n . (2),
l + sin
d dn d dn d d
418
Residual
Since (J,
by
d0)/dz
<
Stresses:
Nondestructive
Table 1
Lattice planes and radiation sources used for residual stress
measurements
Lattice plane
w i t h o u t significant e r r o r a n d , therefore, E q n .
becomes
1 + sin
(3)
dz
Evaluation
Material
Ferritic iron
Austenitic steel
Aluminum
Copper
Magnesium
Nickel
(hkl)
spacings
211
310
651,732
220
420
222
420
511,333
400
420
105
313
420
117.0
90.6
36.4
127.3
80.5
116.9
90.6
77.9
90.4
80.8
97.6
80.8
78.8
X-ray source
3
target
filter
Cr
Co
Mo
Cr
Cu
Cr
Co
Cu
Co
Cu
Fe
Cu
Cu
C
Fe
Zr
V
Ni
V
Fe
Ni
Fe
Ni
Mn
Ni
Ni
a Nominal value in picometers; actual values depend on the alloy and the
strain level b To eliminate K e radiation
419
Residual
Stresses:
Nondestructive
Evaluation
Table 2
Young's moduli: comparison of lattice and bulk values
Material
Direction
Ferritic iron
<ioo>
<111>
Carbon steel
<211>
<220>
<310>
bulk
bulk
Aluminum
<100>
<111>
<420>
Copper
<400>
Nickel
<313>
<420>
bulk
bulk
bulk
Young's
3
modulus (GPa)
132
284
210
205
232
177
210
63
75
67
70
106
120
230
199
200
a Values shown for bulk material are nominal; actual values may vary
somewhat with alloy
A n o t h e r source of e r r o r , w h i c h is s o m e t i m e s signi
ficant, arises from u n c e r t a i n t i e s in t h e elastic c o n
stants. T h e values of a n d w h i c h s h o u l d b e used
with E q n . (4) a r e n o t t h e c o n v e n t i o n a l values for b u l k
polycrystalline m a t e r i a l s . R a t h e r , they s h o u l d be t h e
values t h a t c o r r e s p o n d t o t h e p a r t i c u l a r lattice direc
tion which is m e a s u r e d . (Crystals a r e elastically a n i s o
tropic a n d the b u l k values of t h e elastic c o n s t a n t s only
represent s o m e a v e r a g e of t h e elastic c o n s t a n t s for t h e
v a r i o u s crystalline o r i e n t a t i o n s . ) M e t h o d s for calcu
lating lattice elastic c o n s t a n t s h a v e been p r o p o s e d b u t
the m o s t reliable values a r e t h o s e d e v e l o p e d in calib
r a t i o n e x p e r i m e n t s in which c h a n g e s in lattice strain
are m e a s u r e d as a function of applied stress (Prevey
1977). F o r a l u m i n u m , t h e elastic c o n s t a n t s a r e n o t
particularly sensitive t o lattice direction, while for
steel t h e b u l k elastic c o n s t a n t s c a n b e used for the
<211> direction w i t h o u t excessive e r r o r . F o r o t h e r
directions a n d o t h e r m a t e r i a l s , significant differences
m a y exist b e t w e e n t h e lattice elastic c o n s t a n t s a n d t h e
bulk values ( T a b l e 2).
3.
^ r = \ + B a
(5)
w h e r e V is t h e u l t r a s o n i c w a v e speed in t h e m a t e r i a l ,
V0 is t h e speed in t h e unstressed state, is t h e stress
a n d is t h e c o n s t a n t of p r o p o r t i o n a l i t y , k n o w n as t h e
a c o u s t o e l a s t i c c o n s t a n t . is a function of V0 a n d t h e
second- a n d t h i r d - o r d e r elastic c o n s t a n t s of the
m a t e r i a l . Reliable values of acoustoelastic a n d thirdo r d e r elastic c o n s t a n t s a r e n o t generally available.
E q u a t i o n (5) is overly simplistic because it d o e s n o t
a c c o u n t for t h e fact t h a t V0 a n d b o t h d e p e n d u p o n
t h e m o d e of t h e u l t r a s o n i c w a v e a n d , f u r t h e r m o r e ,
d e p e n d s u p o n t h e relative directions of t h e u l t r a s o n i c
w a v e a n d t h e stresses. F o r a m o r e precise c h a r a c t e r i
z a t i o n , c o n s i d e r a n elastic b o d y w i t h principal stress
directions i, j a n d k. T h e n , for a l o n g i t u d i n a l w a v e
p r o p a g a t i n g in t h e / direction,
^ l + B f a
+ Bfa+Bfa
(6)
l
w h e r e , a n d ak a r e t h e principal stresses a n d B n
represents t h e effect of p r i n c i p a l stress o n Vr
F o r a s h e a r w a v e p r o p a g a t i n g in direction / a n d
p o l a r i z e d such t h a t particle m o t i o n is in direction j ,
^L=\
(7)
+ Bfaj+B*ak
(8)
a n d similarly,
l!L=l+B?ai
v
ik0
C o n s i d e r , n o w , a p l a t e u n d e r p l a n e stress c o n
d i t i o n s , such t h a t / is the thickness direction. T h e n , is
zero. If t h e p l a t e m a t e r i a l c a n be a s s u m e d t o b e
acoustoelastically isotropic, t h e n
Ultrasonics
A l t h o u g h t h e x-ray diffraction m e t h o d of m e a s u r i n g
residual stresses is extremely useful, it h a s t w o s h o r t
c o m i n g s : it c a n n o t be used for noncrystalline m a t e r
ials, such as plastics, a n d it c a n n o t m e a s u r e i n t e r n a l
residual stresses nondestructively. Several o t h e r
a p p r o a c h e s t o t h e n o n d e s t r u c t i v e e v a l u a t i o n of resi
d u a l stresses a r e u n d e r d e v e l o p m e n t a l t h o u g h n o n e of
t h e m c a n claim a level of reliability similar t o t h a t
which characterizes careful x-ray diffraction m e a s u r e
m e n t s . U l t r a s o n i c m e t h o d s for t h e m e a s u r e m e n t of
420
residual stresses a r e c o n s i d e r e d h e r e in s o m e w h a t
m o r e detail t h a n o t h e r a p p r o a c h e s because they a p
p e a r t o h a v e p o t e n t i a l for t r e m e n d o u s capability,
versatility a n d usefulness in t h e future.
T h e u l t r a s o n i c a p p r o a c h is b a s e d o n t h e e x p e r i m e n
tally confirmed o b s e r v a t i o n t h a t t h e speed of s o u n d in
a b o d y varies linearly w i t h stress. T h u s , in c o n c e p t u a l
terms,
B'j=B'k,
B<f=B%,
B'l=
Bf
and
Where
is t h e s h e a r w a v e velocity in t h e unstressed
state. ( T h e c o n d i t i o n s u n d e r w h i c h this a s s u m p t i o n is
justified a r e n o t fully u n d e r s t o o d . It is n o t o b v i o u s
t h a t elastic i s o t r o p y (i.e., a n d isotropic) c o n n o t e s
acoustoelastic isotropy.) U n d e r these c o n d i t i o n s ,
E q n s . ( 6 - 8 ) r e d u c e t o , respectively,
Residual
Table 3
3
Acoustoelastic constants for several materials
Material
Steels
AISI 1018
ASTM A516
0.0001
ASTM A533B
0.00007
17-4 PH (cond. A)
304 SS
Rail steel
0.00015
Aluminum alloys
2024-T351
0.00083
2024-T4
6061-T6
6061-T651
0.00056
7075-T651
0.0013
Copper
-0.003
B*{
-0.00083
0.0000
-0.00087
-0.00074
-0.00075
0.00002
-0.0029
-0.0029
-0.0023
0.00097
0.00091
+ ak)
ij
(9)
(10)
-JL=\+Bfa
j+B jak
y
(11)
s0
S o m e values of t h e a c o u s t o e l a s t i c c o n s t a n t s a r e
t a b u l a t e d in T a b l e 3. N o t e t h a t t h e values for a l u m i
n u m alloys a r e substantially larger t h a n t h o s e for
steels, which enables stresses in a l u m i n u m alloys t o be
d e t e r m i n e d with g r e a t e r precision t h a n stresses in
steels. N o t e , also, t h a t t h e n u m e r i c a l values a r e all
quite small, t h a t is, t h e c h a n g e s in u l t r a s o n i c velocity
d u e t o stress a r e q u i t e small. Specialized electronic
e q u i p m e n t is n e e d e d t o m e a s u r e these velocities a c c u r
ately. It is usually m o r e p r a c t i c a l t o m e a s u r e t h e
transit time of a n u l t r a s o n i c w a v e t h r o u g h a m a t e r i a l
t h a n m e a s u r e its velocity. T h u s , if t h e thickness of t h e
plate is h0 in t h e unstressed state a n d h in t h e
unstressed state,
-{i i)(j J
+Bi
i0
j^-l+Bfa+Bfa
Nondestructive
Evaluation
a Compiled and adapted from various sources. Most of these data have
not been independently verified and are presented here only to illustrate
comparative magnitudes. All values are in percent per MPa
-L=\+B'j{aj
v
Stresses:
(12)
(13)
ik
4. Barkhausen
Noise
Analysis
A n u m b e r of m a g n e t i c p r o p e r t i e s a r e sensitive t o
stress a n d c a n , in principle a t least, b e used t o p r o v i d e
n o n d e s t r u c t i v e e v a l u a t i o n s of residual stresses in fer
r o m a g n e t i c m a t e r i a l s . D e s p i t e a lack of a d e q u a t e
u n d e r s t a n d i n g of t h e u n d e r l y i n g p h e n o m e n a , B a r k
h a u s e n noise analysis h a s b e e n used t o estimate
residual stresses in several engineering a p p l i c a t i o n s .
If a n e l e c t r o m a g n e t is used t o excite a n a l t e r n a t i n g
m a g n e t i c field in a f e r r o m a g n e t i c m e m b e r , e a c h rever
sal of t h e field generates a b u r s t of B a r k h a u s e n noise.
T h e p e a k a m p l i t u d e of t h e b u r s t , as m e a s u r e d , for
e x a m p l e , with a n inductive coil n e a r t h e surface of t h e
m e m b e r , varies with t h e level of stress at t h e surface.
421
Residual
Stresses:
Nondestructive
Evaluation
T h e r e l a t i o n s h i p between t h e noise a m p l i t u d e a n d t h e
stress is n o n e l i n e a r , however, a n d a p p e a r s t o b e m o s t
useful for the e s t i m a t i o n of stress levels well below t h e
yield strength of t h e m a t e r i a l . A l s o , B a r k h a u s e n noise
is influenced by a variety of m a t e r i a l p a r a m e t e r s o t h e r
t h a n stress, such as c o m p o s i t i o n , t e x t u r e a n d w o r k
h a r d e n i n g . H e n c e , it is i m p e r a t i v e in e a c h a p p l i c a t i o n
t o use calibrated reference s a m p l e s with t h e s a m e
c o m p o s i t i o n a n d processing history as t h e m e m b e r
being analyzed.
T h e limitation of t h e m e t h o d t o t h e m e a s u r e m e n t of
near-surface stresses results from t h e fact t h a t t h e
i n d u c t i o n field from a B a r k h a u s e n j u m p is d a m p e d b y
e d d y c u r r e n t s . T h e r e is evidence t h a t stresses a t s o m e
w h a t greater d e p t h s c a n be p r o b e d if t h e B a r k h a u s e n
j u m p s a r e sensed acoustically r a t h e r t h a n inductively
( B u r k h a r d t et al. 1982).
T h e chief a d v a n t a g e s of t h e B a r k h a u s e n noise
a p p r o a c h to residual stress m e a s u r e m e n t a r e t h a t it is
rapid a n d the e q u i p m e n t n e e d e d t o m a k e t h e m e a s u r e
m e n t c a n be conveniently p o r t a b l e .
5. Other
Methods
422
of d e v e l o p m e n t i n t o a field m e t h o d . T h i s m e t h o d
e m p l o y s a s o u r c e of w h i t e r a d i a t i o n , such as is used in
radiographic applications. In contrast to conven
tional x-ray diffraction w h e r e i n t h e wavelength is
preselected a n d t h e diffraction angle is m e a s u r e d , t h e
high-energy x-ray t e c h n i q u e e m p l o y s energy disper
sive s p e c t r o s c o p y t o m e a s u r e t h e w a v e l e n g t h s which
diffract a t preselected diffraction angles (Bechtoldt et
al. 1982).
See also: Residual Stresses: Measurement Using Neutron
Diffraction; Stress Distribution: Analysis Using Thermoelastic Effect
Bibliography
Bechtoldt C J, Placious R C, Boettinger W J, Kuriyama
1982 X-ray residual stress mapping in industrial materials
by energy dispersive diffractometry. Adv. X-Ray Anal. 25:
329-38
Blessing G V, Hsu , Proctor 1984 Ultrasonic-shearwave measurement of known residual stress in aluminum.
Exp. Mech. 24: 218-22
Burkhardt G L, Beissner R E, Matzkanin G A, King J D
1982 Acoustic methods for obtaining Barkhausen noise
stress measurements. Mater. Eval. 40: 669-75
Heyman J S 1977 A CW ultrasonic bolt-strain monitor.
Exp. Mech. 17: 183-7
Hildebrand , Harrington 1981 Mapping of materials
stress with ultrasonic tomography. Mater. Eval. 39: 38390
Hilley , Larson J A, Jatczak C F, Ricklefs R (eds.)
1971 Residual Stress Measurement by X-Ray Diffraction,
2nd edn. Society of Automotive Engineers, New York
Hsu 1974 Acoustical birefringence and the use of
ultrasonic waves for experimental stress analysis. Exp.
Mech. 14: 169-76
Husson D, Bennett S D, Kino G S 1985 Measurement of
stress with surface waves. Mater. Eval. 43: 92-100
James R, Buck 1980 Quantitative nondestructive
measurements of residual stresses. CRC Crit. Rev. Solid
State Mater. Sci. 9: 61-105
James R, Cohen J 1980 The measurement of residual
stresses by x-ray diffraction techniques. In: Herman
(ed.) 1980 Experimental Methods, Treatise on Materials
Science and Technology, Vol. 19, pt. A. Academic Press,
New York, pp. 1-62
Kino G S, Barnett D M, Grayeli N, Herrmann G, Hunter J
B, Ilic D B, Johnson G C, King R B, Scott , Shyne J
C, Steele C R 1980 Acoustic measurements of stress fields
and microstructure. / . Nondestr. Eval. 1: 67-77
Prask J, Choi C S 1984 N D E of residual stress in uranium
by means of neutron diffraction. J. Nucl. Mater. 126: 124
31
Prevey S 1977 A method of determining the elastic
properties of alloys in selected crystallographic directions
for x-ray diffraction residual stress measurement. Adv. XRay Anal. 20: 345-54
Vande Walle L J (ed.) 1981 Residual Stress for Designers and
Metallurgists. ASM, Materials Park, OH
L. M o r d f i n
[ N a t i o n a l B u r e a u of S t a n d a r d s ,
Washington, D C , USA]
s
Scanning Electron Microscopy
I. Electron-Specimen
(a)
(b)
(c)
Elastically scattered e l e c t r o n s t h e s e h a v e a n
energy loss, from a solid target, of typically less
t h a n ~ 1 eV. In s o m e cases, electrons with c h a r
acteristic energy losses c a n also be detected.
Low-loss electrons ( L L E ) t h e s e a r e b a c k s c a t
tered electrons t h a t h a v e lost less t h a n ~ 1 % of
the p r i m a r y energy in t h e specimen. T h e y c a n
either be selected by a n energy filter, o r be
collected t o g e t h e r with the o t h e r b a c k s c a t t e r e d
electrons by a solid-state o r scintillator BSE
detector. Low-loss-electron images are o b t a i n e d
from a thin surface layer a n d c a n s h o w s t r o n g
t o p o g r a p h i c a n d electron c h a n n e l l i n g c o n t r a s t s .
Low-loss-electron i m a g e s a r e similar in s o m e
respects t o t h o s e o b t a i n e d in the t r a n s m i s s i o n
electron m i c r o s c o p e w h e n o p e r a t e d with a solid
specimen in reflection.
C h a r a c t e r i s t i c rays a n d the c o n t i n u u m x-ray
s p e c t r u m (or b r e m s s t r a h l u n g ) t h e s e c a n also be
p r o d u c e d ; they are described elsewhere (see Elec
tron Microprobe
Analysis).
A u g e r e l e c t r o n s t h e s e leave the specimen with
a n energy d i s t r i b u t i o n t h a t is similar ( b u t n o t
identical) t o t h a t of the characteristic rays.
M a t e r i a l s analysis using A u g e r electrons requires
a n u l t r a h i g h v a c u u m a n d is carried o u t via the
Interactions
1 2
(d)
(Camera)
Scanning
generator
Tl
Display / \Display i
tube / \ tube
I /
\ 2
Magnification X and Y\
control
Video
amplifier
(e)
Z7777
Specimen
Figure 1
(f)
423
Scanning
Electron
Microscopy
(a)
(b)
Figure 2
TmSe and other phases of the TmxSr,_JSe system: (a) secondary-electron image showing topographic contrast;
(b) backscattered-electron image also showing compositional contrast (normal incidence; E0 = 20 keV; 1=2*
10" )
(Holtzberg F, Schad R G, unpublished)
s c a n n i n g A u g e r m i c r o p r o b e (see Auger
Spectroscopy).
(g)
Electron
C a t h o d o l u m i n e s c e n c e b e a m - i n d u c e d light sig
nals c a n also give a n i m a g e .
(b)
S o u n d w a v e s t h e s e c a n be excited by a pulsed
electron b e a m b e c a u s e of t h e r m a l e x p a n s i o n a n d
c o n t r a c t i o n of t h e i r r a d i a t e d z o n e . T h e y c a n be
detected with a m i c r o p h o n e .
424
E l e c t r o n - h o l e p a i r s t h e s e c a n be excited in
either s e m i c o n d u c t i n g o r insulating specimens
t h r o u g h o u t t h e v o l u m e t h a t is i r r a d i a t e d b y the
incident electron b e a m . ( W i t h silicon it requires
3.64 eV p r i m a r y energy for e a c h i n d u c e d elec
t r o n - h o l e pair.) F o r a s e m i c o n d u c t o r , these c a n
be collected by m e a n s of a p-n j u n c t i o n o r a
S c h o t t k y - b a r r i e r j u n c t i o n , o r in a biased region
of m a t e r i a l . I n d u c e d c o n d u c t i v i t y c a n also be
o b t a i n e d t h r o u g h insulating t h i n films. T h e t e r m
i n d u c e d signal implies t h e collection of e l e c t r o n hole p a i r s , a n d this c a n therefore be m a n y times
larger t h a n t h e i n c i d e n t - b e a m c u r r e n t . ( T h e spe
cimen c u r r e n t is o b t a i n e d b y c o n n e c t i n g only a
single wire t o t h e s a m p l e a n d d o e s n o t involve
t h e c r e a t i o n of e l e c t r o n - h o l e p a i r s in t h e s a m
ple.) T h e i n d u c e d signal c a n be displayed t o give
an electron-beam-induced conductivity (EBIC)
i m a g e , which c a n s h o w t h e p o s i t i o n s of p-n
j u n c t i o n s (even w h e n covered with a thin m e t a l
layer) a n d crystal defects in a solid specimen.
2. Image
Contrasts
2.1 Topographic
Contrast
T h e ability of t h e s e c o n d a r y - e l e c t r o n i m a g e t o s h o w
the surface t o p o g r a p h y of a r o u g h specimen is, of
c o u r s e , o n e of t h e m o s t striking features of t h e
m e t h o d (Figs. 2, 3, 4). T o p o g r a p h i c c o n t r a s t t h e n
arises from v a r i a t i o n s in t h e angle of p r i m a r y - e l e c t r o n
incidence, from p o i n t - t o - p o i n t v a r i a t i o n s in t h e ef
ficiency with w h i c h s e c o n d a r y electrons a r e collected
a n d from p e n e t r a t i o n effects a t s h a r p edges.
F o r a s a m p l e t h a t h a s a nearly flat surface, it m a y
be possible t o see t o p o g r a p h i c c o n t r a s t s m o r e clearly
in t h e b a c k s c a t t e r e d - e l e c t r o n i m a g e . I n this i m a g e ,
t o p o g r a p h i c c o n t r a s t c a n be e n h a n c e d by p o s i t i o n i n g
t h e d e t e c t o r with a low takeoff angle relative t o the
surface p l a n e . If t w o solid-state ( s e m i c o n d u c t o r
d i o d e ) b a c k s c a t t e r e d - e l e c t r o n d e t e c t o r s a r e used
a b o v e t h e specimen a n d o n t h e o p p o s i t e sides of the
b e a m , t h e n c o n t r a s t c a n be o b t a i n e d by displaying
t h e s u m signal, while t o p o g r a p h i c c o n t r a s t c a n be
o b t a i n e d b y displaying t h e difference. T o p o g r a p h i c
Scanning
Electron
Microscopy
(a)
Figure 3
Application of SEM to silicon integrated-circuit
manufacture: the shell of S i 0 2 that remains when the
underlying polycrystalline silicon conducting line is
dissolved (Hawks S W, unpublished)
(b)
c o n t r a s t from a low-density s a m p l e c a n be i m p r o v e d
by c o a t i n g it with a t h i n layer of a h e a v y m e t a l .
2.2 Contrast
c o n t r a s t ( c o m p o s i t i o n a l c o n t r a s t ) w a s first utilized
o n a w i d e s p r e a d basis as a n extension t o t h e electron
m i c r o p r o b e t e c h n i q u e (see Electron
Microprobe
Analysis). H e r e , t h e s a m p l e is polished a n d m o u n t e d
p e r p e n d i c u l a r t o t h e b e a m so as t o facilitate t h e
calculation of t h e x-ray a b s o r p t i o n a n d s e c o n d a r y xray
fluorescence
corrections. The backscatteredelectron c u r r e n t is t h e n a m o n o t o n i c a l l y increasing
function of t h e a v e r a g e a t o m i c n u m b e r ( Z ) of t h e
s a m p l e , so t h a t t h e t e r m c o n t r a s t is a p p r o p r i a t e .
T h e d e p t h from w h i c h b a c k s c a t t e r e d electrons escape
into a d e t e c t o r with a high takeoff angle is a b o u t half
of t h e electron p e n e t r a t i o n d e p t h . C h e m i c a l analysis is
possible if t h e specimen is a k n o w n b i n a r y system
such as a diffusion c o u p l e .
If the specimen is tilted a t a n angle, t h e n c o n t r a s t
c a n still be o b t a i n e d in t h e b a c k s c a t t e r e d - e l e c t r o n
i m a g e if t h e collector is in a suitable p o s i t i o n relative
to t h e s a m p l e surface. T h e m o n o t o n i c d e p e n d e n c e of
t h e detected b a c k s c a t t e r e d - e l e c t r o n signal o n t h e
average of t h e specimen m a y t h e n n o longer h o l d ,
a n d t h e d e t e c t o r a n d s a m p l e p o s i t i o n s m a y need t o be
adjusted t o give a g o o d i m a g e .
2.3 Electron-Channelling-Pattern
Contrast
E l e c t r o n - c h a n n e l l i n g - p a t t e r n ( E C P ) c o n t r a s t arises if
the s a m p l e is a single crystal either over a large region
using t h e u s u a l b e a m - s c a n n i n g m o d e (large a r e a E C P )
o r over a smaller region b y r o c k i n g t h e b e a m a b o u t a
p o i n t (selected a r e a E C P ) . Briefly, t h e p r o b a b i l i t y of a
b a c k s c a t t e r i n g event will d e p e n d o n t h e angle b e t w e e n
(c)
Figure 4
Thermal cycling of aluminum film (thickness 1.3 ) on
an oxidized silicon substrate: (a) 250 C, (b) 400 C.
(c) after cooling to 250 C (after Lahiri and Wells 1969
Appl. Phys. Lett. 15: 234-5. American Institute of
Physics, New York. Reproduced with permission)
425
Scanning
Electron
Microscopy
(a)
(b)
Figure 5
Thin-film magnetic recording head: (a) BSE image showing the surface topography (normal incidence; EQ = 45 keV);
(b) lock-in processed BSE image showing the magnetic domain walls (20 kHz excitation frequency)
426
d o m a i n b o u n d a r i e s a n d is d e s i g n a t e d type-1 m a g n e t i c
contrast.
T y p e - 2 m a g n e t i c c o n t r a s t s h o w s u p in t h e b a c k scattered electron i m a g e of m a t e r i a l s such as s i l i c o n i r o n a n d nickel, w h i c h h a v e cubic s y m m e t r y a n d a
sufficiently s t r o n g i n t e r n a l field. D e p e n d i n g o n t h e
e x p e r i m e n t a l a r r a n g e m e n t , this c a n s h o w u p either as
d o m a i n c o n t r a s t (in w h i c h t h e a l t e r n a t i n g d o m a i n s
a p p e a r b r i g h t a n d d a r k ) , o r as wall c o n t r a s t (in which
t h e d o m a i n s a p p e a r t o b e equally b r i g h t b u t t h e
d o m a i n walls a p p e a r as b r i g h t o r d a r k n a r r o w b a n d s ) .
T y p e - 2 m a g n e t i c c o n t r a s t s e l d o m exceeds 1 % of t h e
collected c u r r e n t a n d in m a n y cases m a y be c o n s i d e r a
bly smaller even t h a n this. T h e r e f o r e , it is generally
necessary t o p r e p a r e t h e s a m p l e with a flat, s m o o t h
surface a n d t o orient this in the S E M so as t o
minimize competing image contrasts.
W i t h a r o u g h s a m p l e , it m a y b e a d v a n t a g e o u s t o
s t u d y m a g n e t i c c o n t r a s t b y t h e lock-in e n h a n c e m e n t
t e c h n i q u e . I n general, with t h e lock-in m e t h o d , t h e
idea is t o i n t r o d u c e a m o d u l a t i n g signal i n t o t h e
i m a g e - f o r m i n g p r o c e s s in s o m e w a y a n d t h e n t o detect
t h e resulting v a r i a t i o n s in t h e collected c u r r e n t with a
phase-sensitive d e t e c t o r . T h i s m e t h o d h a s also been
used extensively for r e c o r d i n g A u g e r electron spectra,
by a p p l y i n g t h e reference signal t o t h e energy-filtering
d e t e c t o r . It h a s also been applied t o t h e r m a l - w a v e
m i c r o s c o p y . T o a p p l y this m e t h o d t o m a g n e t i c c o n
trast, t h e excitation signal is applied t o m o v e t h e
d o m a i n walls in t h e specimen, either by a p p l y i n g a n
external field t o a thin-film s a m p l e o r by a p p l y i n g the
c u r r e n t t o t h e driving coil o f a thin-film m a g n e t i c
r e c o r d i n g h e a d (Fig. 5).
Scanning
Tunnelling
Microscopy
and
Spectroscopy
oooo
. oooo
ooboooooo
ooooooooo
s
Sample
Figure 1
Schematic of tunnelling between the tip and sample in the
STM configuration: in constant current imaging the
sample-tip separation is held constant as the tip is
scanned over the sample surface; a series of scans
produces a real space image of constant charge density
/.
Fundamental
Principles
of
Imaging
+ eV)]\Ms,\ d{E,
- Et) (1)
w h e r e M s t is t h e tunnelling m a t r i x , f(E) t h e F e r m i
function, e t h e c h a r g e of a n electron, h = h/2n w h e r e h
is P l a n c k ' s c o n s t a n t , a n d t h e subscripts s a n d t refer t o
the electrodes (later specified a s s a m p l e a n d tip,
427
Scanning
Tunnelling
Microscopy
and
Spectroscopy
respectively). T u n n e l l i n g , as it o c c u r s in the S T M
configuration, is described in Fig. 1. O n e electrode is a
metallic p o i n t p r o b e (the tip), the o t h e r a p l a n a r
s e m i c o n d u c t o r o r m e t a l (the sample). Tersoff a n d
H a m a n n (1985) h a v e t a k e n the g e o m e t r y of the S T M
a n d the electronic s t r u c t u r e of t h e tip i n t o c o n s i d e r a
tion a n d e v a l u a t e d the tunnelling m a t r i x in E q n . (1) t o
p r o d u c e a c u r r e n t e q u a t i o n specific t o the S T M .
A s s u m i n g a spherical w a v e function for the tip struc
t u r e a n d using r e a s o n a b l e values for the m a t e r i a l s
p a r a m e t e r s p e r t a i n i n g t o the tip, they o b t a i n for a
c o n s t a n t applied bias:
L ^ y ^ D ^ ^ l ^ d i E . - E )
(2)
7 = C Z ) s e x p ( - 1.025 > )
(3)
s a m p l e surface. T h e r e are a d v a n t a g e s i n h e r e n t in b o t h
m o d e s of o p e r a t i o n ; the former p r o d u c e s c o n t r a s t
directly related t o electron c h a r g e density profiles,
while the latter p r o v i d e s for faster scan rates n o t being
limited by t h e r e s p o n s e time of the vertical driver.
I m a g e d a t a will be displayed differently, d e p e n d i n g o n
the i n f o r m a t i o n required. A s a n e x a m p l e , Fig. 2
illustrates the line scan, p l a n view a n d threed i m e n s i o n a l r e n d e r i n g of a n a t o m i c resolution c o n
s t a n t c u r r e n t i m a g e of the basal p l a n e of highly
o r i e n t e d pyrolytic g r a p h i t e . A t o m i c r e s o l u t i o n images
are possible only u n d e r o p t i m i z e d s a m p l e a n d tip
conditions. Larger sample-tip separations and blunt
tips h a v e t h e effect of s m e a r i n g the localized s t r u c t u r e
a n d p r o d u c e t o p o g r a p h i c images w i t h s o m e w h a t
lower resolution.
2. Tunnelling
Spectroscopy
T u n n e l l i n g s p e c t r o s c o p y (TS) p e r f o r m e d in the S T M
p r o v i d e s i n f o r m a t i o n a b o u t t h e electronic s t r u c t u r e of
the s a m p l e by p r o b i n g the s a m p l e density of states as
a function of energy. T h e c o n c e p t is similar t o t r a d i
tional s a n d w i c h j u n c t i o n spectroscopy (inelastic elec
t r o n tunnelling spectroscopy, H a n s m a (1982)), the
p r i m a r y differences being t h a t a v a c u u m g a p exists
b e t w e e n the t w o electrodes r a t h e r t h a n a n i n s u l a t o r
a n d only elastic processes h a v e been m o n i t o r e d t o
d a t e . T h e r e a r e also t w o m e t h o d s of p e r f o r m i n g T S .
T h e first, referred t o as p o i n t spectroscopy, involves
m o v i n g the tip t o a feature of interest, disengaging the
feedback m e c h a n i s m , m o d u l a t i n g the tip bias a n d
r e c o r d i n g the resulting v a r i a t i o n in c u r r e n t . T h e idea
lized b a n d s t r u c t u r e in Fig. 3 schematically illustrates
c u r r e n t flow in this situation. W h e n a bias is applied
b e t w e e n the s a m p l e a n d tip, the F e r m i levels of the
t w o m a t e r i a l s a r e displaced with respect t o each o t h e r
allowing electrons within the energy w i n d o w t o tra
verse the v a c u u m g a p . A s the bias is r a m p e d , either
positively o r negatively, the c u r r e n t varies in response
t o the c h a n g i n g electron density in the energy win
d o w . R a m p i n g in b o t h directions p r o b e s b o t h the
occupied a n d u n o c c u p i e d energy states, with the
m a g n i t u d e of the c u r r e n t at a specific voltage directly
related t o the density of states of the sample a t t h a t
energy. Since the c o n s t a n t C in E q n . (3) is a linear
function of voltage, s p e c t r o s c o p y d a t a c a n be related
t o the s a m p l e electronic s t r u c t u r e Ds in the f o r m of
conductance:
I/V=
/2
C*DS e x p ( - 1.025 )
(4)
Scanning
Tunnelling
Microscopy
- T i p vacuum
and
Spectroscopy
sample
Surface
BuLk
(a)
+ Tip vacuum
sample
Surface
Bulk
(b)
Figure 3
Idealized representation of the electronic structure of the
sample and tip: Et is the Fermi energy, Ey the valence
band edge, and Ec the conduction band edge; the tip is
modelled as a metal left, the sample as a semiconductor
right; states on the sample surface may be due to surface
reactions or extensions of midgap bulk states; a bias AV
between the sample and tip displaces the Fermi levels with
respect to each other, allowing electrons within the energy
window to traverse the vacuum gap
Figure 2
Comparison of image display modes showing (a) a line
scan, (b) plan view and (c) a three-dimensional rendering
of a constant current image of highly oriented pyrolytic
graphite acquired in air
Scanning
Tunnelling
Microscopy
and
Spectroscopy
3. Microscope
Design
Considerations
T h e h e a r t of a s c a n n i n g tunnelling m i c r o s c o p e c o n
sists of a s c a n n e r a n d a s a m p l e - t i p a p p r o a c h m e c h a n
ism. S c a n n i n g tunnelling m i c r o s c o p e s a r e divided i n t o
t w o classes b a s e d o n t h e configuration of t h e m e c h a n
ism t h a t c o n t r o l s t h e tip. T h e s c a n n e r s a r e m a d e of
piezoelectric elements w h i c h e x p a n d o n a p p l i c a t i o n of
a n electric field, h e n c e the tip c a n be s c a n n e d by
r a m p i n g t h e voltage applied t o t h e different piezoelec
tric elements. F i g u r e 6 schematically illustrates a
s c a n n e r m a d e of three o r t h o g o n a l b a r s a n d o n e m a d e
of a cylinder. E a c h t y p e of s c a n n e r h a s a d v a n t a g e s .
T h e o r t h o g o n a l a r r a n g e m e n t is m o r e linear by virtue
of g e o m e t r y a n d , c o n s e q u e n t l y , requires n o c o m p e n
s a t i o n t o e n s u r e a s q u a r e scan a r e a . T h e cylindrical
s c a n n e r s a r e m o r e stable with respect t o m e c h a n i c a l
v i b r a t i o n s , as indicated b y t h e m e c h a n i c a l r e s o n a n c e
Energy
(eV)
Figure 4
Comparison of density of states by TS point spectroscopy
with photoemission and inverse photoemission spectra;
agreement between various methods verifies the accuracy
of TS data (redrawn after Tromp et al. 1985)
430
Figure 5
Schematic representation of CITS images that would be
obtained at (a) + 0.5 V and (b) - 1.6 V applied bias on
the silicon ( 1 1 1 ) 7 x 7 surface: the unit cell of the
reconstruction is outlined in white (note that the bonding
states occupied by electrons (a) and those not occupied
(b) are in different positions within the unit cell)
Scanning
Tunnelling
Microscopy
and
Spectroscopy
v i b r a t i o n . T u n n e l l i n g c u r r e n t s a r e of t h e o r d e r of 0 . 1 10 A a n d t h e s a m p l e - t i p j u n c t i o n acts like a n
a n t e n n a t o a m b i e n t electric fields; therefore, t h e
m i c r o s c o p e m u s t be effectively shielded a n d electri
cally isolated from external circuits. A t o m i c resolu
tion requires stability of 0.01 n m with respect t o
m e c h a n i c a l v i b r a t i o n s . M e c h a n i c a l noise a t t e n u a t i o n
is achieved b y c o m b i n i n g a series of d a m p i n g stra
tegies. A t a b l e floating o n p n e u m a t i c (air) legs o r
s u s p e n d e d b y l o n g springs will d a m p low-frequency
v i b r a t i o n s ( 0 . 1 - 1 0 0 H z ) . A l t e r n a t i n g stacks of m e t a l
a n d r u b b e r , o r a n y t w o m a t e r i a l s w i t h widely differing
elastic c o n s t a n t s , d a m p m i d r a n g e frequencies ( 5 0 300 H z ) . H i g h e r - f r e q u e n c y v i b r a t i o n s c a n b e elimi
n a t e d b y electrical filtering.
Figure 6
Schematic illustration of orthogonal and cylindrical
arrangements for the piezoelectric elements which move
the STM tip: x, y and refer to the direction of motion
when the controlling voltage is applied as shown
of 12-20 H z c o m p a r e d w i t h 2 - 7 H z for t h e o r t h o g o
nal scanner, b u t a r e intrinsically n o n l i n e a r a n d re
q u i r e h a r d w a r e o r software c o m p e n s a t i o n d u r i n g
scanning. S c a n n e r s a r e c o n t r o l l e d t h r o u g h simple
voltage amplifiers a n d a s t a n d a r d feedback circuit b y
a P C size c o m p u t e r . T h e s e c o n d i m p o r t a n t aspect of
the m i c r o s c o p e design is t h e m e c h a n i s m for b r i n g i n g
t h e s a m p l e a n d tip t o g e t h e r . A s t u n n e l l i n g o c c u r s only
in close p r o x i m i t y t o t h e surface (within 3 n m ) t h e
a p p r o a c h system m u s t b e c a p a b l e of precise r e p r o d u c
ible i n c r e m e n t a l steps of less t h a n 3 n m in o r d e r t o
avoid t i p - t o - s a m p l e c o n t a c t . O n e m e t h o d of s a m p l e tip a p p r o a c h is b a s e d o n differential springs o r levers,
w h e r e t h e sensitivity (i.e., t h e smallest step) is deter
m i n e d b y t h e r a t i o of s p r i n g c o n s t a n t s , o r lengths of
levers, respectively. Electrostrictive w a l k e r s , referred
to as " l o u s e s , " a r e also used. Recently, s t e p p e r m o t o r s
h a v e been d e v e l o p e d with e n o u g h precision t o p r o v i d e
c o n t r o l l e d s a m p l e - t i p a p p r o a c h ; h o w e v e r , these
usually h a v e t h e d i s a d v a n t a g e of n o t being c o m
patible with u l t r a h i g h - v a c u u m ( U H V ) systems. A
general design c o n s i d e r a t i o n is w h e t h e r t h e m i c r o
scope will be c o m p a t i b l e with U H V systems. S u c h
systems p r o v i d e a n e n v i r o n m e n t in w h i c h t o c a r r y o u t
c o n t r o l l e d c h e m i s t r y o n a t o m i c a l l y clean s a m p l e s .
U n d e r these c i r c u m s t a n c e s , i m a g e s a n d T S c a n often
be directly i n t e r p r e t e d . C o m p a t i b i l i t y with U H V im
poses restrictions o n m a t e r i a l choices for s o m e of t h e
components. Commercial microscopes are currently
available for use in a m b i e n t a n d in U H V .
The primary obstacle to attaining atomic resolution
is t h a t i m p o s e d b y electrical noise a n d m e c h a n i c a l
4. Sample
and Tip
Preparation
Scanning
Tunnelling
Microscopy
and
Spectroscopy
F o r use in U H V a n d t o o p t i m i z e r e s o l u t i o n , a t m o s
pheric c o n t a m i n a t e s a r e r e m o v e d from the tip by:
(a)
(b)
(c)
5. Applications
in Materials
Science
Figure 7
Constant current image of reconstructed silicon (001)
surface with several defects and spatially resolved I-V
spectra showing the variation in the surface bandgap with
lateral position (courtesy of Hamers 1989)
faces, v a c a n c y defects a n d d o m a i n b o u n d a r i e s a r e
invariably o b s e r v e d . T h e use of a t o m i c r e s o l u t i o n T S
t o p r o b e t h e electronic s t r u c t u r e of these defects
directly is illustrated in Fig. 7 ( H a m e r s 1989). I-V
curves a c q u i r e d a t different lateral p o s i t i o n s n e a r a
v a c a n c y type defect a r e s h o w n with the c o n s t a n t
c u r r e n t i m a g e of t h e surface (acquired a t - 1.5 eV).
A w a y from t h e defect (Fig. 7) t h e I-V curves indicate
t h e presence of a surface b a n d g a p b y t h e s h a r p
turn-on
of
tunnelling
current
n e a r - 0.45 eV
a n d + 0.25 eV. N e a r t h e defect t h e s h a r p edges d i s a p
p e a r a n d directly over the defect (Fig. 7) t h e t u n n e l
ling c u r v e exhibits a n e x p o n e n t i a l increase in c u r r e n t
b o t h a b o v e a n d below t h e F e r m i level. T h i s b e h a v i o r
d e m o n s t r a t e s t h a t t h e defect causes a v a r i a t i o n in t h e
local density of states; t h a t is, a h i g h density of states
exists a t t h e F e r m i level d u e t o the presence of a
v a c a n c y . T h e spatially d e p e n d e n t m e a s u r e m e n t s also
p r o v i d e a direct m e a s u r e of t h e lateral extent of t h e
w a v e f u n c t i o n s associated with defects a n d impurities,
d e m o n s t r a t i n g t h a t t h e influence of t h e defect e x t e n d s
over 1.5 n m from its c o r e . T h i s local electronic struc
t u r e is directly related t o chemical reactivity. T h e s e
v a c a n c y sites a r e , therefore, expected t o b e m o r e
c o n d u c t i v e , o r less c o n d u c i v e , t o i n t e r a c t i o n w i t h
a t o m s in t h e vicinity of t h e surface t h a n t h e defect-free
surface. Several studies a l o n g this line h a v e investi
g a t e d site-specific c h e m i s t r y o n s e m i c o n d u c t o r sur
faces.
Scanning
Figure 8
Constant current image of 25 nm square area of SiC
observed in moderate vacuum (10" 7 torr): facets resulting
from the crystal growth mechanism are identified
Tunnelling
Microscopy
and
Spectroscopy
5.4 Conductive
Polymers
D u r i n g t h e 1980s, a n e w class of p o l y m e r i c m a t e r i a l s
h a s been d e v e l o p e d h a v i n g electrical conductivities
c o m p a r a b l e t o t h a t of c o p p e r . In the polyaniline
family of p o l y m e r s , t h e d o p i n g m e c h a n i s m is such
t h a t b o t h t h e n u m b e r of p r o t o n s a n d t h e electrons c a n
be varied i n d e p e n d e n t l y b y c o n t r o l l e d chemical reac-
433
Scanning
Tunnelling
Microscopy
and
Spectroscopy
Tunnelling b i a s tl /
-1.4
1.4 -I . 4
-1.4
1.4 - 1 . 4
Energy
(V)
1.4 -I . 4
1.4
1.4 - 1 . 4
1.4
(eV)
Figure 9
Tunnelling spectra from the SiC surface shown in Fig. 8: (a)-(c) show the current-voltage data as they are acquired;
spectra are often displayed as conductance (d)-(f) or normalized conductance (g)(i); spectra were acquired at three
sample-tip separations (increasing from left to right) and the positions of the peaks marked by the arrows are consistent
at all separations
434
A n g e l o p o u l o s 1989). T h e t o p o g r a p h i c s t r u c t u r e is
related t o p r o c e s s i n g c o n d i t i o n s a n d , d u e t o its scale,
c o u l d n o t be detected in extensive s c a n n i n g electron
m i c r o s c o p y ( S E M ) analysis. T h e m a t e r i a l is a m o r
p h o u s ; therefore, i n f o r m a t i o n a b o u t a t o m i c b o n d i n g
is n o t expected from t h e S T M i m a g e s . T h e different
types of electronic s t r u c t u r e f o u n d in fully a n d p a r
tially d o p e d e m e r a l d i n e h y d r o c h l o r i d e a r e also c o m
p a r e d in F i g . 13. T h e first t y p e of b e h a v i o r a p p e a r s
s e m i c o n d u c t i n g ; t h e p o s i t i o n of t h e valence (v) a n d
c o n d u c t i o n (c) b a n d edges is indicated b y a decrease
in c o n d u c t a n c e n e a r - 2.1 eV a n d a n increase in c o n
d u c t a n c e n e a r 2.2 eV, respectively. T h e b a n d g a p
d e t e r m i n e d b y T S (4.3 eV) agrees r e a s o n a b l y with t h a t
d e t e r m i n e d b y optical m e t h o d s (4.1 eV). I n t h e s e c o n d
t y p e of region, t h e b a n d edges c a n n o t be identified
Scanning
Tunnelling
Microscopy
and
Spectroscopy
140.0
4.0
-4.0
-3.0
-2.0
-1.0
1.0
2.0
3.0
4.0
T u n n e l l i n g bias (V)
(a)
Figure 10
A comparison of the resolution of topographic imaging of ZnO in (a) air and (b) UHV with the electronic structure
determined by tunnelling spectroscopy; Schottky barrier formation occurs in air as indicated by the variation in the
position of the valence band edge at three different sample-tip separations and the rectified I-V characteristics shown in
the inset; flat band conditions result in UHV, indicated by the observation of both the valence and conduction band edges
N o n d e s t r u c t i v e e v a l u a t i o n of t h e smallest structures
c u r r e n t l y m a n u f a c t u r e d is n o t possible with o t h e r
t e c h n i q u e s . A n e x a m p l e is illustrated in the S T M
i m a g e s of Fig. 14 w h i c h s h o w a diffraction g r a t i n g a n d
a n i n t e g r a t e d circuit. T h e diffraction g r a t i n g acts as a
p r i s m t o disperse light a n d is a n i n t e r n a l c o m p o n e n t
of infrared s p e c t r o m e t e r s . S E M lacks t h e vertical
r e s o l u t i o n a n d i n t e r f e r o m e t r y lacks t h e lateral resolu
tion t o c h a r a c t e r i z e t h e t o p o g r a p h y of the diffraction
g r a t i n g ; h o w e v e r , F i g . 14a illustrates h o w easily the
surface s t r u c t u r e of the t o p a n d sides of this 1
g r a t i n g is c h a r a c t e r i z e d with S T M . A second e x a m p l e
of S T M use in d e v e l o p i n g m a n u f a c t u r i n g processes is
given in t h e i m a g e of a n i n t e g r a t e d circuit (Fig. 14b).
S T M c a n be used t o c h a r a c t e r i z e p a t t e r n s p r o d u c e d
b y s t a n d a r d l i t h o g r a p h y processes which a r e used in
the p r o d u c t i o n of electronic devices such as c o m -
435
Scanning
Tunnelling
60
Microscopy
Spectroscopy
7^
0
and
20
oxygen
40
60
E l a p s e d t i m e in v a c u u m
80
100
(h)
>
<
Figure 11
Change in surface chemistry due to desorption of
atmospheric adsorbates when ZnO is introduced into an
UHV environment: the change in "apparent" surface
work function, as determined by the changing slope of the
I/z measurement performed in the STM, and the Auger
analysis are consistent with the desorption of oxygen and
carbon dioxide from the ZnO
p u t e r s . T h e s e m a t e r i a l s a r e n o t necessarily c o n d u c
tive; c o n s e q u e n t l y , d e p o s i t i o n of a thin film of m e t a l is
necessary t o p r o v i d e a c o n d u c t i v e surface for i m a g i n g .
T h e t h r e e - d i m e n s i o n a l i n f o r m a t i o n o b t a i n e d in the
S T M analysis of i n t e g r a t e d circuits c a n n o t b e
o b t a i n e d with o t h e r m e t h o d s of process e v a l u a t i o n
Tunnelling bias
(V)
Figure 13
Three types of electronic structure detected in emeraldine
hydrochloride films: (a) a semiconductor-like structure
with no midgap defect states, (b) a metallic-like structure;
and (c) a structure consisting of midgap states between the
valence and conduction bands
c u r r e n t l y in use. I m p o r t a n t t o t h e p o t e n t i a l of S T M in
c o m m e r c i a l a p p l i c a t i o n s is t h a t these images were
a c q u i r e d in air, t h u s a v o i d i n g t h e c o m p l i c a t i o n s , a n d
e x t r a analysis time, associated with v a c u u m systems.
6. Related
Figure 12
Topographic image of partially protonated emeraldine
hydrochloride, indicating the surface structure that results
from the melt spinning process of film deposition
436
Techniques
T h e s c a n n i n g t e c h n o l o g y of S T M is n o w being
exploited t o m e a s u r e q u a n t i t i e s o t h e r t h a n tunnelling
c u r r e n t a n d local densities of states. T h e m o s t d e
veloped of these n e w " n e a r field" o r " s c a n n i n g p r o b e "
t e c h n i q u e s is a t o m i c force m i c r o s c o p y ( A F M ) , w h i c h
r e c o r d s i n t e r a t o m i c forces b e t w e e n t h e s a m p l e a n d
tip. T h e tip is a t t a c h e d t o a cantilever w i t h a spring
c o n s t a n t of a b o u t 1 N m " 1 a n d r e s o n a n t frequency of
1 - 1 0 k H z . A s t h e tip is s c a n n e d over t h e s a m p l e ,
Scanning
Tunnelling
Microscopy
and
Spectroscopy
Figure 14
Constant current images: (a) a 5 scan of a 1 diffraction grating and (b) a 50 scan of an integrated circuit coated
with a thin layer of goldimages were acquired on a Nanoscope in air (courtesy of Digital Instruments)
437
Scanning
Tunnelling
Microscopy
and
Spectroscopy
Bibliography
Bardeen J 1961 Tunneling from a many particle point of
view. Phys. Rev. Lett. 6: 57-9
Bell L D, Kaiser W J 1988 Observation of interface band
structure by ballistic-electron-emission microscopy. Phys.
Rev. Lett. 61: 2368-71
Binnig G, Quate C F, Gerber Ch 1986 Atomic force
microscopy. Phys. Rev. Lett. 56: 930-3
Binnig G, Rohrer 1982 Scanning tunnelling microscope.
Helv. Phys. Acta 55: 726
Binnig G, Rohrer 1987 Scanning tunnelling microscopy
from birth to adolescence. Rev. Mod. Phys. 59: 615-25
Binnig G, Rohrer H, Gerber Ch, Weibel 1982 Surface
studies by scanning tunneling microscopy. Phys. Rev.
Lett. 49: 57-61
Binnig G, Rohrer H, Gerber Ch, Weibel 1983 7 x 7
reconstruction on Si resolved in real space. Phys. Rev.
Lett. 50: 120
Bonnell D A 1988 Characterization of carbides by STM.
J. Mater. Sci. Eng. A 105/106: 55-63
Bonnell D A (ed.) 1990 Scanning Tunneling Microscopy:
Theory and Practice. VCH, New York
Bonnell D A, Angelopoulos 1989 Spatially localized
electronic structure in polyaniline by STM. IBM Re
search Report
Bonnell D A, Clarke D R 1988 Scanning tunneling micros
438
Secondary-Ion
1. Ion-Solid
Interaction:
Sputtering
and
Ionization
S p u t t e r e d species, p r o d u c e d b y 1-30 k e V i o n b o m
b a r d m e n t , u n d e r g o a c h a r g e - e x c h a n g e w i t h their local
e n v i r o n m e n t ( s a m p l e surface) resulting in their c o n
version t o positive a n d negative i o n s . T h e s e a n a l y t i
cally i m p o r t a n t s e c o n d a r y ions o r i g i n a t e from a n a r e a
defined laterally b y t h e p r i m a r y - b e a m p e r i p h e r y , typi
cally 1 - s e v e r a l m m , a n d t h e s a m p l e i n t e r a c t i o n
d e p t h , 5 - 5 0 A. T h e m a s s - s p e c t r o m e t r i c analysis of
these s e c o n d a r y i o n s results in a t e c h n i q u e c a p a b l e of
elemental specificity from h y d r o g e n t o u r a n i u m w i t h
detectabilities in t h e p p m ( a t o m i c ) r a n g e .
T h e a c t u a l p h e n o m e n o n of s p u t t e r i n g w a s first
r e p o r t e d in t h e 1850s in gas-discharge e x p e r i m e n t s .
Since these early b e g i n n i n g s , t h e e r o s i o n of solids
by energetic b e a m s h a s received c o n s i d e r a b l e a t t e n
tion a n d m a n y m e c h a n i s m s h a v e b e e n f o r m u l a t e d t o
rationalize t h e s p u t t e r i n g p r o c e s s . C u r r e n t l y , t h e r e
exists n o single m o d e l w h i c h c a n a c c o u n t for all t h e
e x p e r i m e n t a l results.
T h e general t o p i c of s p u t t e r i n g m a y be divided i n t o
t w o categories: (a) physical a n d (b) c h e m i c a l s p u t t e r
ing. Physical s p u t t e r i n g involves t h e transfer of e n e r g y
from t h e incident ion t o t h e t a r g e t a t o m ( s ) resulting in
its (their) ejection. T h i s p r o c e s s is c o n t r a s t e d t o c h e m
ical s p u t t e r i n g w h e r e t h e incident particle results in
the f o r m a t i o n of a m e t a s t a b l e c o m p o u n d a t t h e t a r g e t
surface. B o t h types of s p u t t e r i n g r e q u i r e t h a t t h e
ejected species h a v e significant energy t o o v e r c o m e
the surface p o t e n t i a l b a r r i e r . S p u t t e r i n g c a n o c c u r
Mass
Spectrometry
Secondary-Ion
Mass
Spectrometry
Figure 1
Schematic illustration of the Cameca IMS-3f ion microscope (courtesy of Cameca Instruments)
Instrumentation
S I M S i n s t r u m e n t a t i o n c a n r a n g e from
simple
discharge-ion g u n / q u a d r u p o l e m a s s analyzers t o
sophisticated ion m i c r o p r o b e s a n d ion m i c r o s c o p e s .
T h e a c t u a l p r i m a r y - i o n s o u r c e a n d optics, s a m p l e h a n d l i n g capabilities a n d s p e c t r o m e t e r d e t e r m i n e t h e
i n s t r u m e n t ' s analytical p o t e n t i a l a n d price. F o r this
discussion, S I M S i n s t r u m e n t s m a y b e categorized i n t o
three general classes: (a) ion m i c r o p r o b e s t h a t use a
highly focused p r i m a r y b e a m ( 2 - 2 0 d i a m e t e r )
allowing lateral m i c r o a n a l y s i s ; (b) ion m i c r o s c o p e s
t h a t i n c o r p o r a t e a relatively large b e a m ( 5 - 5 0 0 p m
d i a m e t e r ) a n d a stigmatic m a s s s p e c t r o m e t e r t o p r o
vide lateral r e s o l u t i o n s of a p p r o x i m a t e l y 1 p m ; a n d (c)
b i g - b e a m i n s t r u m e n t s (100s p m d i a m e t e r ) t h a t a r e
440
Secondary-Ion
Depth
(/im)
Figure 2
9
+
SIMS in-depth profile of a 50 kV/lel4 Be implant in
GaAs
Mass
Spectrometry
441
Secondary-Ion
IxlO
IXIO
Mass
Spectrometry
7
E
I 10
I
0
0.39
0.72
1.08
I
1.44
1.80
Total depth ()
Figure 3
SIMS in-depth profile of a GaAs/AlGaAs superlattice showing all 62 layers of the structure resolved
442
capabilities, a S I M S i n s t r u m e n t s h o u l d o p e r a t e in a
8
v a c u u m of a t least 1 0 ~ t o r r . A l s o , m a n y S I M S
i n s t r u m e n t s a r e b a k a b l e t o t e m p e r a t u r e s of 150
180C, a i d i n g in t h e r e m o v a l of c o n t a m i n a n t s from
t h e walls of t h e system. R e c e n t designs in q u a d r u p o l e
m a s s filters h a v e e n a b l e d m a n y i n s t r u m e n t s t o b e
e q u i p p e d w i t h t h e smaller q u a d r u p o l e filters. T h e
relatively inexpensive q u a d r u p o l e systems m a y b e
m o u n t e d in t h e s a m p l e region t o p r o v i d e a n analysis
of a n y residual c o n t a m i n a n t s . Q u a d r u p o l e analyzers
h a v e also e n a b l e d t h e e x p a n s i o n of analytical c a p a b i l
ities b y " a d d i n g o n " t o existing systems. S u c h a d d - o n ,
h y b r i d systems allow c o m p l e m e n t a r y i n f o r m a t i o n t o
be t a k e n o n a given s a m p l e w i t h o u t it h a v i n g t o b e
r e m o v e d from t h e h i g h - v a c u u m e n v i r o n m e n t .
3. Analytical
Applications
of
SIMS
S I M S h a s been a p p l i e d t o m a n y different p r o b l e m s in
a variety of disciplines. T h e m e t h o d h a s p r o v i d e d
i n f o r m a t i o n o n a m y r i a d o f s a m p l e s r a n g i n g from
m i n e r a l s a n d l u n a r particles t o o r g a n i c molecules a n d
biological tissues.
Secondary-Ion
Mass
Spectrometry
Figure 4
SIMS ion-imaging analysis showing two different
hydrogen distributions in (a) a nickel-base alloy and
(b) 304 stainless steel
D e p t h profiling is o n e of t h e m o s t c o m m o n a n a l y t i
cal m o d e s of S I M S . I n practice, it is d o n e b y r a s t e r i n g ,
o r s c a n n i n g , t h e p r i m a r y b e a m a c r o s s a s a m p l e sur
face. R a s t e r i n g is necessary b e c a u s e of t h e G a u s s i a n
s h a p e of t h e b e a m . Typically, t h e b e a m is r a s t e r e d
over a large a r e a ( 1 0 0 - 5 0 0 ) with s e c o n d a r y i o n s
selected from a central p o r t i o n of t h e c r a t e r u s i n g
either m e c h a n i c a l o r electronic a p e r t u r i n g . T h i s helps
to eliminate c r a t e r - e d g e effects c a u s e d b y t h e b e a m ' s
G a u s s i a n s h a p e w h i c h c o u l d decrease d e p t h resolu
tion d u e t o s e c o n d a r y - i o n emission from sloping
crater walls.
O n e c o m m o n a p p l i c a t i o n o f d e p t h profiling is t h e
investigation of t h e d i s t r i b u t i o n of electrically active
species, d o p a n t s , in s e m i c o n d u c t o r s . T r a c e a m o u n t s
of these d o p a n t s i n t r o d u c e available states i n t o t h e
region of t h e f o r b i d d e n g a p . T h u s , t h e exact c o n c e n
t r a t i o n a n d i n - d e p t h d i s t r i b u t i o n of these species c a n
A n o t h e r c u r r e n t m e t h o d for t h e f o r m a t i o n of novel
device s t r u c t u r e s is m o l e c u l a r - b e a m epitaxy ( M B E ) .
H e r e , m o d u l a t e d s t r u c t u r e s of s e m i c o n d u c t i n g m a t e r
ials a r e d e p o s i t e d o n a n a p p r o p r i a t e s u b s t r a t e with
a c c u r a t e c o n t r o l s o n d o p i n g c o n c e n t r a t i o n a n d film
thickness. T h e interfacial s h a r p n e s s a n d film thickness
of such systems a r e t w o i m p o r t a n t p a r a m e t e r s . A g a i n ,
a S I M S i n - d e p t h profile p r o v i d e s analytical results
p e r t a i n i n g t o t h e s t r u c t u r e of t h e device. F i g u r e 3
s h o w s a S I M S profile of a G a A s - A l G a A s superlattice p r e p a r e d by M B E . T h e s t r u c t u r e from the
surface c o n t a i n s a 40 A G a A s layer, t h e n 60 alter
n a t i n g layers of G a A s a n d A l G a A s - S i , a n d a second
40 A GaAs layer d e p o s i t e d o n a G a A s s u b s t r a t e . T h e
S I M S d a t a were r e c o r d e d using 8.0 k e V 1 3 C
3 s + prim
a r y i o n s a n d negative s p e c t r o m e t r y . T h e profiles of
2 7 Al", 2 S
8 i~ and 6 G
9 a"
a r e s h o w n p l o t t e d as relative
intensity versus t o t a l d e p t h . D u e t o t h e c h a n g e s in
s p u t t e r i n g r a t e from o n e layer t o a n o t h e r , only t h e
t o t a l d e p t h from t h e surface t o t h e e n d of the S I M S
profile is a c c u r a t e . T h e profiles s h o w all 62 layers well
resolved. Typical d e p t h r e s o l u t i o n in a d e p t h profile
is of t h e o r d e r of 50 A a l t h o u g h this c a n be i m p r o v e d
u p o n by a p p r o x i m a t e l y a factor of t w o with o p t i m i z a
tion of i n s t r u m e n t a l p a r a m e t e r s .
A n o t h e r powerful analytical m o d e of S I M S is the
ability t o p e r f o r m ion i m a g i n g , t h a t is, t o d e t e r m i n e
t h e lateral d i s t r i b u t i o n of a n y element in a s a m p l e .
S u c h a n analysis is of u t m o s t i m p o r t a n c e w h e n loca
lized p h e n o m e n a a r e of c o n c e r n , for e x a m p l e , grainb o u n d a r y chemistry, segregation a n d precipitation.
I n t h e field of m e t a l l u r g y , t h e localization of a
variety of elements in a n u m b e r of alloys systems is of
i m p o r t a n c e d u e t o t h e effects of these elements o n
m a t e r i a l s p r o p e r t i e s such as brittleness, tensile
s t r e n g t h a n d t h e o c c u r r e n c e of subcritical crack
g r o w t h . A l t h o u g h m a n y of these elements c a n be
443
Secondary-Ion
Mass
Spectrometry
I0
'Ca
CaH
C aFOe H
Ca
-
I0
Ca
CaO
CaH
Fe
V
TiH
Ca
Cr
VH
Cr
40
42
44
46
48
50
52
Mass/charge (amu)
g
Al2
54
Fe
NiH
FeH
KO
FeH
CrH
56
58
NN
60
Figure 5
SIMS mass spectrum of a coal-ash sample with both elemental and molecular clusters seen
444
a n d positive-ion s p e c t r o m e t r y . T h e d a t a a r e s h o w n as
relative intensity versus t h e m a s s / c h a r g e r a t i o . T h e
+
+
+
+
s p e c t r u m indicates t h e presence of C a , T i , V , C r ,
+
+
N i a n d F e . A l s o , n o t e t h e presence of m o l e c u l a r
+
+
clusters of t h e elements (e.g., C a H , C a O ) . T h e
f o r m a t i o n of such clusters results from t h e s p u t t e r i n g
process a n d t e n d s t o c o m p l i c a t e even t h e simplest of
S I M S m a s s spectra.
T h e e x a m p l e s of systems t o which S I M S is appli
cable, a n d often u n i q u e , a r e by n o m e a n s e x h a u s t e d in
this discussion. T h e v a r i o u s o p e r a t i n g m o d e s of S I M S
offer t r e m e n d o u s analytical p o t e n t i a l a n d scope.
See also: Laser Microprobe Mass Spectrometry; Laser Sam
pling Inductively Coupled Plasma Mass Spectrometry; Or
ganic Mass Spectrometry
Bibliography
Behrisch R (ed.) 1981 Sputtering by Particle Bombardment
1: Physical Sputtering of Single-Element Solids, Topics in
Applied Physics, Vol. 47. Springer, New York
Benninghoven A, Giber J, Laszlo J, Reidel M, Werner W
(eds.) 1982 Secondary Ion Mass Spectrometry: SIMS III,
Chemical Physics Vol. 19. Springer', New York
Evans C A Jr 1975 Surface and thin film compositional
analysis: description and comparison of techniques. Anal.
Chem. 47: 818A-29A
Evans C A Jr 1975 Surface and thin film analysis. Anal.
Chem. 47: 855A-86A
Heinrich F J (ed.) 1982 Secondary ion mass spectrometry.
In: Geiss R (ed.) 1981 Microbeam Analysis. San Francisco
Press, San Francisco, CA, pp. 202-32
Semiconducting
Semiconducting Materials:
Characterization by Etching
S t r u c t u r a l a n d c h e m i c a l i n h o m o g e n e i t i e s a r e t w o of
t h e m a i n r e a s o n s for l o w yields a n d s h o r t lifetimes of
electronic devices m a d e f r o m s e m i c o n d u c t o r s . I n
c o m p o u n d s e m i c o n d u c t o r s t h e n u m b e r of p o s s i b l e
defects is l a r g e r t h a n in t h e case of e l e m e n t a l s e m i
c o n d u c t o r s , d u e t o t h e w i d e r v a r i e t y of n a t i v e defects
which can occur. Both crystallographic a n d chemical
defects a r e i n t r o d u c e d i n t o b u l k m a t e r i a l d u r i n g
g r o w t h a n d l a t e r a t a n y s t a g e of device p r o c e s s i n g .
F o r this r e a s o n , q u i c k a n d reliable c h a r a c t e r i z a t i o n
t e c h n i q u e s a r e essential for r e v e a l i n g defects a n d
assessing t h e r e a s o n s for t h e i r f o r m a t i o n , especially
w h e n s u c h i n f o r m a t i o n is r e q u i r e d b e f o r e f u r t h e r
p r o c e s s i n g t a k e s p l a c e . Selective e t c h i n g m e e t s t h e s e
r e q u i r e m e n t s a n d , in c o m b i n a t i o n w i t h reflection
m i c r o s c o p y , is widely u s e d in s t u d y i n g defects in
semiconductors. Conventional etching techniques
h a v e a l r e a d y b e c o m e a r o u t i n e m e t h o d of e v a l u a t i n g
t h e d e n s i t y a n d d i s t r i b u t i o n of defects s u c h as d i s l o
c a t i o n s (the s t a n d a r d specification of all c o m m e r
cially a v a i l a b l e s e m i c o n d u c t o r s u b s t r a t e s c o v e r s t h e
etch pit d e n s i t y ( E P D ) ) . I m p o r t a n t f e a t u r e s of this
e t c h i n g m e t h o d a r e simplicity, r a p i d d a t a a c q u i s i t i o n
a n d relatively l o w - c o s t e q u i p m e n t . T h e m e t h o d is,
h o w e v e r , a n i n d i r e c t o n e (i.e., t h e e t c h p i t s a r e
f o r m e d d u e t o t h e p r e s e n c e of defects b u t t h e defects
themselves a r e c o n t i n u o u s l y r e m o v e d a s t h e e t c h i n g
proceeds). As a consequence, to avoid misinterpreta
t i o n , c a l i b r a t i o n w i t h d i r e c t m e t h o d s is often
r e q u i r e d ; a l s o , t h e size of t h e p i t s c a n b e easily
controlled by the time a n d / o r temperature of etch
ing, b e i n g u s u a l l y o r d e r s of m a g n i t u d e l a r g e r t h a n
t h e real size of t h e defects. T h i s last p r o p e r t y is very
useful w h e n a u t o m a t i c c o u n t i n g of t h e E P D is
employed.
T h e rules of f o r m a t i o n of d i s l o c a t i o n - r e l a t e d e t c h
pits a r e relatively well r e c o g n i z e d a n d u n d e r s t o o d for
different types of solids, a m o n g t h e m s e m i c o n d u c
t o r s . H o w e v e r , t h e i n c r e a s i n g d e m a n d for h i g h c o m
p o s i t i o n a l a n d s t r u c t u r a l p e r f e c t i o n in c o m p o u n d
semiconductors has brought about new etching
systems w h i c h p o s s e s s a f u n d a m e n t a l l y
differ
e n t m e c h a n i s m of r e v e a l i n g defects. I n s t e a d of
d i s l o c a t i o n - r e l a t e d e t c h p i t s , hillocks o r c o m p l e x
etch features a r e f o r m e d . I n a d d i t i o n , very h i g h
Materials:
Characterization
by
Etching
/. General
Solutions
Characteristics
of Chemical
Etching
in
W e t c h e m i c a l e t c h i n g of s e m i c o n d u c t o r s c a n b e
divided i n t o t w o m a i n categories with respect t o t h e
rate-limiting step of surface r e a c t i o n s . T o t h e first
c a t e g o r y b e l o n g processes w h e r e t h e diffusion of
r e a c t a n t s a n d r e a c t i o n p r o d u c t s t o w a r d s o r from t h e
surface is r a t e limiting. T h e o v e r a l l e t c h r a t e (i.e.,
t h e n u m b e r of molecules r e m o v e d p e r u n i t time from
t h e surface) is in this case d e t e r m i n e d b y F i c k ' s first
law of diffusion:
dt
(1)
w h e r e D is t h e diffusion coefficient of r e a c t a n t s in t h e
liquid, Ax is t h e projected surface a r e a a s s u m i n g small
surface irregularities c o m p a r e d with t h e thickness d of
t h e b o u n d a r y liquid layer depleted of r e a c t a n t s a n d c
is t h e c o n c e n t r a t i o n of r e a c t a n t s . A n ideal diffusionlimited e t c h i n g s o l u t i o n p r o d u c e s flat a n d m i r r o r l i k e
surfaces; n o c o m p o s i t i o n a l o r c r y s t a l l o g r a p h i c defects
a r e revealed (polishing etching).
T h e s e c o n d c a t e g o r y covers selective etching (or
defect revealing) w h e r e selectivity refers t o t h e local
differences in t h e etch r a t e o n s t r u c t u r a l o r chemical
i n h o m o g e n e i t i e s in t h e s a m e m a t e r i a l . ( T h e t e r m
" s e l e c t i v e " is also used t o describe chemical polishing
w i t h different e t c h r a t e s o n c o m p o s i t i o n a l differences,
as in h e t e r o s t r u c t u r e s o r a l o n g different crystal
l o g r a p h i c directions. T h i s last chemical t r e a t m e n t is
called selective, a n i s o t r o p i c , preferential o r profile
etching.) I n this case t h e c h e m i c a l activity of t h e
surface, w h i c h for s e m i c o n d u c t o r s d e p e n d s o n crystal
l o g r a p h i c , electronic a n d p a s s i v a t i o n effects, is t h e
rate-limiting step. T h e r a t e of such a n activationc o n t r o l l e d (kinetically c o n t r o l l e d ) p r o c e s s c a n be d e
scribed b y
^ = kAc
dt
(2)
w h e r e k is chemical r a t e c o n s t a n t a n d A is t h e real
surface a r e a . T h e a c t i o n of a n ideal defect selective
etch d o e s n o t d e p e n d o n mixing b e c a u s e diffusion in
t h e liquid is h i g h e r t h a n t h e r a t e of etching. H o w e v e r ,
445
Semiconducting
Materials:
Lateral distance
(a)
(mm)
Characterization
Lateral distance
by
Etching
(mm)
(b)
Figure 1
Surface profiles for (a) diffusion-limited and (b) defectselective etching of compound semiconductors
(D denotes surface irregularities related to defects)
446
Figure 2
Rapid local etching of -type GaAs due to illumination of
the semiconductor surface using a parallel light beam of
diameter = 50 (scanning electron microscope image,
specimen tilt 45)
Semiconducting
2. Dislocation-Related
2.1 Etch
Etch
Figures
Pits
D e p e n d i n g o n t h e m e c h a n i s m of t h e r e a c t i o n t h a t
takes place o n t h e surface of a c o m p o u n d s e m i c o n
d u c t o r , t w o g r o u p s of etch features f o r m e d o n dislo
c a t i o n s c a n b e discerned, n a m e l y etch pits a n d etch
hillocks. T h e first g r o u p , s h o w n schematically in Figs.
3 a - c , covers preferential a n d n o n p r e f e r e n t i a l pits. T h e
s h a p e of t h e etch pits d e p e n d s o n t h e c r y s t a l l o g r a p h i c
o r i e n t a t i o n o f t h e e t c h e d surface a n d o n t h e inclina
tion of t h e d i s l o c a t i o n line. T h e s h a p e of t h e etch
hillocks d e p e n d s only o n t h e inclination o f t h e linear
defect. E t c h pits o n dislocations p e r p e n d i c u l a r t o t h e
surface a r e c e n t r o s y m m e t r i c a l . D i s l o c a t i o n s with dif
ferent inclinations w i t h respect t o t h e etched surfaces
c a n be recognized in Figs. 4 a , 5 a n d 7a. O n t h e basis o f
the shift of t h e b o t t o m p o i n t o f t h e c r y s t a l l o g r a p h i c
pit vs t h e g e o m e t r i c a l c e n t e r of t h e p i t c o n t o u r a t t h e
surface a n d t h e p i t d e p t h d (see F i g . 3 a ) , t h e inclina
tion angle of t h e s t r a i g h t d i s l o c a t i o n line c a n b e
d e t e r m i n e d from t h e simple r e l a t i o n s h i p : tgcn = d/x.
K n o w i n g this angle a n d t h e c o o r d i n a t i o n system from
the external s h a p e of t h e p i t , t h e c r y s t a l l o g r a p h i c
direction of t h e d i s l o c a t i o n line c a n b e calculated.
T h e r e a r e t w o c o n d i t i o n s for t h e f o r m a t i o n of etch
pits. T h e first is related t o t h e t h e r m o d y n a m i c s o f t h e
c r y s t a l - e t c h a n t system. T h e r e m u s t b e a sufficient
p o t e n t i a l ( G i b b s free energy) difference b e t w e e n t h e
defect site a n d t h e perfect lattice in o r d e r t o c r e a t e a
stable nucleus of t h e p i t . D i s l o c a t i o n - r e l a t e d strain
fields a n d / o r t h e associated C o t t r e l l a t m o s p h e r e s a r e
the r e a s o n s for a local increase o f chemical p o t e n t i a l
which is t h e driving force for t h e n u c l e a t i o n o f a p i t .
O n c e t h e stable n u c l e u s is f o r m e d it g r o w s b y t h e
h o r i z o n t a l m o v e m e n t of steps. D e p e n d i n g o n t h e
a t o m i c perfection of t h e steps (i.e., f o r m a t i o n a n d
kinetics of k i n k m o v e m e n t ) , either c r y s t a l l o g r a p h i c
(preferential) o r n o n p r e f e r e n t i a l pits d e v e l o p (Figs.
3b, c). T h e second necessary c o n d i t i o n for t h e f o r m a
tion of p i t o n a d i s l o c a t i o n d e p e n d s o n t h e kinetics
of dissolution of t h e perfect surface a n d t h e defect
Materials:
Characterization
(d)_i
by
Etching
1-
Figure 3
Schematic representation of (a)-(c) etch pits and
(d) hillocks formed on dislocations intersecting the etched
surface: (a) and (d) are cross sections; (b) and (c) are
surface views of preferential and nonpreferential pits,
respectively
447
Semiconducting
Materials:
Characterization
by
Etching
etching t h a t revealed t h e characteristic
r a d i a l d i s t r i b u t i o n of t h e E P D .
Figure 4
Result of simultaneous etching of two opposite surfaces of
a GaAs wafer in a preferential solution: (a) {11 l}Ga and
(b) { l l l } A s (differential interference contrast (DIC) image)
e l o n g a t i o n of t h e h e x a g o n a l pits, m i g h t be strongly
influenced by the d o p i n g of t h e etched m a t e r i a l .
F i g u r e 5b also s h o w s perfectly h e x a g o n a l pits
o b t a i n e d o n a (001) surface of i n d i u m - a l l o y e d G a A s
after etching in t h e s a m e c o n d i t i o n s as for t h e s a m p l e
in Fig. 5a. I n this case, i n d i u m a t o m s a r e responsible
for t h e c h a n g e in t h e kinetics of step m o v e m e n t o n
different low-index p l a n e s f o r m i n g t h e side walls of
the pits. T h e s a m e effect c a n b e o b t a i n e d using
different etching systems, inhibitors o r by changing the
t e m p e r a t u r e d u r i n g etching. F i g u r e 6 illustrates t h e
effect of variable c o m p o s i t i o n of similar etching sys
tems o n the s h a p e of preferential pits in I n P : H 3 P 0 4 H B r etch is k n o w n to p r o d u c e squarelike pits, t h a t is
with fourfold s y m m e t r y (Fig. 6a), while H N 0 3 H B r etch yields pits elongated a l o n g o n e of the <110>
directions, t h a t is with twofold symmetry (Fig. 6b).
D i s l o c a t i o n s c o n s t i t u t e a c o n t i n u o u s s o u r c e of n u cleation of atomic-size steps. A s a result, t h e size of
t h e pits d e p e n d s o n t h e time a n d / o r t e m p e r a t u r e of
etching. A n y d i s c o n t i n u i t y a l o n g t h e dislocation line
influences the regular n u c l e a t i o n of steps a n d , there
fore, the m o r p h o l o g y of the pits. F i g u r e 7a s h o w s etch
pits f o r m e d o n dislocations heavily d e c o r a t e d b y
precipitates t h a t give rise t o t h e n u c l e a t i o n of m a c r o steps. In t h e e x t r e m e case, dislocation m a y t e r m i n a t e
(or be nucleated) a t a localized microdefect. A s a
c o n s e q u e n c e , t h e c o n t i n u o u s s o u r c e of steps is
r e m o v e d from t h e m a t e r i a l a n d , instead of crystallog r a p h i c pits, shallow (S) pits a r e f o r m e d , as d o c u
m e n t e d in Fig. 7b.
T h e m o s t w i d e s p r e a d use of e t c h i n g p r o c e d u r e s t o
p r o d u c e pits is t o e s t i m a t e t h e density of dislocations
( E P D ) . T h e w h o l e etched wafers (or q u a r t e r s of t h e
(001) o r i e n t e d samples) a r e t h e n subjected t o a u t o m a
tic E P D c o u n t i n g using a m o t o r i z e d m i c r o s c o p e stage
c o u p l e d with a c o m p u t e r i z e d i m a g e analysis system.
F i g u r e 8 s h o w s a (001) G a A s wafer after preferential
448
W-shaped
Figure 5
Change in the morphology of preferential etch pits on the
(001) surface of GaAs due to differing composition of the
samples: (a) silicon-doped and (b) indium-alloyed
materials (DIC image)
Semiconducting
Materials:
Characterization
by
Etching
Figure 6
Change in the morphology of etch pits on the (001) surfaces of InP due to the different compositions of the etchants: (a)
H 3P0 4-HBr solution and (b) H N 0 3 - H B r solution (DIC image)
Figure 7
(a) Effect of decoration of dislocations by precipitates on
the morphology of preferential pitsformation of
macrosteps; and (b) transition from crystallographic to S
pits due to termination of dislocations at microdefects
(DIC images)
Figure 8
Characteristic W-shaped distribution of the EPD on the
(001) oriented 2" GaAs wafer after preferential etching
449
Semiconducting
Materials:
Characterization
by
Etching
0.5
(C) 0.4
0.31-1
0.1
-20-10 0
10 2 0 3 0 4 0
(/urn)
Figure 9
Etch hillock formed on a dislocation in /z-type GaAs during etching in a selective solution without illumination: (a) DIC
image; (b) SEM image, tilt 85; and (c) surface profile along x-x'
3. Revealing
Chemical
Inhomogeneities
diversified d e p e n d i n g o n t h e electronic s t r u c t u r e of
t h e etched m a t e r i a l . I n />-type s e m i c o n d u c t o r s , the
v a r i a b l e etch r a t e o n a r e a s w i t h lower a n d higher p+
carrier c o n c e n t r a t i o n s c a n be explained in t e r m s of
c a t h o d i c p r o t e c t i o n of regions by p+ regions as
illustrated in F i g . 11. T h e open-circuit p o t e n t i a l in this
m i x e d p / p + system a s s u m e s a n i n t e r m e d i a t e value K m ix
b e t w e e n t h e rest p o t e n t i a l s which w o u l d h a v e been
o b t a i n e d in t h e t w o s e p a r a t e a n d p+ samples. A s a
result, t w o different p a r t i a l c u r r e n t s a n d c o r r e s p o n d
ing etch rates a r e established, being higher for the p+
region.
F o r n/n+ systems, a n o t h e r factor b e c o m e s decisive,
n a m e l y t h e w i d t h w of t h e space c h a r g e layer which is
related t o t h e d o p a n t c o n c e n t r a t i o n N. A s increased
d o p a n t c o n c e n t r a t i o n c o r r e s p o n d s t o a d i m i n i s h e d w,
fewer holes a r e available for surface r e a c t i o n in n+
a r e a s c o m p a r e d w i t h a r e a s . T h e s a m e relation h o l d s
for e t c h i n g in t h e d a r k a n d u n d e r i l l u m i n a t i o n b u t t h e
P+
-40
-20
20
40
60
(d)
()
(a)
()
Figure 10
Influence of the electronic properties of the Cottrell
atmospheres on the morphology of etch features formed
during photoetching: (a) and (b) etch hillocks in -type
GaAs grown from arsenic-rich melt; (c) and (d) complex
etch features in -type GaAs grown from gallium-rich
melt; (a) and (c) DIC images; (b) and (d) surface profiles
on the defect-related etch features
450
(b)
Figure 11
(a) Anodic current density ia vs surface polarization V for
/?-type GaAs material with a variable carrier concentration
p/p+ and (b) the corresponding schematic representation
of an etched sample with growth striations due to
segregation of p-type dopant: vp and vp+ are etching
velocities proportional to the partial anodic currents (after
Weyher and van de Ven 1986 J. Crystal Growth 78:
191-217. Reproduced with permission)
Semiconducting
Figure 12
Remarkable alteration of the etch rate during
photoetching of an n/n+ area in GaAs: (a) DIC image of
the surface, (b) surface profile (i.e., relative etch depth)
plotted along x-x' line and (c) well-resolved growth
striations related to the fluctuation of deep recombinative
centers, revealed by photoetching on the (110) longitudinal
section of an undoped GaAs crystal (DIC image)
Materials:
Characterization
by
Etching
Figure 13
Shallow pits formed on arsenic precipitates in GaAs
grown from an arsenic-rich melt: (a) etch depth 1 ; and
(b) the same sample, etch depth 3 (DIC images)
Bibliography
Heimann R 1982 Principles of chemical etching. In:
Grabmaier J (ed.) 1982 Crystals Growth, Properties and
Applications, Vol. 8. Springer, Berlin, pp. 173-224
451
Semiconducting
Materials:
Characterization
by
Etching
zero d i m e n s i o n a l t y p i c a l e x a m p l e s a r e v a c a n
cies, interstitials, v a c a n c y - i n t e r s t i t i a l p a i r s , a n d
so o n ;
(b)
one dimensionaldislocations
category;
(c)
(d)
three d i m e n s i o n a l p r e c i p i t a t e s a n d
b e l o n g t o this c a t e g o r y .
belong to
this
inclusions
452
A l t e r n a t i v e t e c h n i q u e s , such as field-ion m i c r o s c o p y ,
h a v e s h o w n s o m e p r o m i s e for observing t h e m in
different m a t e r i a l s . O n t h e o t h e r h a n d , since its d e
v e l o p m e n t in t h e mid-1950s, T E M h a s played a very
crucial role in u n d e r s t a n d i n g t h e i n t r o d u c t i o n of one-,
t w o - a n d t h r e e - d i m e n s i o n a l defects in s e m i c o n d u c
tors; t h e r e a d e r is referred t o review articles b y
M a h a j a n (1989) a n d Cullis (1990) t o d e v e l o p a n
a p p r e c i a t i o n of this role.
T w o types of specimen a r e used in T E M studies:
p l a n view a n d cross sectional. T h e plan-view speci
m e n s a r e suitable for e x a m i n i n g a s - g r o w n b u l k crys
tals a n d epitaxial layers. H o w e v e r , for e v a l u a t i n g
m u l t i l a y e r s t r u c t u r e s , w h i c h f o r m t h e b a c k b o n e of
state-of-the-art solid-state electronics t e c h n o l o g y ,
cross sections a r e essential. N o t only d o they p r o v i d e
i n f o r m a t i o n o n interfaces b e t w e e n different m a t e r i a l s
c o n s t i t u t i n g a multilayer, b u t also they shed light o n
t h e g e n e r a t i o n a n d p r o p a g a t i o n of defects d u r i n g
g r o w t h a n d processing.
T h e p r e p a r a t i o n of b o t h plan-view a n d crosssectional s a m p l e s t h i n e n o u g h t o p r o v i d e electron
t r a n s p a r e n c y m a y involve either chemical t h i n n i n g o r
ion milling. T h e latter c o n v e n t i o n a l l y e m p l o y s low+
voltage A r ions b u t C h e w a n d Cullis (1987) h a v e
s h o w n t h a t the milling of m a t e r i a l s , such as I n P , C d T e
+
a n d Z n S e , using A r i o n s p r o d u c e s u n w a n t e d surface
artefacts, even a t 77 K . T h e s e c a n , h o w e v e r , b e elim
+
i n a t e d b y t h e a p p l i c a t i o n of reactive I ion milling.
Cross-sectional s a m p l e s c a n be p r e p a r e d using the
p r o c e d u r e p h o t o g r a p h i c a l l y described in Fig. 1. First,
pieces a r o u n d 10 m m x 1 m m a r e cleaved from
polished wafer s a m p l e s . U s i n g a d d i t i o n a l b a c k i n g
b l o c k s of a r o u n d 10 m m x 3 m m x 1 m m (Fig. l a ) of
b u l k silicon, t h e cleaved s a m p l e s a r e b o n d e d face t o
face using s t a n d a r d quick-setting e p o x y resin as
s h o w n in Fig. l b . C a r e is t a k e n d u r i n g t h e b o n d i n g
process t o e n s u r e all b o n d e d surfaces a r e clean a n d
free from p a r t i c u l a t e m a t t e r . C l a m p s with accurately
parallel j a w s a r e used t o h o l d t h e samples t o g e t h e r
u n d e r m o d e r a t e p r e s s u r e d u r i n g setting of the e p o x y
resin. B o n d e d s a m p l e s a r e t h e n polished o n b o t h
e x p o s e d sides (Fig. l c t h e p o s i t i o n of t h e center j o i n
is indicated) a n d specimen disks a r e c u t using a n
u l t r a s o n i c c u t t e r e m p l o y i n g a 600 grit silicon c a r b i d e
abrasive slurry in w a t e r . F o r a d d i t i o n a l s t r e n g t h a n d
ease of h a n d l i n g , thin m e t a l rings a r e b o n d e d t o the
specimen disks w i t h quick-setting e p o x y resin (rings
indicated b y R in Fig. l e ) . T h e disks a r e ultimately
r e m o v e d from t h e s u p p o r t i n g glass slides a n d a r e ion
milled.
T h e following e x a m p l e s h a v e b e e n c h o s e n t o illus
t r a t e t h e roles of T E M a n d H R T E M in s t r u c t u r a l
c h a r a c t e r i z a t i o n of s e m i c o n d u c t o r s :
(a)
replication of dislocations d u r i n g h o m o e p i t a x y ,
(b)
c o p p e r a n d i r o n suicide p r e c i p i t a t i o n o n stacking
faults in silicon as a result of device processing,
(c)
Semiconducting
Materials:
Electron
Microscopy
p r o t r u s i o n a n d a d e p r e s s i o n a t t h e e m e r g e n c e p o i n t of
t h e d i s l o c a t i o n a t t h e surface in F i g . 2 facilitates t h e
replication p r o c e s s .
F i g u r e 3, r e p r o d u c e d f r o m t h e s t u d y of Cullis a n d
K a t z (1974), s h o w s a silicon device s t r u c t u r e with a n
electrically active r o d defect lying a l o n g t h e p l a n e of
a n inclined s t a c k i n g fault w i t h subsidiary precipitate
a r r a y s . T h i s m i c r o g r a p h w a s o b t a i n e d from a n -type
silicon wafer t h a t h a d u n d e r g o n e a processing se
q u e n c e involving o x i d a t i o n , b o r o n drive in a n d reoxid a t i o n . Cullis a n d K a t z (1974) h a v e s h o w n t h a t such
faults (often m u l t i p l e o v e r l a p p i n g s e e Fig. 3a) a r e
extrinsic in n a t u r e , a r e b o u n d e d b y <111>/3 F r a n k
p a r t i a l s a n d t h a t t h e r o d defects result from i m p u r i t y
i r o n p r e c i p i t a t i o n as F e S i 2 . F u r t h e r m o r e , t h e s u b
sidiary precipitates h a v e b e e n identified as c o p p e r
suicides. H a v i n g fully a n a l y z e d these m i c r o s t r u c t u r a l
features in processed silicon wafers, Cullis a n d K a t z
(1974) devised a processing p r o c e d u r e w h i c h elimi
n a t e d metallic suicide f o r m a t i o n . T h e y were t h u s able
t o e n h a n c e t h e yield of devices fabricated from t h e
p r o c e s s e d wafers.
R e t u r n i n g t o t h e t o p i c of I I I - V c o m p o u n d s , Fig. 4
s h o w s a N o m a r s k i interference c o n t r a s t m i c r o g r a p h
Figure 1
(a)-(f) sequence depicting the different stages of
cross-sectional sample preparation (after Chew and Cullis
1987)
(d)
interfaces in I n P - I n G a A s superlattices a n d c o m
p o s i t i o n profiles a c r o s s t h e I n P - I n G a A s a n d
I n G a A s - I n P interfaces.
F i g u r e 2 s h o w s a t r a n s m i s s i o n electron m i c r o g r a p h
o b t a i n e d from a [110] cross section of a n I n P h o m o epitaxial layer g r o w n b y liquid p h a s e epitaxy o n a
(001) s u b s t r a t e . D i s l o c a t i o n s p r e s e n t in t h e s u b s t r a t e
a r e replicated i n t o t h e epitaxial layer a n d a r e o r i e n t e d
close t o t h e [001] direction. It h a s b e e n a s c e r t a i n e d b y
T E M diffraction c o n t r a s t e x p e r i m e n t s t h a t t h e
Burgers vectors of t h e d i s l o c a t i o n s a r e a[\ 10]/2, w h e r e
a is t h e lattice p a r a m e t e r . T h u s , t h e o b s e r v e d disloca
tions a r e close t o b e i n g perfect edge type, w i t h B u r g e r s
vectors lying in t h e g r o w t h surface.
A n interesting q u e s t i o n is t o a s k h o w , if t h e B u r g e r s
vector of a d i s l o c a t i o n in t h e s u b s t r a t e is parallel t o
the surface, is it replicated i n t o t h e o v e r g r o w t h
because it d o e s n o t p r o d u c e a step o n t h e surface.
B e a m et al. (1990) h a v e a d d r e s s e d this issue a n d h a v e
a r g u e d , b a s e d o n B e a m (1989), t h a t t h e presence of a
Figure 2
Examples of dislocations propagating in the [001]
direction: (a) the interactions with other dislocations
denoted by arrows should be noted and (b) the
dislocations which do not rotate to the [001] direction
should be noted. The plane of the images is (110) (after
Beam et al. 1990)
453
Semiconducting
Materials:
Electron
Microscopy
Figure 3
Rod defect lying along the plane of an inclined stacking
fault with subsidiary precipitate structures; compare
(a) and (b) showing outside-inside contrast given by
Frank partial dislocations. Transmission electron
micrographs recorded using Bragg reflections with
opposing g vectors: bright field, strong beam, s>0 (after
Cullis and Katz 1974)
of a n etched wafer of z i n c - d o p e d , b u l k G a A s . D i s l o
c a t i o n s a p p e a r as linear features in F i g . 4 a n d detailed
e x a m i n a t i o n h a s s h o w n t h a t these features a r e ridges,
resulting from differential e t c h a n t a t t a c k a t disloca
tions a n d t h e m a t r i x . T h e circular b e a d l i k e m a r k i n g s
lying o n t h e ridges a r e pits, a n d delineate precipitate
particles w h i c h h a v e b e e n preferentially a t t a c k e d b y
t h e etch. T o discern t h e n a t u r e of these precipitates,
Cullis et al. (1980) h a v e e x a m i n e d t h e a b o v e crystals
b y T E M a n d a n e x a m p l e t a k e n from their w o r k is
r e p r o d u c e d a s F i g . 5. T h e y h a v e s h o w n using d a r k field i m a g i n g (Fig. 5b) a n d selected a r e a electron
diffraction (Fig. 5c) t h a t t h e precipitates consist of
elemental arsenic w i t h its s t a n d a r d h e x a g o n a l struc
ture. T h e presence of arsenic precipitates in b u l k
G a A s crystals is u n w a n t e d b u t u n d e r s t a n d a b l e .
Generally, a G a A s crystal is g r o w n from a n arsenicrich melt, a n d t h e presence of a n excess arsenic in t h e
crystal ( p r o b a b l y as lattice interstitials) a t t h e g r o w t h
t e m p e r a t u r e c o u l d lead t o t h e f o r m a t i o n of arsenic
precipitates d u r i n g cooling.
W i t h t h e a d v e n t of o r g a n o m e t a l l i c v a p o r p h a s e
epitaxy a n d m o l e c u l a r b e a m epitaxy, it is possible t o
g r o w superlattices a n d q u a n t u m well s t r u c t u r e s w h i c h
find extensive a p p l i c a t i o n s in state-of-the-art devices.
T h e s e a p p l i c a t i o n s require s h a r p a n d chemically
a b r u p t interfaces. I n o r d e r t o p r o d u c e such s t r u c t u r e s ,
strong interaction between the growth and structural
c h a r a c t e r i z a t i o n p e r s o n n e l is desirable. T h i s issue is
e m p h a s i z e d in t h e e x a m p l e s w h i c h follow.
454
Figure 4
Optical Nomarski interference micrograph of an etched,
zinc-doped, /?-type GaAs wafer (after Cullis et al. 1980)
Semiconducting
Figure 5
Transmission electron micrographs and diffraction pattern
from a region in chromium-doped, semi-insulating GaAs
containing a precipitate at a dislocation: (a) bright field,
strong beam, 220 GaAs reflection operating; (b) dark
field, 114 precipitate reflection operating; and
(c) diffraction pattern showing precipitate reflection
(circled) used to obtain the image in (b) (after Cullis et al.
1980)
n o t always u n i f o r m l y t w o d i m e n s i o n a l , such t h a t
shallow t h r e e - d i m e n s i o n a l islands c a n b e f o r m e d b y
layer n u c l e a t i o n processes. T h i s c a n greatly d i s r u p t
the g r o w t h of very t h i n I n G a A s wells, as c a n b e seen
in Fig. 6 b , w h e r e a flat-topped island is p r e s e n t
b e t w e e n t h e a r r o w e d l o c a t i o n s w i t h i n a well n o m i n
ally 2.5 n m thick. Clearly, in this case t h e I n G a A s
layer is laterally d i s c o n t i n u o u s . F o r t h i c k e r I n G a A s
wells, careful studies using n a r r o w m a r k e r layers
( N o r m a n et al. 1989) h a v e d e m o n s t r a t e d t h a t u n d u l a
tions c a n also arise d u r i n g r e a c t a n t g a s switching a t
t h e e n d of well g r o w t h . H o w e v e r , e a c h of these
deleterious g r o w t h processes c a n b e c o n t r o l l e d b y
Materials:
Electron
Microscopy
Figure 6
Cross-sectional TEM images of InGaAs quantum wells
(dark) in InP (light), dark field (g = 002): (a) continuous
wells with asymmetrical nonplanarity and (b) narrowest
well shows island growth in arrowed region (after Cullis
1990)
455
Semiconducting
Materials:
Electron
Microscopy
^--interfaces.
typical,
error
p\
25
35
11I
InP
InP
0.2
^
As/
direction of
growth
InGaAs
-10
-5
10
15
Distance ( n m )
Figure 8
Variation of composition, expressed in terms of atomic
fractions, across a lOnm-thick InGaAs well measured by
x-ray microanalysis. Note the asymmetry of elemental
distributions (after Cullis 1990)
s t r a t e d . B o t h plan-view a n d cross-section s a m p l e s a r e
i m p o r t a n t for such studies a l t h o u g h cross sectioning,
in p a r t i c u l a r , is essential for investigation of t h e
s h a r p n e s s of interfaces in superlattices a n d q u a n t u m
well s t r u c t u r e s .
See also: Electron Microscopy, Analytical; Electron Micros
copy, High-Resolution
Figure 7
Cross-sectional TEM images of InGaAs quantum wells in
InP showing improved planarity of well boundaries:
(a) dark-field (g = 002) showing wells of three different
thicknesses and (b) [110] high-resolution lattice image of
narrowest well (after Cullis 1990)
456
Bibliography
Beam A 1989 Dislocation replication and annihilation in
InP homoepitaxial layers grown by liquid phase epitaxy.
Ph.D. dissertation, Carnegie Mellon University
Beam A, Mahajan S, Bonner W A 1990 Dislocation
replication and annihilation in InP homoepitaxial layers
grown by liquid phase epitaxy. Mater. Sci. Eng. 7: 8 3 101
Chew G, Cullis A G 1987 The preparation of transmis
sion electron microscopy specimens from compound
semiconductors by ion milling. Ultramicroscopy 23: 17598
Cullis A G 1990 The structural characterisation of advanced
compound semiconductor heteroeptaxial systems by
transmission electron microscopy. In: Sumino (ed.)
1990 Defect Control in Semiconductors. Elsevier, Amster
dam, pp. 1097-105
Cullis A G, Augustus D, Stirland D J 1980 Arsenic
precipitation at dislocations in GaAs substrate material.
J. Appl. Phys. 51: 2556-60
Cullis A G, Katz L 1974 Electron microscope study of
electrically active impurity precipitate defects in silicon.
Philos. Mag. 30: 1419-43
Mahajan S 1989 Growth- and processing-induced defects in
semiconductors. Prog. Mater. Sci. 33: 1-82
Norman A G, Butler R, Booker G R, Thrush J 1989
TEM studies using marker layers within GalnAs/InP
quantum well structures to determine the origin of inter
face undulations. In: Cullis A G, Hutchison J L (eds.)
Single-Crystal
X-Ray
Diffraction
c a p a b l e of u n a m b i g u o u s l y d e t e r m i n i n g t h e c o m p l e t e
t h r e e - d i m e n s i o n a l m o l e c u l a r s t r u c t u r e s of chemical
s u b s t a n c e s . A l t h o u g h x-ray s t r u c t u r e d e t e r m i n a t i o n
w a s o n c e r e g a r d e d as a difficult a n d t i m e - c o n s u m i n g
p r o c e s s w h i c h c o u l d o n l y b e c a r r i e d o u t b y highly
t r a i n e d c r y s t a l l o g r a p h e r s , recent a d v a n c e s in instru
m e n t a t i o n a n d software h a v e m a d e t h e t e c h n i q u e
available t o chemists as a r o u t i n e analytical t o o l .
C o m p l e t e crystal s t r u c t u r e analyses m a y n o w b e car
ried o u t in less t h a n o n e d a y for simple o r g a n i c
molecules a n d in less t h a n o n e week for c o m p o u n d s
c o n t a i n i n g u p t o 200 n o n h y d r o g e n a t o m s p e r
molecule.
Besides confirming t h e connectivity a n d stereo
c h e m i s t r y of t h e m o l e c u l e , x-ray c r y s t a l l o g r a p h y is
u n i q u e l y c a p a b l e of p r o v i d i n g precise i n f o r m a t i o n
c o n c e r n i n g b o n d lengths, b o n d angles a n d m o l e c u l a r
d i m e n s i o n s . T h i s t y p e of i n f o r m a t i o n is p a r t i c u l a r l y
i m p o r t a n t for t h e analysis of electronic s t r u c t u r e a n d
i n t e r m o l e c u l a r i n t e r a c t i o n s . I n a d d i t i o n , t h e diffrac
tion e x p e r i m e n t s often yield o t h e r i n f o r m a t i o n of
physical significance s u c h a s a m p l i t u d e s of t h e r m a l
m o t i o n of a t o m s o r g r o u p s of a t o m s . Single-crystal xr a y diffraction t e c h n i q u e s h a v e b e e n utilized t o u n
ravel very c o m p l i c a t e d m a c r o m o l e c u l a r s t r u c t u r e s
c o n t a i n i n g m a n y t h o u s a n d s of a t o m s in t h e i n d e p e n
d e n t s t r u c t u r a l unit. Special a t t a c h m e n t s h a v e been
d e v e l o p e d t o allow c o m p o u n d s t o b e studied over
wide r a n g e s of t e m p e r a t u r e s a n d pressures. E x p e r i
m e n t a l x-ray a n d n e u t r o n diffraction studies o n
single crystals h a v e b e e n c o m b i n e d with theoretical
m o l e c u l a r - o r b i t a l c a l c u l a t i o n s in o r d e r t o a n a l y z e t h e
d i s t r i b u t i o n of valence-electron densities.
1.
Fundamentals
457
Single-Crystal
X-Ray
Diffraction
dihkl)
Figure 1
Unit-cell nomenclature: the reference axes JC, y9 are
right-handed, the length of the unit-cell edge parallel to
each reference axis is a, b, c, respectively, and the
interaxial angles are , , y, respectively
nk = 2dsine
(1)
Figure 2
An example of an x-ray diffraction pattern produced by a
randomly oriented single crystal
458
Figure 3
Diagrammatic representation of Bragg's law showing the
diffraction angle and the interplanar spacing d(hkl).
Two rays reflected from the same plane do not suffer any
relative phase change or path difference (AB = CD)
Single-Crystal
X-Ray
Diffraction
I(hkl) = k\F(hkl)\
Akhkl)
Figure 4
Structure factor F(hkl) plotted on an Argand diagram.
<x(hkl) is the phase angle and the amplitude is represented
by OF
(2)
p(xyz)=V- Zll\F(hkl)\
l
2 l/2
+ B(hkl) ]
F(hkl) = l/j
(3)
(4)
w h e r e ^(:/)| is t h e a m p l i t u d e of t h e scattered w a v e
a n d <x(nkl) is its p h a s e angle. F r o m F i g . 4 it m a y b e
seen t h a t
A(hkl) = | F ( A W ) | c o s OL(hkl)
(9)
exp[27ri(Ax,. +
+ lZj)]
(10)
If b o t h t h e a m p l i t u d e \F(hkl)\ a n d t h e p h a s e <x(hkl) of
e a c h reflection a r e k n o w n , t h e electron density within
t h e u n i t cell o f t h e crystal c a n b e calculated directly.
O n t h e o t h e r h a n d , if t h e p o s i t i o n s of t h e a t o m s in t h e
u n i t cell a r e k n o w n , b o t h t h e s t r u c t u r e factor a n d
t h e p h a s e for e a c h reflection m a y b e calculated from
t h e s t r u c t u r e factor e q u a t i o n :
12
[A(hkl)-\B(hkl)]Y
= [A(hkl)
(8)
w h e r e A: is a c o n s t a n t . H o w e v e r , t h e p h a s e angle <x(hkl)
c a n n o t b e m e a s u r e d e x p e r i m e n t a l l y a n d m u s t there
fore b e o b t a i n e d indirectly t h r o u g h a variety of n u
merical t e c h n i q u e s .
T h e c e n t r a l p r o b l e m in t h e s o l u t i o n of a crystal
s t r u c t u r e is t h e a s s i g n m e n t of p h a s e angles t o e a c h
reflection in t h e d a t a set. T h e s o l u t i o n of t h e p h a s e
p r o b l e m is c o n s i d e r a b l y simplified for crystals which
possess c r y s t a l l o g r a p h i c centers o f s y m m e t r y , since, t o
a first a p p r o x i m a t i o n , t h e i m a g i n a r y c o m p o n e n t s
B(hkt) a r e z e r o for c e n t r o s y m m e t r i c space g r o u p s a n d
t h e p h a s e angles a r e therefore restricted t o values of 0
o r 180. A s t r u c t u r e is c o n s i d e r e d solved w h e n a set of
p h a s e angles h a s b e e n f o u n d w h i c h allows t h e a t o m s
t o b e located a n d t h e e x p e r i m e n t a l diffraction p a t t e r n
t o b e m a t c h e d t o t h e calculated diffraction p a t t e r n .
Since t h e electron density in a crystal varies c o n t i
n u o u s l y a n d periodically in t h r e e - d i m e n s i o n a l space,
t h e electron density p(xyz) a t a p o i n t w i t h fractional
c o o r d i n a t e s x, y, in a u n i t cell of v o l u m e V m a y b e
expressed a s a t h r e e - d i m e n s i o n a l F o u r i e r series:
(5)
and
(6)
(7)
and that
2.
Instrumentation
T h e basic h a r d w a r e c o m p o n e n t s of a n a u t o m a t e d
single-crystal x-ray diffractometer system include: (a)
a n x-ray s o u r c e consisting of a high-stability x-ray
g e n e r a t o r , a c o p p e r o r m o l y b d e n u m t a r g e t x-ray t u b e ,
a t u b e shield w i t h associated s h u t t e r s , a t t e n u t o r s a n d
safety i n t e r l o c k s , a m o n o c h r o m a t o r o r ^-filter system,
459
Single-Crystal
X rays
X-Ray
Diffraction
Sample
^Reflections
^ S c i n t i l l a t i o n - c o u n t e r detector
Incident
x-ray beam
X - ray generator
Detector
Figure 5
Block diagram of a typical instrument configuration used
for single-crystal x-ray diffraction analysis
a n d a n i n c i d e n t - b e a m c o l l i m a t o r ; (b) a four-circle
g o n i o m e t e r system w h i c h allows t h e specimen t o b e
precisely o r i e n t e d in a n y p o s i t i o n while r e m a i n i n g in
t h e x-ray b e a m ; (c) a scintillation c o u n t e r d e t e c t o r
system with associated c o l l i m a t o r a n d slits; a n d (d) a n
electronic c o n t r o l console c o n t a i n i n g a m i n i c o m p u t e r
o r m i c r o p r o c e s s o r , a m a g n e t i c t a p e drive a n d / o r
m a s s - s t o r a g e device, a c o m p u t e r t e r m i n a l , a n d inter
faces t o t h e g o n i o m e t e r a n d d e t e c t o r systems. M o d e r n
i n s t r u m e n t s n o r m a l l y include diffractometer c o n t r o l
software w r i t t e n in either B A S I C o r F O R T R A N t o
run on a minicomputer or microprocessor. Structure
d e t e r m i n a t i o n c a l c u l a t i o n s m a y b e carried o u t o n t h e
p r o c e s s o r used for d a t a collection o r they m a y b e
p e r f o r m e d o n a second m i n i c o m p u t e r linked t o t h e
diffractometer c o n t r o l m o d u l e . A large variety of
h a r d w a r e configurations is available commercially,
d e p e n d i n g u p o n t h e r e q u i r e m e n t s of t h e individual
l a b o r a t o r y . A typical i n s t r u m e n t configuration is
illustrated in F i g . 5.
T h e m o s t critical m e c h a n i c a l c o m p o n e n t in a n xr a y diffractometer system is t h e g o n i o m e t e r assembly,
which m u s t b e c a p a b l e of k e e p i n g t h e specimen cen
tered in the incident x-ray b e a m while a t t h e s a m e time
c h a n g i n g its o r i e n t a t i o n in o r d e r t o collect e a c h reflec
tion in reciprocal space. T h e m o s t c o m m o n l y used
t y p e of g o n i o m e t e r is illustrated in Figs. 6 a n d 7. A s
illustrated in F i g . 6, t h e d e t e c t o r m o v e s in a p l a n e
parallel t o t h e i n s t r u m e n t b a s e , referred t o as t h e
e q u a t o r i a l p l a n e , w h i c h c o n t a i n s t h e crystal a n d t h e
incident a n d diffracted x-ray b e a m s for t h e reflection
being m e a s u r e d . T h e value of t h e 20 angle c o r r e s
p o n d s t o twice t h e value of t h e diffraction angle. A
p a r t i c u l a r set of parallel lattice p l a n e s within t h e
crystal m a y b e p o s i t i o n e d in diffracting p o s i t i o n
t h r o u g h t h e a p p r o p r i a t e choice of t h e , a n d
angles. Since only t w o of these three angles a r e
i n d e p e n d e n t , o n e of t h e m m a y be c h o s e n arbitrarily,
t h e r e b y p e r m i t t i n g e a c h reflection t o be m e a s u r e d
from several e q u i v a l e n t o r i e n t a t i o n s . Typically, is
460
Figure 6
Diagram of axes in a four-circle diffractometer
3. Experimental
Procedure
Figure 7
A full-circle goniometer used in a commercial x-ray
diffractometer (courtesy of Nicolet X R D Corporation)
Single-Crystal
Figure 8
Thermal ellipsoid plot of the final structure of an organic
compound ( C 1 8H , 8 0 9 )
X-Ray
Diffraction
Figure 9
Unit-cell diagram showing the arrangement of molecules
within the cell
461
Single-Crystal
X-Ray
Diffraction
1. Theoretical
Outline
I n a n y scattering e x p e r i m e n t , t h e m e a s u r e d intensity
is c o n t r o l l e d b y t h e (total) s t r u c t u r e function St(Q)
(the scattering is a s s u m e d t o be elastic, i.e., n o energy
is e x c h a n g e d b e t w e e n s a m p l e a n d incident r a d i a t i o n )
given b y
St(Q)
= \F(Q)\
(1)
w i t h t h e scattering vector
Bibliography
Glusker J P, Trueblood 1972 Crystal Structure Analy
sis: A Primer. Oxford University Press, New York
International Tables for X-Ray Crystallography
1969
Kynoch Press, Birmingham, UK
Ladd M F C , Palmer R A 1977 Structure Determination by
X-Ray Crystallography. Plenum, New York
Luger 1980 Modern X-Ray Analysis on Single-Crystals.
DeGruyter, New York
Sands D 1969 Introduction to Crystallography. Benjamin,
New York
Stout G H, Jensen L 1968 X-Ray Structure Determi
nation: A Practical Guide. Macmillan, New York
C. F . C a m p a n a
[Nicolet C o r p o r a t i o n , C u p e r t i n o ,
California, U S A ]
462
Q = k-k
(2)
w h e r e k0 a n d k a r e t h e w a v e vectors of t h e incident
a n d t h e scattered r a d i a t i o n . F o r elastic scattering,
\k\ = \k0\ a n d Q = \Q\ is simply
w h e r e is t h e w a v e l e n g t h of t h e incident r a d i a t i o n
a n d 2 is t h e scattering angle. " S m a l l " angles m e a n s
limiting Q t o values smaller t h a n a b o u t n/da w h e r e da
is t h e i n t e r a t o m i c d i s t a n c e . T h u s , t h e discrete posi
tions of t h e individual scattering centers will n o t b e
resolved a n d a c o n t i n u o u s function p(r) describing t h e
d i s t r i b u t i o n of scattering length, locally a v e r a g e d over
a n infinitesimal v o l u m e e l e m e n t dr a r o u n d t h e posi
t i o n vector r, m a y be used, leading t o
F(Q)=lp(r)cxp(-iQ.r)dr
(4)
Small-Angle
Neutron
Scattering
in
Metallurgy
S(Q)>. <.exp(-Q R d)
(10)
()
R d=V^lr dq{rd)drd
Figure 1
Neutron scattering lengths of the lighter elements and of
some isotopes (a compilation is given by Kostorz (1979))
F (Q) = (p ~p )i
P
e x p ( - iQ.r) dr
(5)
w h e r e r is t a k e n from t h e g e o m e t r i c a l center of t h e
particle of v o l u m e Vp, a r e d u c e d single-particle scat
tering function
S(Q)=
(6)
(P -PJ%
(8)
for Qh>
\>Qa
(rods), while
(9)
m a y d e p e n d o n t h e direction of , as rd is m e a s u r e d
from t h e particle center in t h e direction d p e r p e n d i c u
lar t o k0 within t h e p l a n e defined b y Q a n d k0, with
q(rd) ( = cross-sectional a r e a ) p e r p e n d i c u l a r t o d. T h e
a v e r a g e " i n e r t i a l d i s t a n c e " Rd relative t o t h e p l a n e
c o n t a i n i n g k0 a n d t h e center of m a s s of t h e particle is
a n i n d i c a t i o n of its size a l o n g d.
T h e r a n d o m o r i e n t a t i o n a l a v e r a g e of E q n . (10)
yields
(12)
w h e r e t h e r a d i u s of g y r a t i o n is given by
R2 _
\r dr
(13)
2
F o r u n i f o r m spheres of r a d i u s Rs, R G = 3R /5 a n d t h e
G u i n i e r a p p r o x i m a t i o n h o l d s for QRG
1.2. F o r
o t h e r particle s h a p e s , t h e Q r a n g e m a y be smaller.
A n o t h e r useful a p p r o x i m a t i o n for h o m o g e n e o u s
particles with s h a r p b o u n d a r i e s ( b u t n o s h a r p edges o r
c o r n e r s ) h o l d s for larger Q (larger t h a n t h e reciprocal
value of t h e s h o r t e s t linear d i m e n s i o n of t h e particle):
t h e P o r o d a p p r o x i m a t i o n c o m b i n e s particle v o l u m e
a n d particle surface a r e a Ap a c c o r d i n g t o (orienta
t i o n a l average)
SP(Q)^
vlQ
(14)
T h e e x p e r i m e n t a l l y accessible t o t a l s t r u c t u r e func
tion St(Q) for a system c o n t a i n i n g
particles is a
simple s u p e r p o s i t i o n of TV single-particle scattering
functions only for identical a n d widely s e p a r a t e d
particles. T h e general case of a dense system of
particles, w i t h spatial a n d o r i e n t a t i o n a l c o r r e l a t i o n s
a n d a d i s t r i b u t i o n of sizes, c a n n o t b e solved analyti
cally. Size d i s t r i b u t i o n s m a y b e o b t a i n e d with s o m e
confidence if t h e particles a r e n o t t o o a n i s o m e t r i c a n d
n o interparticle interference intervenes (dilute, i.e.,
v o l u m e fractions of a few p e r c e n t ) . M o d e l calcula
tions o r n u m e r i c a l s i m u l a t i o n m e t h o d s a r e helpful in
m o r e c o m p l e x cases.
463
Small-Angle
Neutron
Scattering
in
Metallurgy
7 = V ~ J S t ( dQ = (InYW)
6 4 cm
(15)
6 4 cm
1-20 m
2
I=(2n) Cp(l-CpXPp-pm)
(16)
w h e r e C p = NVJV
is t h e v o l u m e fraction of t h e
2
particles. F o r i s o t r o p i c systems, Toe$S t(Q)Q dQ is t h e
second m o m e n t of t h e scattering d i s t r i b u t i o n .
W i t h its m a g n e t i c m o m e n t , t h e n e u t r o n also p r o b e s
the local m a g n e t i z a t i o n d i s t r i b u t i o n . A s a result of
1
the
this m a g n e t i c dipole i n t e r a c t i o n , only M (Q),
c o m p o n e n t of t h e F o u r i e r t r a n s f o r m M(Q) of t h e
locally a v e r a g e d m a g n e t i z a t i o n density M(r) w h i c h is
p e r p e n d i c u l a r t o Q, c o n t r i b u t e s t o m a g n e t i c smallangle n e u t r o n scattering. U s i n g p o l a r i z e d n e u t r o n s
a n d n e u t r o n spin analysis, quite detailed i n f o r m a t i o n
o n t h e spatial a n d o r i e n t a t i o n a l d i s t r i b u t i o n of m a g
netization m a y b e o b t a i n e d . A l t h o u g h t h e theoretical
b a c k g r o u n d is well d e v e l o p e d (see references given b y
K o s t o r z (1991)), a p p l i c a t i o n s a r e still very scarce
owing t o e x p e r i m e n t a l limitations.
2. Experimental
Considerations
(17)
w h e r e Ts = exp( >) is t h e t r a n s m i s s i o n of t h e
s a m p l e c o n t r o l l e d b y t h e t o t a l r e m o v a l cross section
(linear a b s o r p t i o n coefficient) c o n t a i n i n g t r u e a b s o r p
tion, i n c o h e r e n t a n d inelastic scattering, B r a g g scat
tering a n d s o o n ; Cl is a c o n s t a n t b a c k g r o u n d d u e t o
i n c o h e r e n t scattering; a n d is t h e d e t e c t o r efficiency.
T h e t e r m s 0 , a n d c a n b e eliminated b y a
c a l i b r a t i o n m e a s u r e m e n t with a s a m p l e of k n o w n
scattering p o w e r (e.g., i n c o h e r e n t scattering from
464
3 0 mm
Sample
2 0 mm
Figure 2
Schematic of a small-angle neutron scattering experiment
with typical dimensions. Lines of equal intensity on the
two-dimensional position-sensitive detector are shown on
the right; they were obtained from a rolled aluminum
alloy sheet. Some texture-related azimuthal variation of
scattering intensity is visible
v a n a d i u m o r w a t e r ) . T h e o p t i m u m s a m p l e thickness is
o b t a i n e d from
= 1 a n d , for m o s t m a t e r i a l s ,
a m o u n t s t o a few millimeters t o several centimeters
for n e u t r o n w a v e l e n g t h s b e t w e e n 0.2 n m a n d 0.6 n m .
W i t h r a y s only very t h i n foils c a n b e investigated in
t r a n s m i s s i o n b e c a u s e of high a b s o r p t i o n a n d w a v e
lengths a b o v e t h e B r a g g cutoff c a n n o r m a l l y n o t b e
used a t all. D o u b l e B r a g g scattering m a y often cause
a d d i t i o n a l scattering a t small angles w h i c h m a y b e
a v o i d e d b y u s i n g " c o l d " n e u t r o n s . T h e available
intensities a n d w a v e l e n g t h s ( u p t o a b o u t 2 n m ) limit
t h e size of scattering objects t o b e analyzed with
such a n a r r a n g e m e n t t o a b o u t 1 . L a r g e r i n h o m o
geneities m a y b e studied with special double-crystal
diffractometers.
3.
Applications
M e t a l l u r g i c a l a p p l i c a t i o n s of S A N S m a y r a n g e from a
simple check of s a m p l e h o m o g e n e i t y t o very detailed
studies of p r e c i p i t a t i o n o r defect a g g l o m e r a t i o n . A
few e x a m p l e s a r e given in t h e following; m o r e m a y b e
f o u n d in recent reviews ( K o s t o r z 1988, 1989, 1991).
T h e e v o l u t i o n of t h e m i c r o s t r u c t u r e of a d e c o m p o s
ing alloy m a y b e studied b y c o m p a r i n g a n u m b e r of
s a m p l e s after v a r i o u s h e a t t r e a t m e n t s .
SANS
measurements must then be performed at tempera
tures w h e r e m i c r o s t r u c t u r a l c h a n g e s a r e suppressed.
T h i s a p p r o a c h is viable for relatively slow processes.
I n - b e a m S A N S m o n i t o r i n g of t h e d e c o m p o s i t i o n o r
reversion of a n alloy is possible a t t e m p e r a t u r e s w h e r e
t h e time c o n s t a n t s a r e a p p r o p r i a t e . W i t h p r e s e n t large
d e t e c t i o n systems, a sufficient n u m b e r of S A N S events
c a n b e detected a t t i m e intervals of less t h a n 0.1 s,
close t o t h e time n e e d e d t o establish a h o m o g e n e o u s
t e m p e r a t u r e a c r o s s a n y s a m p l e . (Cyclic c h a n g e s , such
Small-Angle
Neutron
Scattering
in
Metallurgy
Figure 3
Scaled structure function s(x,t) according to Eqn. (18), = QL(t) = Q/Qm, for (a) Al-6.8 at.%Zn aged at 313
and
3
6
(b) Al-10at.%Zn aged at 291 for the indicated (total) aging times; the continuous line is the function 3x /(2 + x ) (after
Komura et al. 1984, 1985. Reproduced with permission)
,
= L\t)s[QL(tlt]
(18)
= At~\
Slm(t)
= Bt
(19)
with c o n s t a n t s A a n d B, c o n s t a n t e x p o n e n t s a a n d b,
a n d b = 3a if scaling h o l d s . Scaling is expected in t h e
O s t w a l d ripening regime w i t h / = c o n s t a n t ( v o l u m e
fraction a n d c o m p o s i t i o n of particles r e m a i n i n g c o n
s t a n t ) a n d 3a = b = 1. M a n y m o r e c o m p l e x s i t u a t i o n s
a r e n o w often p r e s e n t e d in scaled form. F o r p o l y c r y s talline s a m p l e s , t e x t u r e a n d g r a i n - b o u n d a r y effects
465
Small-Angle
Neutron
Scattering
in
Metallurgy
Figure 4
Small-angle scattering pattern for an Al-6.8 at.%Zn single
crystal with {110} faces perpendicular to the incident
beam. The other crystallographic orientations are
indicated. After quenching, the crystal was aged in situ at
room temperature for (a) 2 h and (b) 7.5 h. The azimuthal
dependence of the maximum intensity is visible (after
Kostorz 1991)
spherical t o o b l a t e ellipsoidal s h a p e . T h i s t r a n s i t i o n as
well as t h e l o n g - r a n g e c o r r e l a t i o n s a l o n g <100> a r e
primarily d u e t o t h e elastic misfit of c o h e r e n t precipi
tates. I n nickel-rich n i c k e l - a l u m i n u m w h e r e c o h e r e n t ,
o r d e r e d N i 3 A l precipitates form, t h e elastic misfit is
larger. A single crystal of N i - 1 2 a t . % A l aged a t 833
s h o w s a similarly a n i s o t r o p i c S A N S p a t t e r n (Fig. 5a)
with interference m a x i m a a n d l a r g e - b e h a v i o r
related t o a c u b o i d a l s h a p e . If t h e m i s m a t c h b e t w e e n
precipitates a n d m a t r i x is essentially eliminated by a n
a d d i t i o n of m o l y b d e n u m , t h e precipitates r e m a i n
spherical, a n d n o preferred a l i g n m e n t is visible (Fig.
5b). In situ a g i n g e x p e r i m e n t s o n these alloys also
s h o w a m a r k e d c h a n g e in t h e g r o w t h r a t e of precipi
tates, as illustrated in Fig. 6.
466
Figure 5
Isointensity plots (counts in 20 min) of SANS data for
single crystals of (a) Ni-12 at. %A1 aged for 35 min at
833 K, (b) Ni-6.1 at.%Al-9.4 at.%Mo aged for 3.9 h at
883 K. The incident beam ( = 0.66 nm 10%) was
parallel to [110] (after Calderon and Kostorz 1990)
Small-Angle
50
40
30 L-
20
10
,cP
10
/ (h)
Figure 6
Cube of the radius of gyration i? G as a function of aging
time t for / formation in N i - A l - M o single crystals of
variable mismatch m = Aa/ay: A , Ni-12 at.%Al,
m = 1.2%; , Ni-10.3 at.%Al-5.5 at.%Mo, m = 0.6%;
, Ni-6.5 at.%Al-9.6 at.%Mo, m a 0;
O, Ni-6.1 at.%Al-9.4at.%Mo, m 0. The aging
temperature was 833 except for the open circles where it
was 883 (after Calderon and Kostorz 1990)
Neutron
Scattering
in
Metallurgy
V e r y often in S A N S studies of s t r u c t u r a l m a t e r i a l s ,
h o w e v e r , t h e s i m u l t a n e o u s presence of several inh o m o g e n e i t i e s , such a s d e c o m p o s i t i o n p r o d u c t s ,
c a r b i d e s , inclusions a n d p o r e s , c o m p l i c a t e s t h e inter
p r e t a t i o n o f (possibly small) c h a n g e s . If t h e c h a n g e s
o c c u r in t h e tail region o f t h e S A N S curve, t h a t is, if
t h e n e w scattering objects a r e small, such m e a s u r e
m e n t s m a y nevertheless yield useful i n f o r m a t i o n . A d
d i t i o n a l evidence m a y c o m e from m a g n e t i c scattering
t e r m s a s s h o w n , for e x a m p l e , in F i g . 7. H e r e , t h e e x t r a
S A N S intensity, using u n p o l a r i z e d n e u t r o n s , is s h o w n
for a r e a c t o r p r e s s u r e vessel steel i r r a d i a t e d w i t h fast
19
2
n e u t r o n s (3 10 c m " , E> 1 M e V ) a t 563 a n d
s u b s e q u e n t l y a n n e a l e d (24 h a t 693 K ) , w i t h Q either
parallel o r p e r p e n d i c u l a r t o t h e m a g n e t i c field H. T h e
scattering parallel t o / / i s extremely small. A s t h e r a t i o
/ r e m a i n s essentially i n d e p e n d e n t of Q, there is
s t r o n g evidence for only o n e t y p e of defect cluster
( r a d i u s less t h a n 1 n m , v o l u m e fractions less t h a n
3
2 x 10" ). T h e a u t h o r s suggest t h a t v a c a n c y - c o p p e r
or copper-manganese-vacancy aggregates form dur
ing i r r a d i a t i o n w h i c h a r e modified o n a n n e a l i n g a n d
reirradiation.
See also: Polymers: Neutron Scattering; Polymers: X-Ray
Scattering; X-Ray and Neutron Diffraction Studies of
Amorphous Solids
Bibliography
0.5
1.0
2.0
1
0 (nm" )
4.0
Figure 7
SANS intensities (logarithmic scale) due to the defects in a
reactor pressure vessel steel after irradiation with fast
neutrons and a subsequent anneal (see text). The
scattering from an unirradiated reference sample has been
subtracted. Measurements were performed in magnetic
saturation, parallel ( O ) and perpendicular ( ) to the
magnetic field. The solid lines are calculated for spherical
particles of an average radius R = 0.83 nm; AR/R = 0.246
(after Solt et al. 1989. Reproduced with permission)
467
Small-Angle
Neutron
Scattering
in
Metallurgy
181:
1989
Ves
and
G. Kostorz
[ Z u r i c h , Z u r i c h , Switzerland]
of Track
Production
and
Revelation
T r a c k s a r e f o r m e d in t h e three m a j o r classes of
insulating solids: crystals, glasses a n d p o l y m e r s
= sin" (vcyvj)
Figure 1
Track geometry for constant general dissolution rate v G
and two different track attack rates vT: the track with the
lower v T is smaller, shorter and blunter (Fleischer 1981)
( Y o u n g 1958, Fleischer a n d Price 1963a, b ) . F i g u r e 1
illustrates h o w chemical e t c h i n g reveals t r a c k s a s
holes t h a t a r e conical in i s o t r o p i c m a t e r i a l s such as
glasses. T h e c o n e angle is s h a r p e r t h e g r e a t e r t h e
value of v T / v G (the r a t i o of t h e preferential r a t e of
d i s s o l u t i o n a l o n g t h e t r a c k t o t h e general a t t a c k r a t e ) .
F i g u r e 2 gives e x a m p l e s of t r a c k s in a plastic, a glass
a n d a crystal. I t illustrates t h e w i d e v a r i a t i o n in t h e
o b s e r v e d value of a n d of t h e size t o w h i c h t r a c k s
m a y b e etched. Small values a r e frequent in crystals
a n d high p o l y m e r s , a n d a r e seen in certain glass
Figure 2
Photographs of etched tracks of different sizes in different classes of solids: (a) 2 3 U
5
fission tracks in muscovite mica;
(b) fission tracks in ordinary glass; (c) 700 long track of a heavy cosmic ray nucleus in the plastic of an Apollo helmet
468
Solid-State
c o m p o s i t i o n s . T h e value of d o e s v a r y w i t h d a m a g e
intensity, as is illustrated b y F i g . 2c.
1.3 Particle
Track
Detectors:
2.
Uses of Etched
Particle
Tracks
Table 1
Relative sensitivities of various inorganic detectors"
Detector
Atomic composition
Figure 3
Ionization against velocity for different charged particles
travelling through Lexan polycarbonate (thresholds for
other detectors are also indicated) (Fleischer 1981)
Least-ionizing
ion seen
100 MeV *Fe
MgFeSi64
Diopside
Augite
CaMg(Si0 3) 2
CaMg 3Fe 3Al 2Si 40 19
170 MeV*Fe
56
170 MeV Fe
Oligoclase
Bytownite
Orthoclase
Quartz
Na 4CaAl 6Si 1 4O 40
NaCa^Si,^
KAlSi 3O g
Si0 2
4MeV 2 8Si
4MeV Si
100 MeV <Ar
100 MeV <Ar
Phlogopite
mica
Muscovite
mica
MgSi03
Soda lime
glass
Phosphate
glass
28
20
2MeV Ne
Velocity v/c
Applications
function of i o n i z a t i o n r a t e allows i n d i v i d u a l n u c l e a r
particles t o b e identified b y m e a s u r i n g v T o r a l o n g a
t r a c k (Price et al. 1968. Fleischer et al. 1970). F i g u r e 5
s h o w s h o w t h e t a p e r of a t r a c k s u c h a s is s h o w n in
F i g . 2c is derived geometrically. U s i n g curves such as
t h o s e in F i g . 3 a n d c a l i b r a t i o n d a t a from o t h e r ions,
t h a t p a r t i c u l a r t r a c k is inferred t o b e from a fastm o v i n g zinc ion t h a t c a m e t o rest in t h e d e t e c t o r .
Identification
T h e fact t h a t t h e e t c h i n g r a t e v T a l o n g a t r a c k is a
Nuclear
20
2-4MeV Ne
20 MeV N e
469
Solid-State
Nuclear
Track
Detectors:
Applications
Table 2
Relative sensitivities of various organic detectors*
Detector
Amber
Atomic
composition
C 2H 30 2
Phenoplaste
Polyethylene
C 7H 60
CH 2
Polystyrene
CH
Polyvinylacetochloride
C 6H 90 2C1
PolyvinylchlorideC2H3C1 + C2H2C12
polyvinyledene chloride
copolymer
Least-ionizing
ion seen
Full-energy
fission
fragments
Fission
fragments
32
42 MeV 3 2S
42 MeV S
( b)
Polyethylene
terephthalate (Cronar,
Melinex)
Polyimide
Ionomeric polyethylene
(Surlyn)
C 5H 40 2
Bisphenol
A-polycarbonate
(Lexan, Makrofol)
C, 6H l 40 3
Polyoxymethylene
(Delrin)
CH 20
Polypropylene
CH 2
lMeV He
Polyvinylchloride
Polymethylmethacralate
(Plexiglas)
C2H3C1
C 5H 80 2
3MeV He
CH 40 4N 2
(a)
36 MeV'O
, 6
36 MeV 0
0.3MeV He
Ionization
Electrostatic
displacement
Figure 4
The ion explosion spike mechanism for track formation in
inorganic solids: the original ionization left by passage of
a charged particle (a) is unstable and ejects ions from their
sites, creating vacancies and interstitials (b); later the
stressed region relaxes elastically, straining the undamaged
matrix (Fleischer et al. 1965b)
28 MeV "B
Etched surface
[-Original
surface
C 3H 40 2
Incoming
particle
C, 2H 1 80 7
C 6H 80 9N 2
0.55 MeV
1.5 MeV
5 MeV
470
Figure 5
Diagram illustrating how a measure of a diameter D as a
function of distance X on a residual range R from the end
of the track determines the cone angle at positions along
an etched track, allowing particles to be identified
(Feischer et al. 1970)
Solid-State
2.1 Scientific
Figure 6
Radiograph showing the location of plutonium in the
lumbar vertebra of a dog which had been given 2.7 of
2 3 9P ukg- and killed 28 days later (courtesy of W. S. S.
Jee): labelled are three trabeculae with surface deposits of
2 3 9P u (S), osteoclasts with 2 3 Pu
9
aggregates on bone
surfaces (O), macrophages with star-producing aggregates
in bone marrow (M) and bone image (B)
Nuclear
Track
Uses of
Tracks
Detectors:
Applications
mica
sphene"
1000oooooo
whitlockite
</
^7f
apatite^ mica
apa^ite^homblende
allanite
z i r c o n ^ a p a t i t e , sphene
> mica, apatite
. a ippaattiittee
#'tektites
t e k t i t e s F /CM I 2C < ,
s h a r d s , * ^i P
m a tc
lass
,apatite,epidote,sphene-
<3
o b s i d i a n . ' e b s i nd i a
shards^Pumice
obsidians
tektites
zircon
000000
1000
synthetic
glass
v.
uranium - mica
pair
1000000
1000000000
Figure 7
Graph comparing fission track ages, measured by counting natural tracks formed by spontaneous fission of 2 3 U
8 , with ages
known by other means, either documented ages for man-made samples or ages measured by other radioactive decay
techniques for the geological samples (Fleischer et al. 1975)
471
Solid-State
Nuclear
Track Detectors:
Applications
Figure 8
Airborne salt particles from marine air near Hawaii,
caught by a Nucleopore filter: the uniform, slightly mat
surface of the filter provides good contrast with
particulates, as shown on this scanning electron
micrograph (photograph taken by E. R. Ackerman of the
US National Center for Atmospheric Research)
Figure 9
Detector cup used for track etching measurements of
indoor 2 2 Rn.
2
A high-permeation membrane cover admits
only the longest-lived radon isotope. A desiccant package
in the cup restricts the condensation of moisture. The
track detector is the rectangular piece of plastic at the
bottom of the cup
472
Solid State:
2 2 2
noble, r a d i o a c t i v e gas
R n (Fleischer et al. 1980),
which in h o m e s is a h a z a r d a n d in t h e g r o u n d is a
tracer for u r a n i u m (Fleischer et al. 1972, G i n g r i c h
1975), oil a n d g a s ( F l e i s c h e r a n d T u r n e r 1984)
and impending e a r t h q u a k e s (Fleischer a n d M o g r o C a m p e r o 1985). T h e s i m p l e , p a s s i v e device t h a t is
used t o p r o d u c e l o n g - t i m e a v e r a g e s of r a d o n c o n c e n
t r a t i o n (Alter a n d Price 1972, F l e i s c h e r a n d M o g r o C a m p e r o 1978) is s h o w n in F i g . 9. T h e t r a c k - d e t e c t
ing plastic a t t h e e n d of t h e c u p r e c o r d s a l p h a
2 2 2
particles e m i t t e d b y
R n w h i c h diffuses i n t o t h e
c h a m b e r . B e c a u s e of t h e s h o r t r a n g e of a l p h a p a r t i
cles f r o m n a t u r a l r a d i o n u c l i d e s , t h e c u p walls a n d
m e m b r a n e shield o u t all e x t r a n e o u s a l p h a p a r t i c l e s ;
t h e m e m b r a n e b y its c h o s e n p e r m e a b i l i t y a d m i t s
2 2 2
only
R n , t h e i s o t o p e of i n t e r e s t . F o r use in t h e
ground the desiccant takes u p moisture that other
wise m i g h t c o n d e n s e o n t h e d e t e c t o r a n d shield it
from r a d o n a l p h a p a r t i c l e s .
Study
Using Muon
Beams
Bibliography
Alter W, Price 1972 Radon detection using track
registration material. US Patent No. 3,665,194
DeBlois R W, Bean C 1970 Counting and sizing of
submicron particles by the resistive pulse technique. Rev.
Sci. Instrum. 41: 909-16
Fleischer R L 1981 Nuclear track production in solids.
Prog. Mater. Sci. Chalmers Anniversary Volume: 9 7 123
Fleischer R L, Alter W, Furman S C, Price , Walker
R 1972 Particle track etching. Science 178: 255-63
Fleischer R L, Giard W R, Mogro-Campero A, Turner L
G, Alter W, Gingrich J 1980 Dosimetry of environ
mental radon: methods and theory for low-dose inte
grated measurements. Health Phys. 39: 957-62
Fleischer R L, Hart R Jr, Giard W R 1970 Particle track
identification: application of a new technique to Apollo
helmets. Science 170: 1189-91
Fleischer R L, Mogro-Campero A 1978 Mapping of inte
grated radon emanation for detection of long-distance
migration of gases within the earth: techniques and prin
ciples. J. Geophys. Res. 83: 3539-49
Fleischer R L, Mogro-Campero A 1985 Association of
subsurface radon changes in Alaska and the Northeastern
United States with earthquakes. Geochim Cosmochim.
Acta 49: 1061-71
Fleischer R L, Price 1963a Charged particle tracks in
glass. J. Appl. Phys. 34: 2903-4
Fleischer R L, Price 1963b Tracks of charged particles
in high polymers. Science 140: 121-2
Fleischer R L, Price , Symes 1964 Novel filter for
biological studies. Science 143: 249-50
Fleischer R L, Price , Walker R 1965a Tracks of
charged particles in solids. Science 149: 383-93
Fleischer R L, Price , Walker R 1965b Ion explosion
spike mechanism for formation of charged-particle tracks
in solids. J. Appl. Phys. 36: 3645-52
473
Solid State:
Study
Using Muon
1. Muon
Production
Methods
in Solid-State
Beams
and Detection:
Nuclear
T h e e x p e r i m e n t a l techniques for p r o d u c i n g a n d
detecting m u o n s h a v e c o m e t o be k n o w n collectively
as //SR, s t a n d i n g for m u o n spin r o t a t i o n , r e l a x a t i o n
a n d r e s o n a n c e (Brewer et al. 1975). T h e y are practised
at t h o s e accelerator l a b o r a t o r i e s o r m e s o n factories
w h e r e low-energy m u o n b e a m s a r e available. T h e
m u o n s derive from t h e decay of p i o n s , themselves
p r o d u c e d w h e n a target of g r a p h i t e o r o t h e r light
element is e x p o s e d t o a sufficiently energetic p r i m a r y
p r o t o n b e a m . T h e success of / / S R s p e c t r o s c o p y relies
o n t w o c i r c u m s t a n c e s . T h e first is t h e intrinsically
high degree of spin p o l a r i z a t i o n of t h e m u o n b e a m s
( u p t o 1 0 0 % for t h o s e collected from the d e c a y of
p i o n s a t rest), a n d t h e fact t h a t this initial p o l a r i z a t i o n
is largely preserved w h e n t h e m u o n s a r e s t o p p e d o r
thermalized in t h e s a m p l e of interest. T h e second is
the m a n n e r in which the s u b s e q u e n t e v o l u t i o n of
p o l a r i z a t i o n within t h e s a m p l e m a y t h e n be displayed.
T h e m u o n is itself a n u n s t a b l e particle, a n d decays
with a lifetime of 2.2 . A s e a c h m u o n decays, it emits
a p o s i t r o n in a direction which is closely c o r r e l a t e d
with its i n s t a n t a n e o u s spin o r i e n t a t i o n . T h i s is t h e
classic e x a m p l e of p a r i t y violation in r a d i o a c t i v e
decay, a n d its discovery by G a r w i n et al. (1957)
represented the s t a r t i n g p o i n t for the d e v e l o p m e n t of
this novel spectroscopy; these a u t h o r s were well
a w a r e of the p o t e n t i a l , a n d c o n c l u d e d their article
with the perceptive s t a t e m e n t " . . . it seems possible
t h a t polarized positive a n d negative m u o n s will
b e c o m e a powerful t o o l for e x p l o r i n g m a g n e t i c fields
in nuclei, a t o m s a n d i n t e r a t o m i c r e g i o n s . "
T h e decay p o s i t r o n s ( emission) m a y be c o u n t e d in
o n e or m o r e directions using scintillation d e t e c t o r s .
This use of " n u c l e a r m e t h o d s " of single particle
c o u n t i n g c o n t r i b u t e s hugely t o t h e r e m a r k a b l e sensiti
vity of / / S R spectroscopy. It p r o v i d e s a form of trigger
detection for m a g n e t i c r e s o n a n c e in which t r a n s i t i o n s
of the m u o n spin (typically in a frequency r a n g e
between kilohertz a n d gigahertz) a r e detected a t t h e
energy of the r a d i o a c t i v e decay. C u r i o u s as it s o u n d s
to use such a short-lived e l e m e n t a r y particle for a
solid-state p r o b e , t h e m u o n lifetime in fact defines a n
invaluable timescale for certain d y n a m i c a l studies,
w h e t h e r of h o p rates in diffusive m o t i o n , o r of fluc
t u a t i n g fields in m a g n e t i c m a t e r i a l s . V a r i o u s reviews
of the techniques a n d a p p l i c a t i o n s a r e available
(e.g., S t o n e h a m 1979, 1983, Schenck 1985, C o x 1987);
the following is a selection of highlights a n d recent
developments.
2. Semiconductors
Defect
Centers
and Insulators:
Hydrogenlike
F o r a fully p o l a r i z e d m u o n b e a m , a n d c o u n t i n g
p o s i t r o n s of all energies, t h e emission is a b o u t twice
474
<
10 > / /
Science
Figure 1
Level crossing resonance spectrum for a muonium defect
center in CuCl (after Schneider 1990: the spectrum
represents resonant polarization transfer from the muon
to the neighboring nuclei, defining the defect site and
determining local superhyperfine interactions)
Solid State:
Temperature
(K)
Study
Temperature
(a)
Using Muon
Beams
(K)
(b)
Figure 2
Temperature dependence of muon spin-lattice relaxation rate in KC1, for three values of external field, and the extracted
rates for interstitial hopping (after Kadono 1990)
3. Molecular
Chemistry
Materials:
Muon
and
Muonium
I n m o l e c u l a r m a t e r i a l s , m u o n i u m reacts like a t o m i c
h y d r o g e n t o b e c o m e i n c o r p o r a t e d in a w i d e variety of
m o l e c u l a r species, b o t h d i a m a g n e t i c (closed shell) a n d
p a r a m a g n e t i c ( o p e n shell). T h a n k s t o t h e u n p r e c e
d e n t e d m a s s r a t i o , i s o t o p e effects in t h e r e a c t i o n
kinetics as well as in t h e one-electron m o l e c u l a r
p r o p e r t i e s of t h e p r o d u c t s a r e c o n s i d e r a b l y g r e a t e r
t h a n t h o s e o b s e r v e d w i t h , for e x a m p l e , d e u t e r i u m .
M o s t a t t e n t i o n h a s b e e n p a i d t o t h e hyperfine i s o t o p e
effect in m u o n i u m - s u b s t i t u t e d o r g a n i c radicals, w h i c h
m a y b e t r a c e d t o t h e large z e r o p o i n t energy of
m u o n i u m b o u n d in c o v a l e n t c a r b o n - m u o n i u m o r
o x y g e n - m u o n i u m b o n d s ( R o d u n e r 1988, C l a x t o n et
al. 1990). A similar q u a d r u p o l e i s o t o p e effect h a s
recently b e e n o b s e r v e d in a closed shell species,
n a m e l y t h e m u o n i u m - s u b s t i t u t e d w a t e r molecule
H M u O ( C o x et al. 1990).
T h e labelling of large molecules b y m u o n i u m
a d d i t i o n is a p o t e n t i a l l y i m p o r t a n t t o o l . I n transpolyacetylene, for i n s t a n c e , t h e u n p a i r e d electron
i n t r o d u c e d b y this p r o c e s s is free t o m i g r a t e a l o n g t h e
c h a i n as a b o n d - a l t e r n a t i o n defect o r soliton. T h e
soliton m o t i o n in this a n d o t h e r c o n d u c t i n g p o l y m e r s
475
Solid State:
Study
Using Muon
Beams
Mu*
Mu
15 r
> LULU
0
l
500
1000
Frequency (MHz)
L_
1500
(a)
(b)
Figure 3
(a) The //SR spectrum of GaAs showing frequencies corresponding to the normal (Mu) and anomalous (Mu*) muonium
defect centers (after Kiefl et al. 1985) and (b) the "bond-center"
model for Mu* in which the muon lies close to the node
3
of the singly occupied molecular orbital, constructed from sp hybrids on the host atoms (after Cox and Symons, 1986)
Spin Structure
and
Dynamics
L
I
o o o cPoo
_ 100
Time
()
Temperature
()
(b)
Figure 4
(a) The muon spin rotation signal recorded for L a 2 C u 0 4 in zero external field displays the presence of (antiferro) magnetic
order (after Budnik et al. 1987) and (b) the muon spin relaxation rates recorded for single-crystal erbium with muon spin
parallel (squares) and perpendicular (circles) to the c axis reveal a striking anisotropy in the critical spin fluctuations (after
Hartmann et al. 1990)
476
Solid State:
Study
Using Muon
Beams
2.0
2222
=1.
123
2212
1.0
b
22mT ( R A D
3 5 0 mT ( P S I )
214
_L
1
-40
(a)
()
(b)
Figure 5
(a) Correlation of //SR linewidth with transition temperature Tc for various superconductor families (after Uemura et al.
1990) and (b) its variation with orientation for single-crystal Y B a 2 C u 3 0 7 _ 6 (after Forgan et al. 1990). Linewidth is
proportional to the variance of the internal field and to the inverse square of the London penetration depth
wyvw
w\^vv
(a)
(b)
wvyw
(c)
Figure 6
Interstitial localization of the positive muon as a small
polaron defect in metals (a) and the elemental diffusive
step via phonon-assisted tunnelling (b, c): thermal
fluctuations provide a favorable intermediate
configuration for tunnelling between initial and final sites
Mapping
Internal
Fields
It is p e r h a p s t h e s t u d y of t h e s u p e r c o n d u c t i n g p h a s e s
themselves w h i c h h a s recently b r o u g h t pSR m e a s u r e
m e n t s t o t h e a t t e n t i o n of a wide a u d i e n c e . T h e elimi
n a t i o n of a n y o n m o d e l s of h i g h - r c s u p e r c o n d u c t i v i t y
(Kiefl et al. 1990) is a striking illustration of the
sensitivity of t h e m u o n m a g n e t o m e t e r . F o r t h e mixed
state of all t y p e II s u p e r c o n d u c t o r s , c o n v e n t i o n a l a n d
high-7^, the pSR frequency s p e c t r u m serves t o m a p
the d i s t r i b u t i o n of i n t e r n a l flux within the vortex
system ( H e r l a c h et al. 1990); t h e linewidth is directly
p r o p o r t i o n a l t o the field c o n t r a s t ( r a t h e r t h a n the
s q u a r e of this q u a n t i t y , a s for diffraction m e t h o d s )
a n d u n d o u b t e d l y p r o v i d e s t h e m o s t reliable m e a s u r e
m e n t of L o n d o n p e n e t r a t i o n d e p t h . T h i s q u a n t i t y is
i n t i m a t e l y related t o t h e p a i r i n g m e c h a n i s m of the
s u p e r c o n d u c t i n g carriers, via their c o n c e n t r a t i o n a n d
effective m a s s . Its m e a s u r e m e n t for such a wide var-
477
Solid State:
Study
Using Muon
Beams
10
Time
15
(/zs)
(a)
0.1
10
Temperature
100
(K)
(b)
Figure 7
(a) The zero-field relaxation function for muons in copper metal (this ISIS test spectrum is remarkable for displaying
evolution of the polarization beyond eight muon lifetimes, after Karlsson 1989). pSR provided the first demonstration of
this distinctive function, in which the polarization Pz(t) recovers at long elapsed time to ^ of its initial value, as predicted
by Kubo and Toyabe (1987). Relaxation of the J tail proves sensitive to extremely slow diffusion, (b) Collected results for
muon hop rates reveal quantum mobility at low temperatures as well as thermally activated motion (after Kadono et al.
1986)
iety of m a t e r i a l s a s t h e c u p r a t e high-!T c s u p e r c o n d u c
tors, heavy fermion systems, chevrel p h a s e s a n d even
o r g a n i c s u p e r c o n d u c t o r s , a n d t h e discovery o f a sys
tematic v a r i a t i o n with t r a n s i t i o n t e m p e r a t u r e w h i c h
e m b r a c e s all of these ( F i g . 5a) w o u l d b e u n t h i n k a b l e
w i t h o u t / / S R . Single-crystal m e a s u r e m e n t s also b e a r
o u t t h e p r e d i c t e d t e n s o r p r o p e r t i e s (Barford a n d
G u n n 1988) relating t o t h e a l m o s t t w o - d i m e n s i o n a l
c o n d u c t i o n in t h e layered c u p r a t e systems ( F i g . 5b).
6. Muons
in Metals:
Quantum
Dynamics
In m e t a l s , t h e u s e of m u o n s t o m i m i c p r o t o n b e h a v i o r
h a s been exploited t o t h e full, a n d every v a r i a n t of t h e
/zSR techniques b r o u g h t t o b e a r o n q u e s t i o n s relevant
t o h y d r o g e n in m e t a l s . I n p a r t i c u l a r , m u o n s in m e t a l s
h a v e been used t o clarify issues of q u a n t u m mobility:
they serve a s a testing g r o u n d for t h e f u n d a m e n t a l
p r o b l e m o f a q u a n t u m m e c h a n i c a l system (here a n
interstitial defect light e n o u g h t o t u n n e l ) c o u p l e d t o a
classical system (the electron a n d p h o n o n b a t h s ) . T h e
c o u p l i n g is large, so t h a t t h e initial m u o n state (which
m u s t be e x t e n d e d o n e n t r y a t e p i t h e r m a l energy)
collapses t o a localized state, " s e l f - t r a p p e d " w i t h i n a
single interstitial well. I n s e m i c o n d u c t o r s , t h e p h o n o n
c o u p l i n g is responsible for t h e localization; in m e t a l s
t h e electron c o u p l i n g is d o m i n a n t . Screening o f t h e
m u o n p o t e n t i a l b y a local a c c u m u l a t i o n o f electron
density is such a s t o p r e c l u d e t h e f o r m a t i o n of m u o n i u m (i.e., n o p a r a m a g n e t i c m o m e n t is c e n t e r e d o n
t h e m u o n ) a n d t h e local electronic s t r u c t u r e is d i a m a g n e t i c , a s it is for interstitial p r o t o n s . P h o n o n
478
Solid State:
p a r t of t h e electronic screening c h a n g e t o follow t h e
m u o n m o t i o n ( K o n d o 1985).
7.
Perspectives
T h e s e e x a m p l e s give a glimpse of t h e b r o a d r a n g e of
a p p l i c a t i o n of i m p l a n t e d m u o n studies. Classed w i t h
t h e n u c l e a r - p r o b e spectroscopies, / / S R p r o v i d e s infor
m a t i o n o n local s t r u c t u r e w h i c h ideally c o m p l e m e n t s
t h e fc-space i n f o r m a t i o n o b t a i n e d from diffraction
techniques, a n d c o n t r i b u t e s t o a detailed m i c r o s c o p i c
picture of m a t t e r .
By virtue of t h e m a s s a n d lifetime of t h e m u o n
p r o b e , / / S R studies significantly e x t e n d t h e r a n g e of
d y n a m i c a l p h e n o m e n a accessible t o c o n v e n t i o n a l
magnetic resonance.
T h e p r e s e n t s t a t u s of this relatively novel s p e c t r o s
c o p y is best c o m p a r e d w i t h t h a t of m a g n e t i c r e s o
n a n c e s o m e d e c a d e s a g o . R e s u l t s o n m o d e l systems
validate t h e t e c h n i q u e , b u t h a v e also p r o d u c e d s o m e
surprises ( n o t a b l y a s r e g a r d s h y d r o g e n defects in
s e m i c o n d u c t o r s a n d light interstitial diffusion in
metals) w h i c h h a v e c a u s e d established views t o b e
revised. N e w a n d m o r e c o m p l e x systems m a y n o w b e
tackled w i t h confidence. I n a m o r p h o u s a n d m e s o scopic s t r u c t u r e s , for i n s t a n c e b o t h metallic a n d semi
c o n d u c t i n g ) , issues of site o c c u p a n c y , site c o m p e t i t i o n
with h y d r o g e n a n d diffusion d y n a m i c s a r e well suited
t o m u o n study; such e x p e r i m e n t s a r e in their infancy,
but have considerable potential.
See also: Magnetic Materials: Measurements; Supercon
ducting Materials: Measurements; X-Ray Diffraction,
Time-Resolved
Bibliography
Ansaldo F J, Niedermeyer Ch, Stronach C 1991 Muonium
in Fullerite. Nature 353: 129
Barford W, Gunn J F 1988 The theory of the measure
ment of the London penetration depth in uniaxial type II
superconductors by muon spin rotation. Physica C 156:
515-22
Brewer J H, Crowe , Gygax F N, Schenck A 1975
Positive muons and muonium in matter. In: Hughes V W,
Wu C S (eds.) 1975 Muon Physics. Academic Press, New
York
Brewer J H, Crowe , Johnson R F, Patterson
D,
+
Fleming D G, Schenck A 1973 Anomalous precession
in silicon. Phys. Rev. Lett. 31: 143-6
Budnick J I, Golnick A, Niedermeyer Ch, Recknagel E,
Rossmanith M, Weidinger A, Chamberland B, Filipkowski M, Yang D 1987 Observation of magnetic
ordering in La 2Cu0 4 by muon spin rotation spectroscopy.
Phys. Lett. A 124: 103-6
Claxton A, Graham A M, Cox S F J, Marie D M, Meier
F, Vogel S 1990 Vibrationally averaged spin densities on
muons and protons in the hydroxyl and ethyl radicals.
Hyperfine Interact. 65: 913-26
Cox S F J 1987 Implanted muon studies in condensed matter
science. J. Phys. C 20: 3187-319
Study
Using Muon
Beams
479
Solid State:
Study
Using Muon
Beams
/.
Design
Considerations
I o n s are p r o d u c e d by a n rf s p a r k in w h i c h a n a l t e r n a t
ing c u r r e n t p o t e n t i a l of 10100 k V is g e n e r a t e d in
m i c r o s e c o n d pulses. T h e s p a r k o c c u r s between t w o
s a m p l e electrodes a n d i o n i z a t i o n m a y o c c u r as t h e
result of electron b o m b a r d m e n t of n e u t r a l v a p o r
p r o d u c e d in t h e s p a r k . T h e length of the s p a r k pulse
a n d t h e repetition r a t e a r e c o n t r o l l a b l e .
Since t h e i o n i z a t i o n energy available is m u c h
greater t h a n the i o n i z a t i o n p o t e n t i a l of the v a r i o u s
elements, essentially u n i f o r m i o n i z a t i o n efficiency is
o b t a i n e d . I n t h e o r y this allows a direct d e t e r m i n a t i o n
of elemental c o n c e n t r a t i o n by m e a s u r e m e n t of p h o toplate darkening.
O n e result of t h e e n o r m o u s a m o u n t of energy
involved in t h e i o n p r o d u c t i o n process by rf s p a r k is
a n i o n b e a m w i t h a large energy s p r e a d . E l e c t r o n
i m p a c t a n d t h e r m a l ion sources, for e x a m p l e , use
m u c h less energy in the i o n i z a t i o n process a n d as a
c o n s e q u e n c e energy s p r e a d s of less t h a n 1 eV are t o b e
f o u n d in ion b e a m s from these sources. T h e r e are t w o
3
far-reaching effects of t h e large ( 1 0 eV) energy s p r e a d
in rf s p a r k i o n b e a m s . T h e first dictates the use of a
double-focusing analyzer (Fig. 1) a n d t h e second
requires t h e use of a p h o t o g r a p h i c detector.
F i g u r e 1 illustrates t h e s p a r k - s o u r c e i n s t r u m e n t
s h o w i n g t h e source region w h e r e ions a r e formed, a n d
t h e double-focusing analyzer w h e r e t h e ions are first
energy filtered, t h e n m a s s analyzed a n d
finally
detected by the p h o t o g r a p h i c e m u l s i o n . T h e d o u b l e focusing analyzer used in all S S M S i n s t r u m e n t s is the
M a t t a u c h - H e r z o g analyzer. T h e resolution a t t a i n a b l e
d e p e n d s u p o n t h e energy s p r e a d in t h e ion b e a m , a n d
resolutions in the r a n g e 1000-5000 a r e n o r m a l for
s p a r k i n s t r u m e n t s . T h e p h o t o g r a p h i c emulsion is t h e
best d e t e c t o r for S S M S because its i n t e g r a t i n g p r o p e r
ties n e g a t e t h e wide v a r i a t i o n s in i o n - b e a m intensity
p r o d u c e d by the rf s p a r k source. I n a d d i t i o n , a n entire
m a s s s p e c t r u m from lithium t o u r a n i u m c a n b e s h o w n
o n the p h o t o p l a t e d u e t o t h e focusing p r o p e r t i e s of
t h e M a t t a u c h - H e r z o g analyzer. T h i s ability t o see t h e
Spark-Source
Mass
Spectrograph);
High-voltage
leads for spark
a n d ion
Figure 1
Spark-source instrument showing the source region and double-focusing analyzer
entire c o m p o s i t i o n of a s a m p l e is a g r e a t aid in
analytical s i t u a t i o n s . T h e universally used p h o t o
g r a p h i c e m u l s i o n is t h e llford Q - p l a t e .
2. Sample
Requirements
Since t h e i o n i z a t i o n p r o c e s s d e p e n d s o n b r e a k d o w n of
t h e g a p b e t w e e n t w o electrodes, a p a i r of solid c o n
d u c t i n g electrodes is o b v i o u s l y r e q u i r e d . S a m p l e s a r e
best c o n s i d e r e d a s o n e of t h e following types: solid
c o n d u c t o r s , p o w d e r e d c o n d u c t o r s , solid i n s u l a t o r s ,
p o w d e r e d i n s u l a t o r s , small s a m p l e s a n d liquids.
Solid c o n d u c t o r s n e e d o n l y b e c u t t o a c o n v e n i e n t
size. P o w d e r s , either c o n d u c t o r s o r i n s u l a t o r s , c a n b e
pressed i n t o solid s h a p e s w i t h c o m m e r c i a l s a m p l e
p r e p a r a t i o n dies a n d presses. S o m e m e t a l p o w d e r s
(e.g., silver) m a y b e pressed i n t o electrodes directly,
b u t m o s t m e t a l s a n d all i n s u l a t o r s will need t o b e
mixed w i t h a c o n d u c t o r before b e i n g pressed i n t o
electrodes. By far t h e m o s t useful c o n d u c t o r for these
s a m p l e s is h i g h - p u r i t y g r a p h i t e p o w d e r . U s u a l l y a
50:50 m i x t u r e of s a m p l e a n d g r a p h i t e is t h o r o u g h l y
mixed a n d pressed i n t o h o m o g e n e o u s , d u r a b l e
electrodes.
Solid i n s u l a t o r s a m p l e s p r e s e n t a challenge. If they
are true insulators then n o spark a n d consequently n o
ions c a n b e o b t a i n e d . If a t t e m p t s a r e m a d e t o g r i n d
t h e solid t o a p o w d e r , it will b e c o n t a m i n a t e d t o t h e
p o i n t w h e r e it b e a r s n o r e s e m b l a n c e t o t h e original
s a m p l e . T h e best c o u r s e h e r e is t o try t o r u n solid
i n s u l a t o r s directly. U p t o 100 k V of s p a r k v o l t a g e is
available o n c o m m e r c i a l i n s t r u m e n t s a n d 7 0 - 1 0 0 % of
3. Spark-Source
Mass
Spectra
S p a r k - s o u r c e m a s s s p e c t r a a r e u n i q u e in their p r o d u c
t i o n of m u l t i p l y c h a r g e d species. M o s t m a s s s p e c t r o m e t r i c sources p r o d u c e singly c h a r g e d species since
t h e high energy r e q u i r e d for t h e s e c o n d i o n i z a t i o n
p o t e n t i a l is n o t available. W i t h t h e excess energy
available in rf s p a r k sources m a n y stages of multiple
i o n i z a t i o n a s well a s t h e p r o d u c t i o n of m o l e c u l a r
species a r e seen. T h e m o s t intense lines a r e t h o s e d u e
t o singly c h a r g e d i o n s . M u l t i p l e stages of i o n i z a t i o n
a r e visible a s ions w i t h c h a r g e s of + 8 o r m o r e . T h e s e
fall a t
i, i, . . I
of t h e a t o m i c m a s s .
I n a d d i t i o n , certain e l e m e n t s such as c a r b o n a n d
+
silicon will f o r m p o l y a t o m i c clusters (e.g., Si 2 ). T a b l e
1 s h o w s t h e v a r i o u s i o n s p r o d u c e d from a silicon
s a m p l e . O b v i o u s l y , i m p u r i t i e s of interest in t h e 5 6 - 6 0
m/e ( m a s s / c h a r g e ) region will be seriously i m p a i r e d by
interferences from S i ^ . A t h i r d a n d less intense g r o u p
of i o n s arises from i o n i z a t i o n s of m o l e c u l a r species,
+
+
such as S i C in silicon c a r b i d e s a m p l e s o r G a A s
f r o m gallium a r s e n i d e . L a s t of t h e spectral types a r e
481
Spark-Source
Mass
Spectrograph};
Table 1
Ions produced from silicon in an rf spark source
Ion type
detectable o n a 1 n C e x p o s u r e is e q u i v a l e n t t o a n
a t o m i c c o n c e n t r a t i o n of 1 p p m .
m/e
Multiply charged
+
Sii,+ Si2 9,2 +SiJ
Sil 8 +, Si2 9 , Si3V
Si*8 , Si*,*, SiV
Molecular
+
Si2+ (28, 28)
Si2+ (28, 29)
Si2+ (29, 29)
Si2+ (29, 30)
Si2 (30, 30)
Complex
+
SiC + (28, 12)
SiC + (29, 12) (28, 13)
SiC + (30, 12) (29, 13)
SiC (30, 13)
28, 29, 30
14, 14.5, 15
7, 7.25, 7.5
56
57
58
59
60
40
41
42
43
4. Interpretation
and
Quantitation
482
4.1
Interpretation
O n c e t h e p l a t e h a s b e e n e x p o s e d a n d d e v e l o p e d it is
t h e n r e a d y for i n t e r p r e t a t i o n . T h i s step, w h i c h
involves c h o o s i n g a n analytical line o r lines for t h e
q u a n t i t a t i o n of e a c h element, is p r o b a b l y t h e source
of t h e largest e r r o r s in q u a n t i t a t i n g S S M S .
Since S S M S spectra c a n b e q u i t e c o m p l e x t h e task
of c h o o s i n g a n d identifying t h e analytical line is often
difficult. W h e n e v e r possible, t h e identity o f t h e line
c h o s e n s h o u l d b e confirmed b y t h e presence of its
d o u b l y ionized c o u n t e r p a r t a t a p p r o x i m a t e l y t h e cor
rect intensity. F o r e x a m p l e , if t h e line a t m/e 75 is t o
be used t o e s t i m a t e t h e arsenic c o n t e n t of a s a m p l e ,
t h e n t h e a n a l y s t m u s t b e a s s u r e d t h a t there is a line a t
2 +
m/e 37.5 c o r r e s p o n d i n g t o A s , t h a t it is a b o u t o n e t e n t h t h e intensity of t h e line a t m/e 75 a n d t h a t n o
interfering species exist w h i c h c o u l d c o n t r i b u t e t o t h e
lines being used. T h e a n a l y s t m u s t c o n s t a n t l y b e
a w a r e o f t h e m a t r i x u n d e r analysis a n d of all possible
line misidentifications a n d interferences.
T r u e spectral interferences a r e relatively r a r e in t h e
i n t e r p r e t a t i o n of s p a r k s o u r c e spectra a n d m o s t of
these involve m o n o i s o t o p i c elements. I t is difficult, for
e x a m p l e , t o a n a l y z e for trace p h o s p h o r u s (mass 31) in
3+
a n i o b i u m m a t r i x (mass 93) b e c a u s e t h e N b
line a t
m/e 31 is of high intensity a n d completely o b s c u r e s t h e
low-level p h o s p h o r u s line also a t m/e 3 1 .
4.2
Quantitation
O n c e t h e a n a l y s t is certain t h a t t h e lines c h o s e n a r e
valid h e m a y u s e either of t w o m e t h o d s for q u a n t i
tationvisual estimation or microphotometry. T h e
t w o m e t h o d s p r o d u c e essentially t h e s a m e degree of
q u a n t i t a t i o n . T h e visual m e t h o d involves e s t i m a t i o n
of t h e e x p o s u r e necessary t o p r o d u c e a j u s t - d e t e c t a b l e
line of t h e e l e m e n t o f interest. T h i s is related t o a n
i n t e r n a l s t a n d a r d ( m o s t often a small i s o t o p e o f t h e
m a t r i x ) b y t h e following f o r m u l a :
6
C=(EJEi)(X/\00)(IJIi)^l0
(1)
w h e r e C is t h e c o n c e n t r a t i o n of t h e e l e m e n t s o u g h t in
a t o m i c p p m , t h e subscripts s a n d i refer t o t h e
s t a n d a r d a n d i m p u r i t y , is t h e e x p o s u r e necessary t o
p r o d u c e t h e j u s t - d e t e c t a b l e line, X is t h e c o n c e n t r a
t i o n of t h e i n t e r n a l s t a n d a r d a n d / is t h e a b u n d a n c e
( % ) of t h e i s o t o p e used.
T h e m i c r o p h o t o m e t e r m e t h o d involves m e a s u r e
m e n t of t h e b l a c k e n i n g ( o r actually t r a n s m i s s i o n ) o f
t h e spectral lines. A c a l i b r a t i o n curve for e a c h e m u l
sion b a t c h m u s t b e p r e p a r e d b y p l o t t i n g e x p o s u r e
versus b l a c k e n i n g for a n u m b e r of isotopes o f a
s t a n d a r d . T i n is a n excellent element for this p u r p o s e
since it h a s a large n u m b e r o f i s o t o p e s of widely
v a r y i n g a b u n d a n c e . T h i s c a l i b r a t i o n c u r v e is t h e n
used t o o b t a i n a c c u r a t e values of E{ a n d Es from E q n .
(1).
Stress
T h e r e a r e t w o cases w h e r e a c c u r a t e analytical d e
t e r m i n a t i o n s m a y be p e r f o r m e d w i t h S S M S . T h e s e a r e
instances w h e r e electrical d e t e c t i o n is used i n s t e a d of
p h o t o p l a t e detection a n d w h e r e i s o t o p e d i l u t i o n is
used. Electrical d e t e c t i o n involves t h e use of a n elec
t r o n multiplier replacing t h e p h o t o p l a t e in t h e focal
p l a n e . Accuracies of 5 % h a v e b e e n a t t a i n e d r o u
tinely w h e r e s t a n d a r d s a r e available. I s o t o p e d i l u t i o n
is useful in c o m b i n a t i o n w i t h S S M S since all e l e m e n t s
are ionized. T h e N a t i o n a l B u r e a u of S t a n d a r d s r o u
tinely uses S S M S in c o n j u n c t i o n w i t h i s o t o p e d i l u t i o n
for the certification of s t a n d a r d reference m a t e r i a l s .
5.
Applications
Distribution:
Analysis
Using
Thermoelastic
Effect
1.
The Thermoelastic
Effect
*v e = c . | ? +
2
r f
0
(1)
in w h i c h is t h e t e m p e r a t u r e difference a b o v e a
reference t e m p e r a t u r e T0; k, p, Ct a n d a r e the
m a t e r i a l coefficients of t h e r m a l c o n d u c t i v i t y , density,
specific h e a t u n d e r c o n s t a n t strain a n d coefficient of
linear t h e r m a l e x p a n s i o n , respectively; S is t h e s u m
of t h e p r i n c i p a l stresses (bulk stress), a n d / d e n o t e s
time.
A further simplification c a n be m a d e w h e n a d i a b a tic c o n d i t i o n s a p p l y , t h a t is w h e n t h e r m a l c o n d u c t i o n
c a n b e c o n s i d e r e d insignificant; t h e left-hand side of
E q n . (1) m a y b e neglected a n d i n t e g r a t i n g with respect
t o / leads t o K e l v i n ' s law:
^ = - K A S
(2)
w h e r e a n d AS a r e t h e c h a n g e s in t e m p e r a t u r e a n d
b u l k stress, respectively, a n d = oil(pCe) is k n o w n as
the thermoelastic constant.
K e l v i n ' s law p r o v i d e s a simple a n d direct link
b e t w e e n t h e d y n a m i c t e m p e r a t u r e a n d b u l k stress a n d
so f o r m s t h e basis for e x p e r i m e n t a l stress analysis b y
t h e m e a s u r e m e n t of t e m p e r a t u r e .
2. Thermometric
Stress
Analysis
A l t h o u g h t h e t h e r m o e l a s t i c effect h a s b e e n well
u n d e r s t o o d since t h e f o u n d i n g w o r k of Kelvin, its
potential practical application was not demonstrated
483
Stress
Distribution:
Analysis
Using Thermoelastic
SPATE
T h e S P A T E system consists of t h r e e p r i n c i p a l c o m
ponents.
(a)
T h e d e t e c t o r h e a d c o n t a i n s a liquid-nitrogencooled c a d m i u m - m e r c u r y - t e l l u r i d e ir d e t e c t o r
which is sensitive in t h e 8 - 1 2 spectral r a n g e .
A small p o i n t l i k e a r e a o n a cyclically l o a d e d
s t r u c t u r e is focused o n t o t h e d e t e c t o r b y a ger
m a n i u m lens a n d either a line o r a n a r e a r a s t e r
scan m a y be p e r f o r m e d via a built-in s c a n n i n g
m i r r o r system.
(b)
(c)
T h e c o m p u t e r system p r o v i d e s t h e overall c o n
trol of t h e s c a n n i n g a n d d a t a acquisition u n i t s , as
well as being c a p a b l e of p e r f o r m i n g v a r i o u s
p o s t p r o c e s s i n g , display a n d s t o r a g e functions.
linear spatial r e s o l u t i o n of
d i s t a n c e of 0.25 m a n d a
0.001 C ( c o r r e s p o n d i n g t o
1 M P a for mild steel).
Applications
484
Effect
Stress
Distribution:
Analysis
Using
Thermoelastic
- 5 0
Effect
50
(MPa)
Figure 1
t o r q u e t o a h e x a g o n a l - h e a d e d bolt. T h e s h a n k section
s h o w s t h e classical b e n d i n g b e h a v i o r w h e r e t h e t o p
side experiences c o m p r e s s i o n while t h e lower side
u n d e r g o e s tension. I n this case, h o w e v e r , t h e n a t u r e of
the contact reactions between the spanner jaws and
t h e b o l t w o u l d b e extremely difficult t o k n o w in
a d v a n c e , a n d t h u s a n a c c u r a t e n u m e r i c a l m o d e l of
this region w o u l d n o t be easy t o achieve.
5. Current
and Future
Developments
A s a relatively n e w t e c h n i q u e , T S A h a s been u n d e r g o
ing a g r e a t deal of d e v e l o p m e n t a n d e v o l u t i o n . M a n y
h a r d w a r e i m p r o v e m e n t s h a v e a l r e a d y been developed
for t h e S P A T E system. Refinements such as a m a c r o lens a t t a c h m e n t , m o t i o n c o m p e n s a t o r a n d a m o r e
powerful c o m p u t e r system h a v e a l r e a d y b e c o m e
485
Stress
Distribution:
Analysis
Using Thermoelastic
486
Effect
200
Q_
5
-200
Figure 2
Residual stress profile of a four-point straightened
specimen; the vertical bars represent the standard error of
the TSA results and the continuous line is the predication
based on the strain gauge data (after Wong et al. 1988.
Reprinted by permission from Nature 332: 613-15.
Copyright 1988 Macmillan Magazines Ltd.)
Superconducting
Superconducting Materials:
Measurements
M a t e r i a l s m a y b e in t h e f o r m of single crystals,
polycrystalline pellets o r cast s a m p l e s , t h i n films o r
c o m m e r c i a l wires. T h e c h a r a c t e r i z a t i o n of t h e super
c o n d u c t i n g p r o p e r t i e s of a m a t e r i a l involves a n u m b e r
of different m e a s u r e m e n t s ; t h e types of m e a s u r e m e n t
a p p r o p r i a t e for a p a r t i c u l a r m a t e r i a l d e p e n d o n t h e
size, s h a p e a n d h o m o g e n e i t y of t h e s a m p l e available.
M o s t m a t e r i a l s exhibit s o m e i n h o m o g e n e i t y a n d
s o m e , for i n s t a n c e g r a n u l a r m a t e r i a l s o r m a t e r i a l s
with high critical c u r r e n t densities, h a v e intrinsic
i n h o m o g e n e i t y . T h e c h a r a c t e r i z a t i o n of i n h o m o g e n
e o u s m a t e r i a l s is c o m p l e x ; even t h e simplest of
m e a s u r e m e n t s r e q u i r e careful i n t e r p r e t a t i o n .
E m p h a s i s is p l a c e d o n t e c h n i q u e s for t h e c h a r a c t e r
ization of e x t r e m e t y p e II s u p e r c o n d u c t i n g m a t e r i a l s .
T w o types of m e a s u r e m e n t c a n b e used t o derive a
n u m b e r of different p a r a m e t e r s . T h e first is a resistive
m e a s u r e m e n t in w h i c h a c u r r e n t is p a s s e d t h r o u g h a
s a m p l e a n d t h e v o l t a g e m e a s u r e d . T h e s e c o n d is a n
inductive m e a s u r e m e n t w h i c h gives i n f o r m a t i o n o n
the m a g n e t i c m o m e n t of t h e s a m p l e . T h i s article
begins b y describing these t w o t e c h n i q u e s a n d t h e
p r e c a u t i o n s t o b e t a k e n if reliable results a r e t o b e
o b t a i n e d . T h e m e a s u r e m e n t of individual m a t e r i a l
p a r a m e t e r s is t h e n described.
1. Resistive
Measurements
I n a resistive m e a s u r e m e n t a c u r r e n t is p a s s e d t h r o u g h
the s a m p l e a n d t h e v o l t a g e b e t w e e n t w o p o i n t s in t h e
current path measured. There are two separate
regimes. I n t h e first regime, very low c u r r e n t s a r e u s e d
t o m e a s u r e t h e critical t e m p e r a t u r e Tc. F o r this p u r
p o s e , t h e g e o m e t r y is n o t very i m p o r t a n t a n d t h e m a i n
Materials:
Measurements
Measurements
2.1 DC
Magnetization
T h e m a g n e t i z a t i o n c u r v e gives a g r e a t deal of infor
m a t i o n a b o u t a s u p e r c o n d u c t i n g m a t e r i a l . M o s t stan
d a r d m e t h o d s c a n be used b u t s o m e a r e m o r e suitable
t h a n o t h e r s (see Magnetic Materials:
Measurements).
I n e x t r e m e t y p e II m a t e r i a l s t h e large value of the
G i n z b u r g - L a n d a u parameter poses particular prob
lems. A t low a p p l i e d fields, t h e m a g n e t i z a t i o n curve
c o n t a i n s detail u p t o a few millitesla with a relatively
high susceptibility, while t h e high-field e n d of t h e
487
Superconducting
Materials:
Measurements
488
m e a s u r e m e n t of c h a n g e s in m a g n e t i z a t i o n c a u s e d b y
flux creep p r e s e n t fewer p r o b l e m s since the c h a n g e
c a n be p i c k e d u p directly as a voltage in the search
coils. T h e signal is m e a s u r e d b y a n i n t e g r a t o r w h i c h
t e n d s t o drift, b u t use of a S Q U I D d e t e c t o r will a v o i d
this p r o b l e m . H o w e v e r , m o s t flux creep e x p e r i m e n t s
m u s t b e m a d e in a fairly large external field so t h a t
flux c r e e p in t h e m a g n e t is t h e d o m i n a n t e r r o r .
Commercial instruments have p o o r coupling between
s a m p l e a n d search coils a n d m a g n e t creep is a m a j o r
limitation.
T e c h n i q u e s w h i c h m e a s u r e the force, o r t o r q u e , o n
a s a m p l e h a v e n o t been u s e d m u c h b u t are sensitive
a n d direct, a l t h o u g h delicate. T h e y h a v e been of
c o n s i d e r a b l e value in m e a s u r e m e n t s o n high-!T c
m a t e r i a l s ( H a g e n a n d Griessen 1989, H a m z i c et al.
1990). T h e F a r a d a y b a l a n c e as n o r m a l l y supplied is
n o t suitable as it p u t s a large a n d variable field
g r a d i e n t a c r o s s t h e s a m p l e . H o w e v e r , by p u t t i n g the
s a m p l e in a u n i f o r m m a i n field a n d a d d i n g a small
g r a d i e n t field w i t h external coils w h i c h c a n b e
c h o p p e d a n d detected w i t h a lock-in amplifier, a
sensitive m a g n e t o m e t e r c a n b e m a d e w h i c h d o e s n o t
m o v e t h e s a m p l e significantly. T h e g r a d i e n t coils
s h o u l d n o t m o v e the flux vortices in t h e s a m p l e b y
m o r e t h a n t h e p i n n i n g i n t e r a c t i o n distance for linear
d i s p l a c e m e n t , a s will be discussed later.
T o r q u e m e a s u r e m e n t s h a v e t h e s a m e a d v a n t a g e s as
a F a r a d a y b a l a n c e in t h a t it is n o t necessary t o m o v e
the s a m p l e p o s i t i o n in t h e m a g n e t field. T o r q u e m a g
n e t o m e t e r s c a n n o t m e a s u r e the reversible c o m p o n e n t
of t h e m a g n e t i z a t i o n , b u t they c a n m e a s u r e a n i s o
t r o p y a n d flux v o r t e x p i n n i n g forces, a l t h o u g h the
g e o m e t r y c a n m a k e q u a n t i t a t i v e i n t e r p r e t a t i o n diffi
cult, p a r t i c u l a r l y if b o t h a r e present.
2.2 AC Techniques
T h e r e s p o n s e of a s u p e r c o n d u c t o r t o a n a l t e r n a t i n g
field allows a n u m b e r of p a r a m e t e r s t o b e m e a s u r e d .
M a n y of t h e s a m e c o n s i d e r a t i o n s a p p l y as t o d c
m e a s u r e m e n t s b u t a c t e c h n i q u e s , particularly w i t h the
a d d i t i o n of a lock-in amplifier, c a n be extremely
c o n v e n i e n t a n d sensitive. T h e simplest configuration
is t o m e a s u r e t h e c h a n g e in i m p e d a n c e of a coil
c o n t a i n i n g the s a m p l e . T h i s m a y b e small a n d greater
sensitivity c a n b e o b t a i n e d by l o o k i n g for the t h i r d
h a r m o n i c , since a s u p e r c o n d u c t o r c a n b e dis
tinguished from o t h e r m a g n e t i c m a t e r i a l s b y the
g e n e r a t i o n of a s t r o n g t h i r d - h a r m o n i c signal.
H o w e v e r , m o s t m e t h o d s use a m u t u a l i n d u c t a n c e
so t h a t the p i c k u p coil voltage is i n d e p e n d e n t of the
m u c h larger drive coil voltage. F o r q u a n t i t a t i v e
m e a s u r e m e n t s the drive coil s h o u l d p r o v i d e a u n i f o r m
field over t h e s a m p l e a n d t h e p i c k u p coils s h o u l d b e
such t h a t the voltage is easily related t o t h e m a g n e t i
z a t i o n , as for d c m a g n e t i c m e a s u r e m e n t s . It is
generally necessary t o use a b a l a n c i n g n e t w o r k t o
cancel o u t u n w a n t e d signals d u e t o m u t u a l i n d u c t a n c e
in t h e leads, capacitive effects a n d g r o u n d l o o p s . T h e
Superconducting
system c a n b e b a l a n c e d either w h e n t h e s a m p l e is
n o r m a l o r w h e n it is s u p e r c o n d u c t i n g , a c c o r d i n g t o
the m e a s u r e m e n t . If it is b a l a n c e d w h e n n o r m a l , t h e
b a l a n c e need only b e set o n c e since it is i n d e p e n d e n t
of s a m p l e size. H o w e v e r , if it is desired t o o b s e r v e
small p e n e t r a t i o n s of flux in a m a i n l y s u p e r c o n d u c t
ing s a m p l e , it is necessary t o b a l a n c e in t h e fully
superconducting state.
T h e a p p a r a t u s is generally a c o m p r o m i s e b e t w e e n
conflicting r e q u i r e m e n t s . M a k i n g t h e system small
reduces t e m p e r a t u r e differences, b u t also r e d u c e s
sensitivity. A n y m e t a l s used t o r e d u c e t e m p e r a t u r e
gradients carry eddy currents which produce spurious
signals. T h e s e o u t - o f - b a l a n c e signals t e n d t o b e t h e
m a i n limitation r a t h e r t h a n noise o r sensitivity. T h e y
arise from d i m e n s i o n a l c h a n g e s in t h e p r o b e , f r o m
c o n v e n t i o n a l soldered j o i n t s , from t h e r m o m e t e r c a n s
t o o close t o t h e coils a n d from e d d y c u r r e n t s in c a n s
r o u n d t h e system a n d t h e s u p e r c o n d u c t i n g m a g n e t .
T h i s last factor is very n o n l i n e a r a t high drive a m p l i
tudes a n d t h e r e is also a d a n g e r o f q u e n c h i n g t h e
m a g n e t if it is close t o its m a x i m u m field. T o m i n i m i z e
external e d d y c u r r e n t s t h e drive coil c a n b e w o u n d a s
t w o coils of t h e s a m e n u m b e r o f a r e a t u r n s excited in
o p p o s i t i o n , a l t h o u g h this reduces t h e available a m p l i
t u d e . A t e c h n i q u e t o limit t h e effects o f t h e r m a l
e x p a n s i o n is t o w i n d drive coils o n q u a r t z t u b e s a n d
p u t t h e search coils o u t s i d e t h e m . T h e signal is t h e n
i n d e p e n d e n t o f c h a n g e s t o t h e search coil d i m e n s i o n s
a n d t h e drive coils c a n b e w o u n d t o b e m o r e n e a r l y
identical since they a r e of t h i c k e r wire ( C o o p e r et al.
1990).
T h e signal f r o m t h e search coils c a n b e t r e a t e d in a
n u m b e r of w a y s d e p e n d i n g o n t h e p a r a m e t e r being
investigated. T h e s e a r e discussed in Sect. 3 .
3. Individual
Parameters
3.1 Critical
Temperature
T h i s section describes m e a s u r e m e n t s of Tc in z e r o
m a g n e t i c field.
(a) Resistive measurements. I n a h o m o g e n e o u s s u p e r
c o n d u c t o r t h e resistance goes t o z e r o o v e r a few
millikelvin a n d p r o v i d e s a n a c c u r a t e m e a s u r e m e n t o f
Tc. T h e c o n v e n t i o n a l definition is t h e t e m p e r a t u r e t o
reach half t h e n o r m a l state resistivity. W h a t is
actually m e a s u r e d is t h e t e m p e r a t u r e a t w h i c h t h e
Materials:
Measurements
critical c u r r e n t is e q u a l t o t h e m e a s u r i n g c u r r e n t , so a
check s h o u l d b e m a d e t h a t t h e c u r v e is i n d e p e n d e n t of
t h e m e a s u r i n g c u r r e n t . T h i s is n o r m a l l y t h e case for
c u r r e n t s of a few m i l l i a m p e r e s . A b r o a d t r a n s i t i o n o r
a finite resistance a t l o w t e m p e r a t u r e s is indicative
of i n h o m o g e n e i t y , a l t h o u g h c u r v a t u r e a t t h e hight e m p e r a t u r e e n d of t h e t r a n s i t i o n m a y b e d u e t o
fluctuations. If t h e p r o p o r t i o n of s u p e r c o n d u c t o r is
less t h a n t h e p e r c o l a t i o n t h r e s h o l d , t h e relative r e d u c
t i o n in resistance gives a n i n d i c a t i o n of t h e p r o p o r t i o n
of s u p e r c o n d u c t o r p r e s e n t . A l t h o u g h , in principle, a
n e t w o r k o f fine s u p e r c o n d u c t i n g t h r e a d s c o u l d give
z e r o resistance, this seems t o o c c u r r a t h e r rarely; grain
b o u n d a r y p h a s e s a r e usually less s u p e r c o n d u c t i n g
t h a n t h e b u l k , a l t h o u g h a n o t a b l e e x c e p t i o n is seen in
dilute s o l u t i o n s of i r o n in t i t a n i u m .
(b) Inductive measurements.
A s t h e s a m p l e goes
t h r o u g h Tc it b e c o m e s d i a m a g n e t i c a n d t h e size of t h e
signal a t a n y t e m p e r a t u r e d e p e n d s o n t h e r a t i o of t h e
magnetic penetration depth at that temperature to
t h e d i a m e t e r of t h e s a m p l e . T h e half-way p o i n t of t h e
t r a n s i t i o n is w h e n is a p p r o x i m a t e l y e q u a l t o t h e
r a d i u s of t h e s a m p l e . T h i s p o i n t will b e close t o
t h e p e a k in t h e i m a g i n a r y p a r t of t h e susceptibility o r
in t h e t h i r d h a r m o n i c if t h e a m p l i t u d e is large e n o u g h .
Small s a m p l e s will therefore h a v e wide t r a n s i t i o n s
even if they a r e h o m o g e n e o u s . T h e a m p l i t u d e d e p e n
d e n c e m u s t b e c h e c k e d since small a p p l i e d fields c a n
i n d u c e c u r r e n t densities g r e a t e r t h a n t h e critical cur
r e n t density.
T h e i n d u c e d signal is p r o p o r t i o n a l t o t h e p r o d u c t of
t h e a m p l i t u d e a n d t h e frequency a n d g r e a t e r sensiti
vity c a n b e o b t a i n e d a t high frequencies; u p t o several
m e g a h e r t z is used for oxide s u p e r c o n d u c t o r s . H o w
ever, it is i m p o r t a n t t h a t t h e n o r m a l state resistivity is
such t h a t t h e skin d e p t h is m u c h g r e a t e r t h a n t h e
s a m p l e size; this limits t h e frequency t o less t h a n 1
k H z for b u l k metallic s a m p l e s . T h e d c m a g n e t i z a t i o n
m e a s u r e d b y first c o o l i n g in z e r o field a n d t h e n raising
t h e t e m p e r a t u r e in a small a p p l i e d field gives t h e s a m e
m e a s u r e m e n t a s t h e inductive t e c h n i q u e s e x t r a p o l a t e d
t o z e r o frequency.
(c) Specific heat anomaly. T h i s is a very reliable
m e t h o d o f m e a s u r i n g Tc since it is i n d e p e n d e n t of t h e
s h a p e of a n y i n h o m o g e n e o u s regions a n d m e a s u r e s a
b u l k p r o p e r t y . H o w e v e r , it is time c o n s u m i n g a n d
n e e d s large s a m p l e s a n d s o is n o t very suitable for
s t a n d a r d testing.
(d) The effect of magnetic fields. T h i s is considered in
m o r e detail in Sect. 3.7. I n general, t h e t r a n s i t i o n is
broadened. This m a y be d u e to a greater inhomoge
neity in t h e u p p e r critical field Hc2 t h a n in Tc. H o w
ever, t h e r e a r e o t h e r r e a s o n s for b r o a d e n i n g even in
h o m o g e n e o u s s a m p l e s . F o r a type I I s u p e r c o n d u c t o r
in t h e m i x e d state, z e r o resistance is only achieved b y
t h e p i n n i n g of vortices. If t h e p i n n i n g energy is less
t h a n kBT, t h e r m a l l y a c t i v a t e d flux flow gives a linear
resistivity a n d t h e a c susceptibility will b e slightly
489
Superconducting
Materials:
Measurements
Fraction
T h e t e r m s u p e r c o n d u c t i n g fraction is generally t a k e n
t o m e a n t h e p r o p o r t i o n of a fully d i a m a g n e t i c signal
m e a s u r e d either in a n i n d u c t i v e t r a n s i t i o n o r in a
s a m p l e w a r m e d in a small field (i.e., less t h a n Hcl a t
low t e m p e r a t u r e s ) . It will give t h e p r o p o r t i o n of
s u p e r c o n d u c t o r p r e s e n t o n l y in t h e following r a t h e r
unusual circumstances. The superconducting phase
m u s t consist o f particles t h a t a r e large c o m p a r e d w i t h
the m a g n e t i c p e n e t r a t i o n d e p t h w h i c h d o n o t f o r m a n
interconnected structure. Large samples with a con
nected n e t w o r k of s u p e r c o n d u c t o r will give perfect
d i a m a g n e t i s m even with very large v o l u m e fractions
of n o r m a l m a t e r i a l . C o n v e r s e l y , h o m o g e n e o u s s u p e r
c o n d u c t o r s c a n give a very small d i a m a g n e t i s m if t h e
particle size is smaller t h a n t h e m a g n e t i c p e n e t r a t i o n
d e p t h a n d t h e g r a i n s a r e d e c o u p l e d . Since newly
p r e p a r e d m a t e r i a l s a r e often well a w a y from t h e
o p t i m u m c o m p o s i t i o n with a c o r r e s p o n d i n g l y large
p e n e t r a t i o n d e p t h , it is easy t o a s s u m e i n h o m o g e n e i t y
w h e r e n o n e exists. I n t e r p r e t a t i o n of t h e inductive
signal s h o u l d be m a d e in c o n j u n c t i o n with resistive
m e a s u r e m e n t s t o m a k e sure they a r e consistent. A
large d i a m a g n e t i c signal is a l m o s t certainly indicative
of t h e presence of a s u p e r c o n d u c t o r , a l t h o u g h c a r e
m u s t be t a k e n in m e a s u r e m e n t s u s i n g b r i d g e systems
t o m a k e sure t h a t it is n o t a decrease in p a r a m a g n e
tism w h i c h is b e i n g o b s e r v e d . A discussion is p r e
sented by C a m p b e l l et al. (1991).
3.3 Meissner
Fraction
T h e M e i s s n e r effect is t h e e x p u l s i o n of flux w h i c h
o c c u r s w h e n a s u p e r c o n d u c t o r is c o o l e d in a field.
A l t h o u g h s o m e t i m e s q u o t e d as t h e best test of a
s u p e r c o n d u c t o r , it is in fact a c o m p l e x p r o c e s s a n d
m a n y good superconductors have almost no Meissner
effect. I n a t y p e II s u p e r c o n d u c t o r , significant flux
begins t o m o v e t o w a r d s t h e n e a r e s t surface w h e n t h e
t e m p e r a t u r e is low e n o u g h for t h e e x t e r n a l field t o b e
below Hcl. T h e e x t e n t t o w h i c h it c a n get o u t is
d e t e r m i n e d b y flux p i n n i n g , o r the critical c u r r e n t
density Jc, a t this t e m p e r a t u r e . T h e M e i s s n e r fraction
490
is t h e m a g n e t i c m o m e n t expressed as a fraction of t h e
full d i a m a g n e t i c m o m e n t ; it is a c o m p l e x c o m b i n a t i o n
of t h e a p p l i e d field, t h e s a m p l e size a n d t h e s t r e n g t h of
t h e p i n n i n g a n d its v a r i a t i o n w i t h t e m p e r a t u r e . Little
useful i n f o r m a t i o n c a n be o b t a i n e d from it ( C a m p b e l l
et al. 1991).
3.4 Magnetic
Penetration
Depth
Different t e c h n i q u e s h a v e b e e n u s e d t o m e a s u r e the
magnetic penetration depth according to the nature
of t h e s a m p l e s available. If t h e m a t e r i a l is available a s
small particles w h i c h c a n be sized, t h e susceptibility a s
a function of particle size c a n b e used t o give .
Alternatively, t h e size d i s t r i b u t i o n of a r a n d o m sized
s a m p l e c a n be m e a s u r e d a n d t h e susceptibility a s a
function of t e m p e r a t u r e c a n b e fitted t o give t h e best
v a l u e of ( C o o p e r et al. 1989). A similar t e c h n i q u e is
t h e m e a s u r e m e n t of t h e i m a g i n a r y p a r t of t h e m i c r o
w a v e i m p e d a n c e . T h e i m p e d a n c e of a thin-film strip
line of t h e m a t e r i a l h a s also b e e n u s e d ( F i o r y et al.
1988, D r a b e c k et al. 1989). T h e p r o p e r t i e s of t h e
v o r t e x s t a t e n e a r Hcl a n d t h e v a l u e of Hcl a r e directly
related t o . If hysteresis is small, t h e s h a p e of t h e
reversible m a g n e t i z a t i o n c u r v e a t fairly low fields c a n
b e expressed in t e r m s of , a l t h o u g h p a r a m a g n e t i c
c o n t r i b u t i o n s m a k e this difficult in s o m e oxide m a t e r
ials ( M i t r a et al. 1989). T h e r m s field fluctuations of
t h e vortices c a n b e directly r e l a t e d t o a n d values
o b t a i n e d f r o m p o s i t r o n spin r e l a x a t i o n h a v e b e e n
widely q u o t e d ( H a r s h m a n et al. 1989). T h e r e a r e ,
h o w e v e r , o t h e r c o m p o n e n t s t o t h e r m s field fluctua
t i o n s c a u s e d b y p i n n i n g effects w h i c h affect t h e v a l u e
of derived. Finally, a v a l u e for c a n be calculated
f r o m a k n o w l e d g e o f Hcl a n d u s i n g t h e G i n z b u r g L a n d a u theory.
P r o b l e m s arise in all m e t h o d s t h a t use t h e t h e o r y of
flux vortices if t h e particle size is c o m p a r a b l e w i t h t h e
p e n e t r a t i o n d e p t h since, in these c i r c u m s t a n c e s , t h e
a p p a r e n t v a l u e s of Hcl a n d t h e m a g n e t i z a t i o n c u r v e
a r e affected b y t h e p r o x i m i t y of t h e s a m p l e surface.
C o n v e n t i o n a l s u p e r c o n d u c t o r s h a v e small p e n e t r a
t i o n d e p t h s a n d c a n usually be t r e a t e d as large s a m
ples. H o w e v e r , t h e o x i d e s u p e r c o n d u c t o r s c a n h a v e
large p e n e t r a t i o n d e p t h s , p a r t i c u l a r l y w h e n off stoic h i o m e t r y , a n d a r e often only available as small
i n d e p e n d e n t g r a i n s , so t h a t t h e s i t u a t i o n w h e n is
c o m p a r a b l e w i t h t h e p a r t i c l e size frequently o c c u r s .
3.5
Thermodynamic
Critical
Field
Superconducting
Materials:
Measurements
m a g n e t i z a t i o n is linear n e a r Hc2 so e x t r a p o l a t i o n of
t h e m a g n e t i z a t i o n c u r v e t o zero m a g n e t i z a t i o n is a
g o o d w a y of d e t e r m i n i n g Hc2. Since t h e slope is 1/
2
(2 - 1), t h e c h a n g e in slope m a y be difficult t o
detect, especially if t h e r e is a p a r a m a g n e t i c m o m e n t .
A clearer t r a n s i t i o n for large is generally seen if t h e
field is k e p t c o n s t a n t a n d t h e t e m p e r a t u r e varied.
E x t r a p o l a t i o n of t h e linear section t o m e e t t h e n o r m a l
state susceptibility gives t h e best value for Hc2 ( W e l p
et al. 1989).
Resistive m e a s u r e m e n t s m a y b e t h e only possible
t e c h n i q u e a t very high fields w h i c h a r e invariably
pulsed so t h a t t h e m e a s u r e m e n t t i m e is limited b u t , as
p o i n t e d o u t previously, this m e a s u r e s t h e irreversibi
lity line r a t h e r t h a n Hc2. A n o t h e r c o m p l i c a t i o n with
resistive m e a s u r e m e n t s is t h a t resistanceless surface
c u r r e n t s c a n b e carried u p t o Hc3, t h e critical field for
t h e n u c l e a t i o n of surface s u p e r c o n d u c t i v i t y . T h e cur
r e n t s a r e n o t large o n r o u g h surfaces a n d c a n b e
e l i m i n a t e d b y p l a t i n g with a n o r m a l m e t a l . H o w e v e r ,
this d o e s m e a n t h a t a resistive t r a n s i t i o n m a y b e
rather uncertain and current dependent.
3.8 Surface Nucleation
Field
491
Superconducting
Materials:
Measurements
Distance
T h e p i n n i n g i n t e r a c t i o n d i s t a n c e dpin is t h e d i s t a n c e
flux lines c a n m o v e before they b e c o m e u n p i n n e d . I t is
typically a b o u t a t e n t h o f t h e v o r t e x spacing ( C a m p
bell 1971, C a m p b e l l a n d E v e t t s 1972). T h e v o r t e x
m o v e m e n t a t t h e surface c a n b e derived directly from
t h e susceptibility since t h e voltage in t h e search coils is
p r o p o r t i o n a l t o t h e flux c h a n g e in t h e s a m p l e . If t h e
vortices a t t h e s a m p l e surface m o v e a distance y w h e n
t h e applied flux density is B, t h e flux c h a n g e is By p e r
u n i t length o f surface. N o t e t h a t t h e r e is a n u p p e r
limit t o t h e m o v e m e n t o f t h e m a g n e t i c lines o f force
which applies even in t h e n o r m a l state. F o r a cylindri
cal s a m p l e o f r a d i u s a a n d a n oscillating field o f
a m p l i t u d e Z>, t h e a m p l i t u d e o f t h e flux v o r t e x m o v e
m e n t a t t h e s a m p l e surface is ab/2B. If this is less t h a n
a b o u t a t e n t h o f t h e v o r t e x spacing, t h e r e s p o n s e o f
t h e system will always b e linear a n d t h e critical state
model does n o t apply.
A n alternative t e c h n i q u e f o r investigating t h e dis
p l a c e m e n t o f t h e flux lattice for a n applied force less
t h a n t h e critical d e p i n n i n g force d e p e n d s o n m e a s u r
ing t h e voltage i n a resistive m e a s u r e m e n t f o r a n a c
c u r r e n t with p e a k a m p l i t u d e below t h e critical cur
rent. T h e f o r c e - d i s p l a c e m e n t r e s p o n s e f o r p i n n e d
vortices h a s b e e n m e a s u r e d u s i n g this t e c h n i q u e b y
M c L e a n a n d results a r e given b y Evetts (1983). T h e
initial slope o f t h e f o r c e - d i s p l a c e m e n t r e s p o n s e is
related t o dpin a n d ? b y t h e relations
492
Superconducting
VocI". F o r m a g n e t a p p l i c a t i o n s w h i c h r e q u i r e ex
tremely low electric fields in c o m p o s i t e c o n d u c t o r s t h e
value of is very i m p o r t a n t for design p u r p o s e s ; in
such c o n d u c t o r s the value m a y b e related directly t o
the spatial i n h o m o g e n e i t y in Jc ( P l u m m e r a n d E v e t t s
1987).
(b) Inductive techniques. A n u m b e r of t e c h n i q u e s d e
rive Jc by analysis of t h e signal from a search coil of
the s a m e type as is used t o m e a s u r e inductive transi
tions. T o o b t a i n valid results t h e v o r t e x m o v e m e n t
m u s t b e sufficient t o build u p a critical state (i.e.,
i2
b>(Q)0By /a
w h e r e a is t h e r a d i u s of t h e s a m p l e a n d
0 is the flux q u a n t u m ) . T h e n o n l i n e a r i t y c a u s e d by
flux p i n n i n g c a n b e u s e d in a n u m b e r of w a y s t o
d e t e r m i n e t h e critical c u r r e n t density.
If t h e critical c u r r e n t density is a s s u m e d c o n s t a n t ,
the B e a n critical state m o d e l c a n b e used t o p r e d i c t the
w a v e f o r m , a n d h e n c e t h e t h i r d h a r m o n i c , o r t h e real
a n d i m a g i n a r y p a r t s of t h e susceptibility in t e r m s of
Jc. T h e value c a n t h e n b e c h o s e n t o give t h e best fit t o
the results ( B e a n 1964). T h i s t e c h n i q u e c a n b e
e x t e n d e d by a s s u m i n g a v a r i a t i o n of Jc w i t h such a s
Jcccl/B
a n d fitting t h e p a r a m e t e r s t o the signal a t
v a r i o u s a m p l i t u d e s . If viscous forces a r e t o b e
ignored, t h e frequency m u s t b e such t h a t t h e skin
d e p t h o b t a i n e d from t h e flux flow resistivity is m u c h
greater t h a n t h e s a m p l e size. F r e q u e n c i e s b e t w e e n
100 H z a n d 1000 H z a r e c o m m o n l y used. P a r a m e t e r s
t o describe t h e difference b e t w e e n i n t e r g r a i n a n d
i n t r a g r a i n c u r r e n t s in oxide s u p e r c o n d u c t o r s c a n also
be fitted ( M u l l e r a n d P a u z a 1989, T a k a c s a n d
G o m o r y 1989).
A n o t h e r g r o u p of m e a s u r e m e n t s m e a s u r e s t h e flux
in the s a m p l e directly ( C a m p b e l l 1969, Rollins et al.
1974). T h i s c a n b e d o n e either by i n t e g r a t i n g the
signal in a c o m p u t e r o r from t h e signal from a lock-in
amplifier w h i c h gives t h e flux directly. T h i s requires a
b r o a d e r b a n d d e t e c t o r t h a n the h a r m o n i c analysis, so
increasing t h e noise, b u t it h a s t h e m a j o r a d v a n t a g e
t h a t the t o t a l flux in the s a m p l e is m u c h easier t o
interpret a n d it is n o t necessary t o fit a n u m b e r of
p a r a m e t e r s in c o m p l e x expressions w h i c h m a y b e
based o n invalid a s s u m p t i o n s . A c o m p a r i s o n of the
techniques h a s b e e n m a d e b y K r o e g e r et al. (1975).
F o r a n external field c o n s i d e r a b l y g r e a t e r t h a n
the a m p l i t u d e of t h e a c drive field it c a n generally
be a s s u m e d t h a t Jc is a c o n s t a n t . Differentiation of
the signal from t h e p i c k u p coils with respect t o the
a m p l i t u d e t h e n gives t h e profile of Jc a c r o s s the
sample. T h i s is p a r t i c u l a r l y useful in distinguishing
surface p i n n i n g from b u l k p i n n i n g . I n zero a p p l i e d
field a similar analysis yields t h e critical c u r r e n t
density as a function of for m u c h lower values of
t h a n c a n be achieved in t r a n s p o r t m e a s u r e m e n t s
because of the self-field of t h e c u r r e n t . T h e t e c h n i q u e
c a n b e e x t e n d e d t o give the c o m p l e t e force-displace
m e n t curve for the p i n n e d lattice ( C a m p b e l l 1971,
C a m p b e l l a n d Evetts 1972).
Materials:
Measurements
A p r o b l e m w i t h h i g h - T c m a t e r i a l s is t h a t it is
difficult t o find o u t the effective size of t h e region in
w h i c h c u r r e n t s a r e flowing. T h e m o s t convincing w a y
is t o b r e a k t h e s a m p l e i n t o smaller sizes t o see if the
m a g n e t i z a t i o n c h a n g e s , b u t this is destructive a n d
m a y c h a n g e t h e p r o p e r t i e s . It h a s recently been
p o i n t e d o u t t h a t if the d e m a g n e t i z i n g factor is large,
the slope of the differential susceptibility c a n b e used
t o give t h e size of the c u r r e n t l o o p s a n d this a p p e a r s t o
be a useful t e c h n i q u e ( A n g a d i et al. 1991). H i g h - r c
m a t e r i a l s a r e also a n i s o t r o p i c a n d it m u s t b e a p p r e
ciated t h a t inductive t e c h n i q u e s will always involve
c u r r e n t s flowing in m o r e t h a n o n e direction; if Jc
varies with the direction of c u r r e n t flow a q u a n t i t a t i v e
analysis is difficult.
(c) DC hysteresis. T h e critical c u r r e n t density c a n be
calculated from the hysteresis in the d c m a g n e t i z a t i o n
using t h e critical state m o d e l . T h e m e t h o d is less
sensitive t h a n t e c h n i q u e s b a s e d o n m e a s u r e m e n t of
t h e a c susceptibility b u t since t h e d c m a g n e t i z a t i o n
s h o u l d always be m e a s u r e d it is c o n v e n i e n t t o derive
Jc from such m e a s u r e m e n t s . T h e s a m e p r o b l e m s arise
in deciding o n t h e effective size of the s a m p l e in t h e
case of g r a n u l a r h i g h - T c m a t e r i a l s ; a n u n a m b i g u o u s
c o n c l u s i o n c a n only b e o b t a i n e d from a series of
m e a s u r e m e n t s w h e r e t h e s a m p l e is progressively
r e d u c e d in size.
3.13 Flux Creep
F l u x creep is generally accepted t o b e a result of the
t h e r m a l a c t i v a t i o n of flux lines p a s t p i n n i n g centers. It
leads t o a l o g a r i t h m i c decay of the m a g n e t i z a t i o n if
the a c t i v a t i o n energy U is m u c h g r e a t e r t h a n kBT and
t o c o m p l e t e reversibility a n d zero critical c u r r e n t if U
is c o m p a r a b l e with o r less t h a n kBT. T h e first
m e a s u r e m e n t s were m a d e by m e a s u r i n g t h e decay of a
field t r a p p e d in a h o l l o w cylinder by m e a s u r i n g the
v o l t a g e of a coil inside it ( K i m et al. 1962, Beasley et
al. 1969). Alternatively, t h e coil c a n b e w o u n d r o u n d
t h e o u t s i d e of a solid specimen. T o o b t a i n meaningful
values it is i m p o r t a n t t h a t t h e critical state h a s penet
r a t e d t o t h e center of t h e s a m p l e . A n y t e c h n i q u e
w h i c h m e a s u r e s m a g n e t i z a t i o n c a n b e used t o
m e a s u r e flux creep by m e a s u r i n g t h e m a g n e t i z a t i o n as
a function of time, a l t h o u g h t h e m o s t sensitive tech
n i q u e s m e a s u r e j u s t t h e c h a n g e in m a g n e t i z a t i o n .
M e a s u r e m e n t s a r e easiest in zero applied field b u t it
is i m p o r t a n t t o k n o w h o w a c t i v a t i o n energies v a r y
with field. Since t h e m a g n e t m a y creep a t a similar r a t e
t o t h e specimen, it is n o t easy t o distinguish between
the t w o . I n a d d i t i o n , small c h a n g e s in m a g n e t field,
c a u s e d either by m a g n e t o v e r s h o o t d u r i n g r a m p i n g t o
the m e a s u r e m e n t field o r i n h o m o g e n e i t y over the
region w h e r e t h e s a m p l e is m o v e d , affect the flux creep
r a t e at t h e s a m p l e surface. T o r q u e m a g n e t o m e t r y h a s
p r o v e d a successful t e c h n i q u e , largely eliminating
p r o b l e m s of m a g n e t o v e r s h o o t a n d i n h o m o g e n e i t y .
Simple t h e o r y predicts t h a t AM/M =
(kBT/U)\n(t),
493
Superconducting
Materials:
Measurements
w h e r e is t h e m a g n e t i z a t i o n a n d t is time, so t h a t
w h a t is derived is a n effective a c t i v a t i o n energy.
Statistical effects m a k e this difficult t o i n t e r p r e t in a n y
simple w a y b u t it gives a g o o d g u i d e as t o t h e creep
r a t e in m a g n e t a p p l i c a t i o n s .
3.14 The Irreversibility
Line
T h e t e r m irreversibility line Bixx(T) is a n e w p a r a m e t e r
i n t r o d u c e d for t h e oxide s u p e r c o n d u c t o r s . W h e n t h e
activation energy for flux creep is c o m p a r a b l e t o kBT,
p i n n i n g is ineffective a n d t h e m a g n e t i z a t i o n of t h e
s a m p l e b e c o m e s completely reversible. T h e resistivity
is linear for small c u r r e n t s a n d a l t h o u g h it is less t h a n
t h e flux flow resistivity t h e m a t e r i a l is useless for
practical p u r p o s e s . N o d i a m a g n e t i s m is o b s e r v e d ,
a p a r t from a skin effect a t high frequencies, a n d t h e
low-frequency a c susceptibility is slightly p a r a m a g n e
tic. T h e irreversibility line is n o t precisely defined a n d
c a n be t a k e n as the p o i n t w h e r e t h e m a g n e t i z a t i o n
curve b e c o m e s reversible, t h e p o i n t of z e r o resistance,
t h e start of t h e d i a m a g n e t i c t r a n s i t i o n o r t h e p e a k in
t h e lossy c o m p o n e n t of t h e susceptibility. All these
occur a t similar p o i n t s b u t research is c o n t i n u i n g i n t o
their r e l a t i o n s h i p . O f these t e c h n i q u e s , t h e least reli
able is t h e closing of t h e d c hysteresis c u r v e since this
is ill defined a n d c a n be o b s c u r e d b y i n h o m o g e n e i t y in
t h e m a g n e t . H o w e v e r , l o o k i n g for d i s t o r t i o n in t h e
r e s p o n s e function of a S Q U I D m a g n e t o m e t e r c a n
give g o o d results. It c a n b e seen t h a t m o s t m e t h o d s of
detecting t h e s u p e r c o n d u c t i n g t r a n s i t i o n in a m a g
netic field detect t h e irreversibility line a n d n o t Hc2.
T h e existence of such a line s h o u l d n o t h a v e b e e n
u n e x p e c t e d since t h e energy wells w h i c h p i n flux lines
m u s t r e a c h a d e p t h c o m p a r a b l e with kBT before they
g o t o z e r o a t Hc2. H o w e v e r , t h e d e e p wells a n d low Tc
values e n c o u n t e r e d in c o n v e n t i o n a l s u p e r c o n d u c t o r s
m e a n t t h a t this o c c u r r e d very close t o Hc2 a n d t h e
p h e n o m e n o n w a s n o t o b s e r v e d o r l o o k e d for. I n highTc m a t e r i a l s t h e energy wells a r e smaller relative t o
kBT; t h e irreversibility line is easily distinguished from
Hc2 a n d c a n b e a m a j o r p r o b l e m in practical applica
tions. I n sintered h i g h - T c m a t e r i a l s t h e r e a r e t w o such
lines, o n e for t h e i n t e r g r a i n c u r r e n t s a n d o n e for t h e
intragrain currents.
5.75 AC Losses
M e a s u r e m e n t s of a c losses a r e of t w o types: calori
metric and electromagnetic.
(a) Calorimetric methods. I n o n e t e c h n i q u e t h e h e a t
g e n e r a t e d by losses in t h e s u p e r c o n d u c t o r is m e a s u r e d
by t h e increase in boil-off of t h e cryogenic c o o l a n t .
T h i s gives a n u n a m b i g u o u s loss m e a s u r e m e n t b u t for
a c c u r a t e results it is necessary for t h e loss t o b e
c o n s i d e r a b l y g r e a t e r t h a n t h e b a c k g r o u n d boil-off.
Even with a c a l o r i m e t e r r o u n d t h e s a m p l e t o collect
the gas this m a y b e difficult t o achieve because of t h e
boil-off d u e t o c o n d u c t i o n , p a r t i c u l a r l y if electrical
leads a r e a t t a c h e d t o t h e s a m p l e . T h e b a c k g r o u n d
boil-off is usually d e p e n d e n t o n t h e level of c r y o g e n
494
p r e s e n t a n d t h e c o o l i n g d u e t o increased boil-off c a n
c h a n g e t h e c o n d i t i o n s m a r k e d l y . T h e m o s t reliable
t e c h n i q u e is t o use a null m e t h o d in w h i c h t h e p o w e r
t o a resistor adjacent t o t h e s a m p l e is r e d u c e d in such
a w a y as t o k e e p t h e boil-off c o n s t a n t . T h e r e d u c t i o n
in p o w e r t o t h e resistor is t h e n e q u a l t o t h e dissipation
in t h e s u p e r c o n d u c t o r .
T h i s t e c h n i q u e is used for large v o l u m e s of m a t e r i a l
a n d p a r t i c u l a r l y for m a g n e t coils, w h e r e t h e large
inductive voltage m a k e s electrical m e a s u r e m e n t s inac
c u r a t e . It is generally limited t o t e m p e r a t u r e s for
w h i c h a liquid c r y o g e n c a n b e used, a l t h o u g h in
principle t h e rise in t e m p e r a t u r e of a g a s e o u s c o o l a n t
m i g h t b e used. T h e u l t i m a t e sensitivity is a b o u t 1 m W .
A n o t h e r t e c h n i q u e is t o t h e r m a l l y isolate t h e s a m
ple a n d m e a s u r e t h e r a t e of t e m p e r a t u r e rise. T h i s h a s
n o t b e e n used m u c h as t e m p e r a t u r e g r a d i e n t s a n d t h e
c o n t i n u o u s l y c h a n g i n g t e m p e r a t u r e m a k e t h e results
difficult t o analyze. H o w e v e r , a modification of this
m e t h o d in w h i c h t h e s a m p l e is c o n n e c t e d t o t h e
h e l i u m b a t h b y a t h e r m a l resistance a n d t h e t e m p e r a t
u r e rise is m e a s u r e d in t h e steady state c a n give g o o d
results. S c h m i d t a n d Specht (1990) h a v e used t h e
t e c h n i q u e t o m e a s u r e losses w i t h a r e s o l u t i o n of
10 n W . T h i s m e t h o d is n o t suitable if losses in t h e
presence of a t r a n s p o r t c u r r e n t a r e r e q u i r e d because
of t h e h e a t leak d o w n t h e c u r r e n t leads.
(b) Electrical methods. T h e s e a r e c o n v e n i e n t a n d sen
sitive p r o v i d e d t h e r e is only o n e s o u r c e of p o w e r ,
either a c u r r e n t in a wire o r a m a g n e t i z a t i o n loss. If
t h e p o w e r is c o m i n g from t w o sources such a s a
solenoid a n d a t r a n s p o r t c u r r e n t supply, it is neces
sary t o m e a s u r e b o t h m a g n e t i z a t i o n a n d l o n g i t u d i n a l
voltage. T h i s is t r u e even if o n e of t h e m is n o t
oscillating since a wire c a r r y i n g a n a c c u r r e n t in a n
oscillating m a g n e t i c field will h a v e a voltage i n d u c e d
a l o n g its length w i t h a c o n s e q u e n t p o w e r loss from t h e
supply, leading t o a d y n a m i c resistance. T h e r e c a n b e
c o n s i d e r a b l e p r o b l e m s in b a l a n c i n g o u t inductive
signals from t h e t w o sources a n d a criterion for
b a l a n c e b a s e d o n t h e expected s h a p e of t h e w a v e f o r m
m a y h a v e t o be used. C a l o r i m e t r i c m e t h o d s a r e
p r o b a b l y m o r e reliable in this s i t u a t i o n .
If t h e losses a r e p u r e l y m a g n e t i c , t h e s a m p l e is
placed in a n oscillating field a n d t h e m a g n e t i c res
p o n s e is m e a s u r e d b y o n e of t h e t e c h n i q u e s described
previously. It is t h e n possible t o m e a s u r e t h e a r e a of a
hysteresis l o o p o n t h e M-H curve. H o w e v e r , a m o r e
sensitive m e t h o d is t o m e a s u r e t h e i m a g i n a r y p a r t of
t h e susceptibility. F o r this t e c h n i q u e , it is only t h e
o u t - o f - p h a s e c o m p o n e n t of t h e f u n d a m e n t a l w h i c h
gives t h e loss, so a t u n e d filter is n e e d e d t o eliminate
h a r m o n i c s . T h e m a i n p r o b l e m is in b a l a n c i n g o u t
signals w h i c h a r e n o t d u e t o t h e s a m p l e . It is i m p o r t
a n t t o d o t h e b a l a n c i n g in such a w a y t h a t there is n o t
a large i n - p h a s e c o m p o n e n t since, if this is p r e s e n t , a
very small e r r o r in setting t h e p h a s e leads t o a large
e r r o r in t h e loss. T h e r e f o r e , if t h e p e n e t r a t i o n of t h e
Superconducting
Bibliography
Angadi A, Caplin A D, Laverty J R, Shen X 1991
Nondestructive determination of the current-carrying
length scale in superconducting crystals and thin films.
Physica C 179: 479-87
Bean C 1964 Magnetisation of high field superconductors.
Rev. Mod. Phys. 36: 31-9
Beasley R, Labusch R, Webb W W 1969 Flux creep in
type II superconductors. Phys. Rev. 181: 682-700
Campbell A 1969 The response of pinned flux vortices to
low frequency fields. / . Phys. C 2: 1492-1501
Campbell A M 1971 The interaction distance between flux
lines and pinning centres. J. Phys C 4: 3186-98
Campbell A M, Blunt F J, Johnson J D, Freeman A 1991
Quantitative determination of percentage superconductor
in a new compound. Cryogenics 31: 732-7
Campbell A Evetts J 1972 Flux vortices and transport
currents in type II superconductors. Adv. Phys. 21: 199
428
Cooper J R, Chu C T, Zhou L W, Dunn B, Griiner G 1989
Determination of the magnetic field penetration depth in
superconducting YBaCuO: deviations from the Bardeen
Cooper Schrieffer laws. Phys. Rev. 37: 638-41
2
Cooper J R, Forro L, Collin G, Henry J Y 1990 T
behaviour in the low temperature penetration depth of
oxygen depleted YBaCuO crystals. Solid State Commun.
75: 737-41
Drabeck L, Carini J P, Griiner G, Hylton J, Char K, Beasley
R 1989 Power law temperature dependence of the
electrodynamic properties in oriented YBa 2Cu 30 7_ (5 and
Y ^ C U g O , ^ , films. Phys. Rev. 39: 785-8
Evetts J 1970 Flux pinning by phase boundaries in type II
superconductors. Phys. Rev. 2: 95-6
Materials:
Measurements
495
Texture: Nondestructive
Characterization
T e x t u r e is t h e t e r m a p p l i e d t o t h e presence of a
preferred c r y s t a l l o g r a p h i c o r i e n t a t i o n of t h e crystal
lites (grains) in a polycrystalline m a t e r i a l . F i b e r s
b e c o m e t e x t u r e d d u r i n g g r o w t h o r processing.
M e c h a n i c a l o p e r a t i o n s such as d r a w i n g , rolling o r
swaging i n d u c e t e x t u r e . All such t e x t u r i n g i n t r o d u c e s
a n i s o t r o p y in t h e m e c h a n i c a l p r o p e r t i e s of t h e a g
gregate w h i c h affects t h e r e s p o n s e of t h e m a t e r i a l
d u r i n g further f o r m i n g , f a b r i c a t i o n o r in-service
operations.
/.
General
T h e c o m p l e t e c h a r a c t e r i z a t i o n of t e x t u r e in a s a m p l e
entails t h e d e t e r m i n a t i o n of t h e o r i e n t a t i o n d i s t r i b u
tion function ( O D F ) . T h i s is t h e v o l u m e fraction of
crystallites h a v i n g a specific c r y s t a l l o g r a p h i c orien
t a t i o n relative t o a c o o r d i n a t e system fixed in t h e
s a m p l e . D e t e r m i n a t i o n of t h e O D F requires diffrac
tion d a t a a n d r a t h e r s o p h i s t i c a t e d series-expansion
analysis. O w i n g t o t h e i n t e r a c t i o n s of g r a i n s w i t h their
neighbors, to anisotropically distributed second
p h a s e s o r v o i d s a n d t o o t h e r factors, a k n o w l e d g e of
the O D F is n o t , in general, sufficient t o p r e d i c t all t h e
a n i s o t r o p i c p r o p e r t i e s of a polycrystalline a g g r e g a t e .
Nevertheless, from a k n o w l e d g e of t h e O D F a n d
a p p r o p r i a t e single-crystal p r o p e r t i e s such q u a n t i t i e s
as the a n g u l a r v a r i a t i o n of Y o u n g ' s m o d u l u s a n d t h e
yield locus in t h e rolling p l a n e of steel sheet, a n d t h e
quantitative correlation between texture and the ani
s o t r o p y of m a g n e t o c r y s t a l l i n e energy in F e - S i steel
sheet h a v e b e e n d e t e r m i n e d .
I n the c o n t e x t of n o n d e s t r u c t i v e e v a l u a t i o n ( N D E ) ,
m e a s u r e d a n i s o t r o p y c a n b e a n i n d i c a t o r of degree of
texture. I n h e x a g o n a l , t r i g o n a l o r t e t r a g o n a l crystals
texture gives rise t o a n i s o t r o p y in electrical a n d t h e r
m a l resistance, coefficients of t h e r m a l e x p a n s i o n , ther
moelectric force a n d m a g n e t i c susceptibility. I n cubic
crystals such p r o p e r t i e s as elastic m o d u l u s a n d m a g
n e t i z a t i o n p o w e r losses a r e t e x t u r e d e p e n d e n t . S o m e
of these p r o p e r t i e s h a v e b e e n explicitly e m p l o y e d as
n o n d e s t r u c t i v e p r o b e s of t e x t u r e in m e t a l s .
T e x t u r e in p o l y m e r s is a n i m p o r t a n t special case
because of t h e g r e a t difference in s t r e n g t h b e t w e e n t h e
covalent b o n d s f o r m i n g t h e c h a i n o r b a c k b o n e a n d
the i n t e r c h a i n forces. O r i e n t a t i o n is easily p r o d u c e d in
polymers by deformation, shearing molten material,
film e x t r u s i o n o r b y g r o w t h processes in n a t u r a l
p o l y m e r s . Studies of t e x t u r e in p o l y m e r s h a v e b e e n
reviewed b y W e c k e r a n d M o r r i s (1978).
2. Diffraction
Techniques
Scattering plane
(b)
Figure 1
(a) A schematic illustration of scattering geometry for a
diffraction experiment. The arrows in the scattering plane
show incoming and diffracted radiation, (b) Details of
symmetric reflection-geometry measurement. The upper
portion shows masking effects (shaded); is the Bragg
angle
497
Texture:
Nondestructive
Characterization
One plate
Cu (400)
Lower
Cu (200)
two plates
Upper
two plates
Figure 2
Pole figures for texture versus depth measurement for two
stacked copper plates, each 0.08 cm thick misoriented by
45. In each figure, the center represents = 90, the
periphery = 30. ranges from 0 to 360,
circumferentially. The contour lines are drawn in multiples
of random intensity (i.e., intensity for a completely
random-orientation sample). The left-hand column shows
the measured (200) and (400) pole densities for the
two-plate sample, and the (200) pole density for the lower
plate measured alone. The right-hand column shows the
(200) pole density for each plate extracted from the
two-plate data by the difference technique
498
Bibliography
Bunge J 1969 Mathematische Methoden der Texturanalyse. Akademie-Verlag, Berlin
Choi C S, Prask J, Trevino S F 1979 Nondestructive
investigation of texture by neutron diffraction. J. Appl.
Crystallogr. 12: 327-31
Klug , Alexander L 1974 X-ray Diffraction Procedures
for Polycrystalline and Amorphous Materials, 2nd edn.
Wiley, New York, Chap. 10, pp. 709-54
Szpunar J 1976 Texture and neutron diffraction. At. Energy
Rev. 14: 199-261
Wecker S M, Morris R 1978 Modern methods of texture
analysis. / . Appl. Crystallogr. 11: 211-20
H . J. P r a s k a n d C . S. C h o i
[ N a t i o n a l B u r e a u of S t a n d a r d s ,
Washington, D C , USA]
Thermal
Analysis:
An
Overview
Table 1
Thermal analysis techniques
Technique"
Thermometry
Differential thermal analysis
Calorimetry
Dilatometry
Thermomechanical analysis
Thermogravimetry
Dynamic mechanical analysis
Electrate thermal analysis
Electrical conductivity analysis
Emanation thermal analysis
Evolved-gas analysis
Thermal conductivity analysis
Thermal diffusivity analysis
Thermoacoustimetry
Thermofractography
Thermoluminescence analysis
Thermomagnetic analysis
Thermooptical analysis
Thermosonimetry
Measurement
(in addition to
temperature)
time
temperature difference
heat
length or volume
stress, strain
mass
stress, strain, time
electrical discharge current
electrical resistance
release of radioactive
material
pyrolysis with gas analysis
thermal conductivity
thermal diffusivity
sound effects
thermal fractionation
coupled with thin-layer
chromatography
light emission
magnetic susceptibility
microscopy
sound effect
1 s h o w s a selection of t h e r m a l analysis t e c h n i q u e s ,
illustrating t h e b r e a d t h of t h e field. I n fact, a n y
measuring technique can be m a d e into a thermal
analysis t e c h n i q u e b y a d d i n g t h e r m a l c o n t r o l . Simul
t a n e o u s use of m u l t i p l e t e c h n i q u e s increases t h e
p o w e r of t h e r m a l analysis, a n d m o d e r n i n s t r u m e n
t a t i o n h a s p e r m i t t e d extensive g r o w t h of a p p l i c a t i o n .
T h e basic theories of t h e r m a l analysis ( e q u i l i b r i u m
t h e r m o d y n a m i c s , irreversible t h e r m o d y n a m i c s a n d
kinetics) a r e well d e v e l o p e d , b u t h a v e t o d a t e n o t b e e n
applied t o a c t u a l e x p e r i m e n t s t o t h e fullest e x t e n t
possible.
1.
Thermometry
Time
( c o n s t a n t heat
input)
Concentration
(a)
(b)
Figure 1
(a) A simple eutectic phase diagram and (b) the
corresponding heating curve, with constant heat input
leading to an almost linear temperature rise
C o u p l i n g of t h e r m o m e t r y w i t h o t h e r t e c h n i q u e s
such as m i c r o s c o p y , x-ray diffraction a n d spectros
c o p y is frequent. M e l t i n g t e m p e r a t u r e s a r e readily
seen a n d easily verified b y m i c r o s c o p i c o b s e r v a t i o n .
G l a s s t r a n s i t i o n s , w h i c h c a u s e only a c h a n g e in slope
in t h e t i m e - t e m p e r a t u r e r e c o r d i n g , r e q u i r e higher
precision a n d a r e m o r e s h a r p l y defined b y o b s e r v a t i o n
of t h e d i s a p p e a r a n c e of strain b y p o l a r i z i n g m i c r o s
c o p y . C o n s t a n t t r a n s i t i o n t e m p e r a t u r e r e c o r d i n g is
frequent in t h e f o r m of freezing-point d e t e r m i n a t i o n
(cryoscopy) o r b o i l i n g - p o i n t d e t e r m i n a t i o n (ebulliometry). T h r o u g h two-phase equilibrium thermo
d y n a m i c s t h e c h a n g e s in t r a n s i t i o n t e m p e r a t u r e s a r e
coupled to concentration (mass and molecular mass)
a n d h e a t s of t r a n s i t i o n ( e n t r o p i e s of t r a n s i t i o n ) . H i g h
est a c c u r a c y is r e a c h e d in t h e analysis of linear
macromolecules (polymers). Transition temperature
5
c h a n g e s of as little as 1 0 " a r e m e a s u r e d for t h e
5
d e t e r m i n a t i o n of m o l e c u l a r m a s s e s of t h e o r d e r of 10 .
2. Differential
Thermal
Analysis
499
Thermal
Analysis:
An
Overview
AT
Recorder
amplifier
7"
Ice
bath
Programmer
f u r n a c e - control
thermocouple
reference
DTA
sample
P o w e r to heater
furnace
dQT/dt
K(Tb-Tr)
0)
dQJdt
K(Tb-Ts)
(2)
w h e r e t h e t h e r m a l c o n d u c t i v y is d e p e n d e n t o n t h e
g e o m e t r y a n d m a t e r i a l of t h e cell, b u t is i n d e p e n d e n t
of t h e s a m p l e . F o r simplicity, t h e cell a r r a n g e m e n t is
a s s u m e d t o b e s u c h t h a t s a m p l e a n d reference h a v e
t h e s a m e K. Th is t h e D T A furnace o r h e a t i n g b l o c k
t e m p e r a t u r e a n d , a n d Ts a r e t h e reference a n d
s a m p l e t e m p e r a t u r e s , respectively. E q u a t i o n s (1) a n d
(2) a r e simple r e p r e s e n t a t i o n s of N e w t o n ' s law of
c o o l i n g . T h e h e a t flow e q u a t i o n c a n be derived f r o m
E q n s . (1) a n d (2) b y m a k i n g Tb increase linearly w i t h
t h e h e a t i n g r a t e q (i.e., Th= T0 + qt) a n d . a s s u m i n g
t h a t all s a m p l e h e a t flow is u s e d t o increase t h e s a m p l e
T0)),with C pr e p r e s e n t i n g
t e m p e r a t u r e ( i . e . , Q s = Cp(Tsthe (constant) sample heat capacity:
dQJdt
Figure 2
Schematic diagram of a DTA apparatus
500
(3)
T h e s o l u t i o n s of t h e h e a t flow e q u a t i o n in t e r m s of
t o t a l h e a t flow u p t o time t o r t e m p e r a t u r e a r e
(initial c o n d i t i o n s t = 0, Th = Ts = T0 = 0, Q = 0):
Qs = qCpt-
p e r a t u r e m e a s u r e m e n t s . U n d e r such c o n d i t i o n s t h e
t e c h n i q u e is frequently called differential s c a n n i n g
calorimetry (DSC).
D T A o r i g i n a t e d a t t h e t u r n of t h e c e n t u r y w h e n
s i m u l t a n e o u s p h o t o g r a p h i c r e c o r d i n g of t w o t h e r m o
c o u p l e o u t p u t s b e c a m e possible. T h e first m a j o r a p p l i
c a t i o n s were in t h e s t u d y of p h a s e d i a g r a m s a n d
t r a n s i t i o n t e m p e r a t u r e s , a n d q u a l i t a t i v e a n a l y s e s of
m e t a l s , oxides, salts, c e r a m i c s , glasses, m i n e r a l s a n d
soils. By 1952, 1000 r e s e a r c h r e p o r t s o n D T A w e r e
published; by 1972, t h e a n n u a l r a t e of p u b l i c a t i o n s
exceeded 1000. T h i s increase w a s b r o u g h t a b o u t b y
the use of electronics t o increase m e a s u r i n g a c c u r a c y
a n d t o a u t o m a t e d a t a collection a n d t r e a t m e n t . A t
present, D T A is used in a l m o s t all fields of scientific
investigation a n d is especially useful for t h e analysis
of m e t a s t a b l e systems. A m o d e r n design for use w i t h
t e m p e r a t u r e s from 100 t o 1000 is s h o w n in F i g . 3.
1
Typical sensitivies of 10-100 s " h a v e been c l a i m e d
for such i n s t r u m e n t s for 1-10 m g s a m p l e size. H e a t i n g
1
rates m a y r a n g e from 0.5 t o 50 m i n . H e a t c a p a
city m e a s u r e m e n t s as a c c u r a t e as 0 . 5 % h a v e b e e n
r e p o r t e d in f a v o r a b l e cases. T r a n s i t i o n t e m p e r a t u r e s
m a y be d e t e r m i n e d t o 0 . 1 K . E x t r e m e c o n d i t i o n
D T A m a y s p a n h e a t i n g r a t e s from 0.01 t o 10 000
1
m i n " , t e m p e r a t u r e s of m e a s u r e m e n t m a y r e a c h
a b o v e 3000 a n d m e a s u r e m e n t s u p t o p r e s s u r e s of
500 M P a h a v e b e e n achieved.
D T A without a temperature gradient within the
s a m p l e ( < 1.0 K ) , w h i c h c a n easily b e i n t e r p r e t e d
q u a n t i t a t i v e l y , is limited for 1 g s a m p l e s t o a b o u t a
1
1 m i n " h e a t i n g r a t e a n d for 1 m g s a m p l e s t o a b o u t
1
100 m i n " . T h e h e a t flow i n t o t h e reference
(dQJdt)
a n d s a m p l e (dQJdt)
c a n be given b y
= K[qt-(QJCp)]
Ts = qt~
(qC\lK)[\
(qCv/K)[\
- e x p ( - Kt/Cp)]
(4)
- e x p ( - Kt/Cp)]
(5)
Silver ring
Thermoelectric
(constanton)
disk
Dummy
Alumel wire
Heating block
Alumel
wire
Chromel wire
Figure 3
A typical DTA (DSC) measuring cell (courtesy of Du
Pont, Analytical Instruments Division)
Thermal
Analysis:
An
Overview
(a)
Time
Figure 4
A typical DTA trace showing first the approach to steady
state ATj, then melting (between times /; and i f), and
finally the renewed approach to steady state
s a m p l e t e m p e r a t u r e r e m a i n s c o n s t a n t , so t h a t AT
increases w i t h a slope e q u a l t o t h e h e a t i n g r a t e q.
W h e n m e l t i n g is c o m p l e t e , a r e n e w e d a p p r o a c h t o
steady state, described b y E q n . (5), o c c u r s . T h e verti
cally a n d h o r i z o n t a l l y s h a d e d a r e a s a r e p r o p o r t i o n a l
t o t h e t o t a l h e a t of fusion. T h e c r o s s h a t c h e d a r e a A is
expressed b y
0
t{yexv[-K(t-tr)/Cp]dt
(6)
T h i s is easily i n t e g r a t e d t o
A =
q(tf-ti)CJK
(7)
300
600
Temperature
900
(C)
Figure 5
Qualitative analysis by DTA. Four D T A curves of pure
substances, (a) Amyl alcohol (2 sample in air
at
- 1
atmospheric pressure, heating rate l O K m i n .
Transitions: 1, some crystallization at - 119C; 2, melting
at - 79 C; 3, boiling at 139 C). (b) Polyethylene
terephthalate) (10 mg sample in_ nitrogen
at atmospheric
1
pressure, heating rate 2 0 K m i n . Transitions: 1, glass
transition at about 75 C, characteristic of noncrystalline
e
materials; 2, crystallization at 145 C; 3, melting at 253 C ;
4, exothermic decomposition above 360 C). (c) Iron
( ~ 30 mg sample in helium
at atmospheric pressure,
_ I
heating rate 2 0 K m i n . Transitions: 1, a- to -
transition at 757 C; 2, - to y-iron transition at 910 C; 3,
y- to <5-iron transition at 1389 C; 4, melting at 1533 C).
(d) Barium chloride ( ~ 10 mg sample
in air at atmospheric
_ l
pressure, heating rate 2 0 K m i n . Transitions: 1 and 2,
loss of water in two stages at 130 and 187 C, respectively;
3, orthorhombic-to-cubic transition at 923 C; 4, melting
at 950 C)
501
Thermal
Analysis:
Exotherm
An
Overview
Endotherm
Ld
k.
<
/ V 2= I . O
Concentration
/V, =1.0
Figure 6
Hypothetical phase diagram of reasonable complication
(eutectic points, compound formation, partial solid-state
solubility and a peritectic point). The curves a-f drawn
above the phase diagram illustrate typical heating curves
that could be obtained with a differential scanning
calorimeter
3.
temperature
(C)
Figure 7
Typical set of melting curves of polyoxymethylene taken
at the indicated heating rates, for sample masses between
10 and 1 mg. The samples represent solution-grown stacks
of thin, lamellar crystals
Calorimetry
C a l o r i m e t r y w a s first d e v e l o p e d in t h e e i g h t e e n t h
c e n t u r y . Since t h e r e is n o direct h e a t m e t e r , m e a s u r e
m e n t s of h e a t m u s t rely o n s e c o n d a r y effects such a s
t e m p e r a t u r e rises, c h a n g e s of s t a t e , o r c h e m i c a l , elec
trical o r m e c h a n i c a l h e a t - e n e r g y c o n v e r s i o n s . T h e
m a j o r difficulty of c a l o r i m e t r y is t h e fact t h a t t h e r e is
n o perfect i n s u l a t o r for h e a t . T h e r e f o r e , loss calcula
t i o n s t o c o r r e c t for imperfect c o n t a i n m e n t of t h e h e a t
t o b e m e a s u r e d a r e basic t o all c a l o r i m e t r y . I s o t h e r
m a l o r nearly i s o t h e r m a l c a l o r i m e t e r s p e r m i t t h e best
h a n d l i n g of t h e h e a t loss p r o b l e m . A typical e x a m p l e
of a n i s o t h e r m a l c a l o r i m e t e r is s h o w n in F i g . 8. T h e
i s o t h e r m a l e n v i r o n m e n t is c r e a t e d b y a w a t e r - i c e
m i x t u r e . T h e s a m p l e t o b e investigated is d r o p p e d
from a c o n s t a n t - t e m p e r a t u r e reservoir, o r a r e a c t i o n
o r o t h e r c h a n g e of s t a t e is i n d u c e d after t h e e q u i
l i b r i u m t e m p e r a t u r e is achieved. A c h a n g e in t h e h e a t
c o n t e n t of t h e s a m p l e is d e t e c t e d b y t h e v o l u m e
c h a n g e d u e t o t h e m e l t i n g o r crystallization of t h e ice
in t h e i n n e r c a l o r i m e t e r c o n t a i n e r . T h e v o l u m e c h a n g e
502
Sample
Dewar vessel
Figure 8
Bunsen ice calorimeter
Thermal
Adiaoatic d e v i a t i o n :
Temperature:
Analysis:
An
Overview
m e t e r s , w h i c h c a n o p e r a t e o n the a d i a b a t i c o r the
differential c a l o r i m e t e r principle. D S C h a s seen t h e
largest d e v e l o p m e n t recently b e c a u s e of ease of h a n d
ling a n d c o m p u t e r c o u p l i n g . H e a t c a p a c i t y accuracies
h a v e r e a c h e d 0.1 % for s a m p l e m a s s e s as small as
10 m g . T e m p e r a t u r e r a n g e s from 100 t o 1000 a n d
1
h e a t i n g rates b e t w e e n 1 a n d 20 m i n " a r e c o m m o n .
T h e goal of m o s t c a l o r i m e t r y is t h e e s t a b l i s h m e n t of
t h e t h e r m o d y n a m i c functions of systems of interest.
H e a t s of t r a n s i t i o n a n d h e a t capacities lead t o
enthalpy data at various temperatures. Using the
t h e r m o d y n a m i c r e l a t i o n s h i p s for e q u i l i b r i u m ,
H-
H0 +
CpdT
(8)
[\cp/T)dt
(9)
J
S=S0+
jacket
4m
heating and
flow
mm\mi
cooling
Heat:
watthour
meter
pump
pressure
/C^N
+ ++ * L ~ ~
ingoing outgoing
Figure 9
Example of a typical adiabatic calorimeter
is m e a s u r e d by d e t e c t i o n of t h e c h a n g e in m e r c u r y
m a s s inside t h e c a l o r i m e t e r .
Closely related t o i s o t h e r m a l c a l o r i m e t e r s a r e a n e r
oid a n d liquid c a l o r i m e t e r s , in w h i c h a small t e m p e r a
t u r e rise in a solid (metal b l o c k ) o r liquid (water)
reservoir is m e a s u r e d precisely ( 0.001 K ) t o deter
m i n e the c h a n g e in h e a t c o n t e n t of t h e u n k n o w n .
B o m b c a l o r i m e t e r s a r e well k n o w n , being c o m m o n l y
used t o m e a s u r e h e a t s of c o m b u s t i o n t o a precision of
up to 0 . 0 1 % .
A n o t h e r type of c a l o r i m e t e r is t h e a d i a b a t i c calori
meter, in which a n a t t e m p t is m a d e t o m i n i m i z e t h e
h e a t loss by raising o r lowering t h e t e m p e r a t u r e of t h e
s u r r o u n d i n g s t o m a t c h t h e s a m p l e t e m p e r a t u r e (Fig.
9). A d i a b a t i c c a l o r i m e t e r s a r e c o m m o n l y built for
o p e r a t i o n from 10 t o a b o u t 700 K , a n d m a y r e a c h a
precision of 0 . 0 1 % in h e a t c a p a c i t y d e t e r m i n a t i o n s
for large s a m p l e m a s s e s ( 1 0 0 - 5 0 0 g). Special i n s t r u
m e n t a t i o n is available for very low t e m p e r a t u r e s .
In c o m p e n s a t i n g c a l o r i m e t e r s , t h e effect of a c h e m
ical reaction is c o m p e n s a t e d b y h e a t i n g o r cooling.
The best-known compensating calorimeters are those
t h a t m a k e use of t h e Peltier effect ( T i a n - C a l v e t calori
meters) a n d stirred-liquid c a l o r i m e t e r s ; their c o n
struction is usually a d a p t e d t o t h e specific a p p l i c a t i o n .
A b r i d g e t o D T A is achieved with s c a n n i n g calori-
G =
H-TS
(10)
Tt =
AHJASt
()
allows c o m p l e t e t h e r m a l analysis w h e n e v e r h e a t
capacities C p a n d t r a n s i t i o n e n t h a l p i e s AHt a n d
t e m p e r a t u r e s Tt a r e given. S t a n d a r d functions a r e
widely t a b u l a t e d a n d t h e t h e o r y of h e a t capacities is
well d e v e l o p e d .
4. Dilatometry
and Thermomechanical
Analysis
503
Thermal
Analysis:
An
Overview
-tU^-*
W e i g h t tray
Float
I suspension
Linear - variable
transformer
di f f e r e n t i a l
X
Gas
purge -x
(LVDT)
LVDT c o r e
Probe coupling
\Sample tube
5.
Thermogravimetry
T h e r m o g r a v i m e t r y w a s d e v e l o p e d a r o u n d 1900 a n d
basically involves t h e m a s s d e t e r m i n a t i o n of a s a m p l e
u n d e r c o n t r o l l e d i s o t h e r m a l o r linearly v a r y i n g t e m
p e r a t u r e in a given a t m o s p h e r e . A p l o t of m a s s a s a
function of time o r t e m p e r a t u r e is t h e result of a
Figure 10
TMA apparatus (courtesy of Mettler Instrument
Company)
Furnace control
Temperature
program
S a m p l e temperature
T-i
DTA
Weight i n d i c a t i o n
DTG
V a c u u m ind.ication
Diffusion
pump
Thermostat
Power supply
Temperature
Figure 11
TMA of a drawn polyester fiber
504
Figure 12
Schematic diagram of a thermogravimetry apparatus with
differential thermogravimetry (DTG) facility (courtesy of
Mettler Instrument Company)
Thermal
Figure 13
Thermogravimetric analysis of calcium oxalate with the
corresponding DTA curve
t h e r m o g r a v i m e t r i c e x p e r i m e n t . A b l o c k d i a g r a m of a
typical t h e r m o g r a v i m e t r i c a p p a r a t u s is s h o w n in F i g .
12. C o n t i n u o u s m a s s r e c o r d i n g a n d c o m p e n s a t i o n is
possible b y e l e c t r o m a g n e t i c weight c o m p e n s a t i o n .
Sensitivities a r e usually several m i c r o g r a m s . T o t a l
sample m a s s e s m a y r a n g e from milligrams t o g r a m s .
T e m p e r a t u r e r a n g e s a r e usually from r o o m t e m p e r a
ture t o a s high a s 2700 K .
M a j o r a p p l i c a t i o n s of t h e r m o g r a v i m e t r y involve
stability analysis of m a t e r i a l s in different a t m o s p h e r e s
or v a c u u m . A typical e x a m p l e is s h o w n in F i g . 13. T h e
analyzed C a C 2 0 4 . H 2 0 is seen t o d e c o m p o s e in t h r e e
stages:
C a C 20 4. H 2 0 - C a C 20 4 + H 2 0
(12)
C a C 20 4 - C a C 0 3 + CO
(13)
C a C 0 3- C a O + C0
(14)
F i g u r e 13 also s h o w s a D T A c u r v e w h i c h reveals t h a t
the first a n d t h i r d r e a c t i o n s a r e e n d o t h e r m i c , w h e r e a s
the second r e a c t i o n is c o m p l e x , involving a t least o n e
e x o t h e r m i c a n d o n e e n d o t h e r m i c stage.
T h e q u a n t i t a t i v e d a t a analysis of t h e n o n i s o t h e r m a l
reactions is usually a t t e m p t e d using s t a n d a r d r e a c t i o n
kinetics:
d[A]/dt
= k[A]
(15)
w h e r e [A] is t h e r e a c t a n t c o n c e n t r a t i o n , k is t h e
specific r a t e c o n s t a n t a n d is t h e o r d e r of t h e r e a c
tion. T h e t e m p e r a t u r e d e p e n d e n c e o f k is i n c o r p o r
ated in E q n . (15) using t h e A r r h e n i u s e q u a t i o n :
dk/dT=
A e x p ( - EJRT)
(16)
w h e r e E& is t h e a c t i v a t i o n energy. F r e q u e n t l y , h o w
ever, E q n . (15) is a n oversimplification; m o r e c o m p l i
cated a n d m u l t i p l e r e a c t i o n p a t h s often m a k e a simple
Analysis:
An
Overview
Bibliography
Benedict R 1977 Fundamentals of Temperature, Pressure
and Flow Measurements, 2nd edn. Wiley, New York
Buzas I (ed.) 1975 Thermal Analysis, Proc. 4th Int. Conf.
Thermal Analysis. Heyden, London
Chihara (ed.) 1977 Thermal Analysis, Proc. 5th Int. Conf.
Thermal Analysis. Heyden, London
Duval C 1963 Inorganic Thermogravimetric Analysis, 2nd
edn. Elsevier, Amsterdam
MacKenzie R C (ed.) 1970,1972 Differential Thermal Analy
sis. Interscience, New York
Madorsky S L 1964 Thermal Degradation of Organic
Polymers. Interscience, New York
Miller (ed.) 1982 Thermal Analysis, Proc. 7th Int. Conf.
Thermal Analysis. Wiley, New York
Redfern J (ed.) 1965 Thermal Analysis, Proc. 1st Int. Conf.
Thermal Analysis. Macmillan, London
Rossini F D, Sumner S (eds.) 1979 Experimental Thermo
chemistry, Vol. 3. Pergamon, New York
Schwenker R F Jr, Gam D (eds.) 1969 Thermal Analysis,
Proc. 2nd Int. Conf. Thermal Analysis. Academic Press,
New York
Touloukian Y S, Ho C Y (eds.) 1970-79 Thermophysical
Properties of Matter; The TPRC Data Series. A Compre
hensive Compilation of Data. IFI/Plenum, New York
Turi 1981 (ed.) Thermal Analysis of Polymeric Materials.
Academic Press, New York
Weissberger A, Rossiter W (eds.) 1971 Physical Methods
of Organic Chemistry, Physical Methods of Chemistry,
Vol. 1, Pt. V: Determination of Thermodynamic and
Surface Properties. Wiley, New York
Wendlandt W W 1974 Thermal Methods of Analysis, 2nd
edn. Wiley, New York
Wiedemann G (ed.) 1972 Thermal Analysis, Proc. 3rd Int.
Conf Thermal Analysis. Birkhauser, Basel
Wiedemann G (ed.) 1980 Thermal Analysis, Proc. 6th Int.
Conf. Thermal Analysis. Birkhauser, Basel
Wunderlich 1981 Thermal Analysis, Audio Course and
Text. Rensselaer Polytechnic Institute, Troy, N Y
B. W u n d e r l i c h
[Rensselaer P o l y t e c h n i c I n s t i t u t e ,
Troy, New York, USA]
505
Thermal
Analysis:
Recent
Developments
/.
Thermogravimetry
and
Thermomagnetometry
of TG and
TM
506
Thermal
- maximum
Analysis:
Recent
Developments
oxidation
0.02
9.96
-stoichiometric composition -
I IOC
Temperature
I
80C
1000
I
700
(C)
Figure 1
Excess oxygen coefficient and corresponding weight of Nio^Zno 1 7 F
7 e2 1 30
8 4 vs temperature and oxygen content of the gas
phase
Temperature
1400
1300
1200
1100
(C)
1000
precise c o m p o s i t i o n a t s o m e reference p o i n t . T h e r e
a r e a variety of analytical m e t h o d s available: r e d u c
t i o n in h y d r o g e n o n a t h e r m o b a l a n c e t o yield t h e
alkaline e a r t h a n d r a r e - e a r t h oxides p l u s c o p p e r a n d /
o r lead m e t a l s is o n e of t h e m o s t c o m m o n l y u s e d
m e t h o d s . It d o e s n o t w o r k for t h e b i s m u t h o r t h a l l i u m
c o m p o u n d s , b e c a u s e of t h e volatility of t h e m e t a l s .
O t h e r w a y s T G is used effectively in s t u d y i n g these
104.0
B a 2Y C u 30 7
103.5
B i 2S r C a 2C u 20 8
103.0
P b 2S r 2Y C u 30 8
102.5
^
102.0
101.5
101.0
100.5
100.0
99.5
99.0
\/T
I0
(K )
Figure 2
Isocompositional phase diagram for ^ 1 7 7F3 e 2 , 3 80 4
constructed with interpolated values from Fig. 1: the
oxygen excess coefficient is indicated on each
isocompositional line
98.5
9
08
100.0
200.0
300.0 400.0
500.0 600.0
Temperature
700.0 800.0
900.0
(C)
Figure 3
-1
TG curves for several oxides heated at 1 C m i n in
oxygen
507
Thermal
Analysis:
Recent
Developments
temperature
to I05C
magnet out
nitrogen
oxygen
ash from
Fig. I
Time
Time
(a)
(b)
Figure 4
Proximate analysis scheme for coal analysis based on T G and T M
systems is t o follow t h e d e c o m p o s i t i o n of p r e c u r s o r
c o m p o u n d s s u c h a s t h e m i x e d o x a l a t e s ( O z a w a 1988)
o r for assaying t h e initial s t a r t i n g c o m p o u n d s . T h e
alkaline a n d r a r e - e a r t h oxides a r e n o t o r i o u s for
a b s o r b i n g large q u a n t i t i e s of H 2 0 a n d C 0 2 , d u r i n g
s t o r a g e a n d m a n y of t h e soluble salts, s u c h as n i t r a t e s
a n d acetates, frequently used for synthesis h a v e
u n c e r t a i n w a t e r c o n t e n t s . D e g r a d a t i o n of t h e
B a 2Y C u 30 7 material on exposure to C 0 2 and H 2 0 has
also been investigated b y T G ( G a l l a g h e r et al. 1988a).
Studies involving p e r m a n e n t gases o r m a t e r i a l s of
high volatility a t relatively low t e m p e r a t u r e (e.g.,
H 2 0 ) a r e easy t o set u p a n d c o n t r o l . It is m o r e difficult
t o p e r f o r m e x p e r i m e n t s t h a t involve t h e v a p o r t r a n s
p o r t of Z n O , P b O , L i 2 0 a n d so o n . T h e t e c h n i q u e
utilized b y H o l m a n (1974) is useful if suitably inert
furnace t u b e s , s a m p l e c o n t a i n e r s a n d s u s p e n s i o n
m a t e r i a l s a r e available. A s a n e x a m p l e , lead-deficient
lead t i t a n a t e ( P b T i 0 3 ) is s u s p e n d e d from a b a l a n c e
a n d s u r r o u n d e d b y t h e t w o - p h a s e m i x t u r e a t either
p h a s e b o u n d a r y . A s t h e t e m p e r a t u r e is raised t o a
p o i n t for a r e a s o n a b l e r e a c t i o n r a t e , t h e lead v a p o r
pressure is m a i n t a i n e d c o n s t a n t a t t h e v a l u e e s t a b
lished b y t h e t w o - p h a s e buffer m a t e r i a l a t t h a t t e m
p e r a t u r e . T h e c h a n g e of t h e s a m p l e c a n b e followed
until it reaches its e q u i l i b r i u m value a t t h a t t e m p e r a
t u r e a n d t h e p a r t i a l p r e s s u r e of t h e lead. If t h e
c o m p o s i t i o n a t t h e p h a s e b o u n d a r y is k n o w n a c c u r
ately, t h e n t h e original lead deficiency c a n be deter
m i n e d . If n o t t h e n only relative values for different
c o n d i t i o n s c a n b e established.
T h e use of c o m b i n e d T G a n d T M for t h e p r o x i m a t e
analysis of coal is s h o w n in F i g . 4 ( A y l m e r a n d R o w e
1982). Clearly resolved weight losses o c c u r for m o i s
t u r e a n d volatiles in n i t r o g e n . Switching t o a n oxi
dizing a t m o s p h e r e allows c o m b u s t i o n of t h e fixed
c a r b o n . After c o o l i n g t o r o o m t e m p e r a t u r e t h e origi-
508
n a l pyrite c o n t e n t is d e t e r m i n e d b y a T M r e d u c t i o n of
t h e i r o n oxide in t h e a s h t o i r o n m e t a l b y h y d r o g e n .
A s i r o n m e t a l f o r m s , t h e a p p a r e n t weight increases
b e c a u s e of t h e s t r o n g m a g n e t i c a t t r a c t i o n of i r o n . T h e
relatively r a p i d a n d simple analysis of these five
c o m p o n e n t s of c o a l agrees very well w i t h results
obtained using the previous m o r e cumbersome
methods.
C h a r l e s (1982) p r o v i d e s a n excellent e x a m p l e of t h e
use of T M t o s t u d y c o r r o s i o n . A T M a p p a r a t u s is
s h o w n in F i g . 5a a n d s o m e results for t h e r a t e of
c o r r o s i o n of steel b y a n a q u e o u s a m m o n i a c a l E D T A
s o l u t i o n a r e p r e s e n t e d in F i g . 5b. T h e o x i d a t i o n of
thin c o b a l t films o r their r e a c t i o n with a silicon
s u b s t r a t e w a s also studied b y T M ( G a l l a g h e r et al.
1987b). O t h e r metallurgical e x a m p l e s of T M a r e given
b y H a g l u n d (1982). T h e use of T M t o establish t h e
presence of m a g n e t i t e a s a n i n t e r m e d i a t e d u r i n g t h e
d e c o m p o s i t i o n of siderite ( F e C 0 3 ) in air o r oxygen
h a s also b e e n described. M a g n e t i t e did n o t f o r m in air
o r oxygen a n d t h e m a g n e t i t e t h a t did f o r m u n d e r inert
c o n d i t i o n s i n c o r p o r a t e d m o s t of t h e divalent i m p u r i
ties (e.g., m a g n e s i u m , c a l c i u m o r m a n g a n e s e ) . U s e of
w e l l - k n o w n values of Tc for p u r e m e t a l s a n d alloys is
a c o m m o n m e t h o d t o c a l i b r a t e t h e t e m p e r a t u r e scale
d u r i n g T G . G a l l a g h e r a n d G y o r g y (1986) described
s o m e of t h e factors t h a t affect t h e a c c u r a c y a n d
c o m p a r e d this m e t h o d w i t h t h e use of m e l t i n g p o i n t s
for t e m p e r a t u r e c a l i b r a t i o n .
2. Differential
Thermal
Scanning
Calorimetry
Analysis
and
Differential
Thermal
,Cahn m o d e l RH
recording balance
nm
^Counter weights
Sealed glass or t i t a n i u m
"reaction tube
Corroding solution
F o i l or powdered
specimen
- Electromagnet
Thermocouple probe
(a)
9 0 C
I20C
I30C
I40C*V^
0
40
80
120
160
200
Recent
Developments
Furnace
150
Analysis:
240
Time (min)
(b)
Figure 5
A TM study of the aqueous corrosion of steel: (a) TMA
apparatus as used for aqueous corrosion work; and
(b) corrosion of 2 mil type 285 carbon steel in 5%
ammoniated EDTA solutions
3. Evolved
Gas
Analysis
509
Thermal
Analysis:
Recent
Developments
<
900
100
200
Temperature
300
400
500
(C)
Temperature
(C)
Figure 6
(a) DTA curves for oxidation of CO using catalysts with
a
-1
wide variety of activities (the heating rate is 2 C m i n in
a gas stream
of 2% CO, 2% 0 2 and 96% N 2 at
3
-1
2
100 cm m i n ) : (i) copper chromite,
16.0 mg, 18.0 m g~
2
(ii) Lao 5Sr 0 5Mn0 3, 16.0mg, 31.5 2m g ' ; (iii)
La 0 7 5Ko 2 5Mn0 3, 15.3 mg, 18.7 m g ' ; 2 (iv) La 0 7Pb 0 3MnO 3,
crystals, 3000 ppm Pt, 16.4 mg, 3.1 m g " a n d (vj 2 1
La 0 7Pb 0 3MnO 3, crystals, 1600 ppm Pt, 16.3 mg, 2.0 m g .
(b) DTA curves for the catalytic2 oxidation
of CO using
-1
Lae0 5Sr 0 5MnO
(the heating rate is
3, 15.7 mg, 28.6 m g
1
10 C min" in3 a gas1 stream of 2% CO, 2% 0 2 and 96%
N 2 at 500 cm m i n ) : (i) first cycle, no S 0 2 ; (ii) second
cycle, 150 ppm S 0 2 in gas stream; and (iii) third cycle,
150 ppm S 0 2 in gas stream
c o n t e n t , a n d t h e chemical c o n s e q u e n c e s inferred.
Evolved gas detection is a n a l o g o u s in t h a t t h e p r e s
ence of volatile species is detected b u t n o t their
specific n a t u r e . T h e r e a r e m a n y such q u a l i t a t i v e detec
t o r s t h a t c a n b e used t o sense t h e e v o l u t i o n of volatile
p r o d u c t s (e.g., t h e r m a l c o n d u c t i v i t y , g a s density,
flame i o n i z a t i o n , b r o a d - b a n d optical a t t e n u a t i o n ,
etc.). Evolved gas analysis ( E G A ) , h o w e v e r , utilizes
techniques t h a t a r e c a p a b l e of specifically a n a l y z i n g
the evolved gas (e.g., F o u r i e r t r a n s f o r m infrared
s p e c t r o s c o p y ( F T I R ) , gas c h r o m a t o g r a p h y ( G C ) ,
m a s s s p e c t r o m e t r y ( M S ) , etc.). D e t e c t o r s sensitive t o
510
1000
T e m p e r a t u r e (C)
Figure 7
-1
D T A curves of Ba 2YCu 30 7 at 10 C m i n in various
atmospheres
of EGA
T h e r e d u c t i o n of oxides b y h y d r o g e n offers a n o p p o r
t u n i t y t o use a specific g a s d e t e c t o r for H 2 0 ( R o w e et
al. 1983). T h e small r e a c t o r p a c k a g e used in this
research w a s c o n v e n i e n t t o o p e r a t e b e t w e e n t h e poles
of a n e l e c t r o m a g n e t in o r d e r t o d e t e r m i n e t h e effect of
a n e x t e r n a l m a g n e t i c field o n t h e r a t e of r e a c t i o n . T h e
m i n e r a l c o m p o n e n t s in a s b e s t o s v a r y c o n s i d e r a b l y
from o n e t o a n o t h e r . A T G m e t h o d h a d been p r o
p o s e d for analysis; h o w e v e r , E G A analysis b y M S
revealed t h e p r o b l e m s associated with s o m e of the
u n d e r l y i n g a s s u m p t i o n s ( K h o r a m i et al. 1984).
T h e laser h e a t i n g s c h e m e m e n t i o n e d in Sect. 3.1
w a s used b y L u m a n d Feinstein (1981) t o s t u d y the
d e c o m p o s i t i o n of a N o v o l a c e p o x y used t o e n c a p s u
late s e m i c o n d u c t o r s . A n isometric p l o t of t h e t o t a l ion
c u r r e n t a n d m a s s i o n profiles o v e r t h e r a n g e of a t o m i c
Thermal
Analysis:
Recent
Developments
e v o l u t i o n c a n also be o b s e r v e d in F i g . 9, w h e r e t h e
p e a k s n e a r 300 C c o r r e s p o n d w i t h t h e a m o r p h o u s - t o crystalline p h a s e t r a n s i t i o n revealed b y D S C .
4. Dynamic Mechanical
Thermodilatometry
Analysis
Temperature (C)
Figure 8
Isometric plot of mass profiles of evolved gases vs
temperature for Novolac epoxy
and
Considerations
A typical d y n a m i c m e c h a n i c a l analysis ( D M A )
a p p a r a t u s is s h o w n schematically in F i g . 10 ( W e n d l a n d t a n d G a l l a g h e r 1981). T h e a m o u n t of energy
necessary t o m a i n t a i n t h e s a m p l e in r e s o n a n t oscilla
t i o n a t c o n s t a n t a m p l i t u d e is p r o p o r t i o n a l t o t h e
e n e r g y lost d u e t o i n t e r n a l friction. T h e driven s a m p l e
a r m is displaced several t e n t h s of a millimeter a n d
released t o s t a r t t h e oscillation. A feedback m e c h a n
ism from t h e linear t r a n s f o r m e r t o t h e driver m a i n
tains t h e a m p l i t u d e of oscillation. D M A is p r i m a r i l y
used in p o l y m e r science t o s t u d y relationships
b e t w e e n s t r u c t u r e a n d p r o p e r t i e s . T h e difference
b e t w e e n a n e l a s t o m e r a n d a stiff plastic c a n b e readily
seen in a p l o t of t h e m o d u l u s vs t e m p e r a t u r e . T h e
v a r i o u s p e a k s in t h e loss ( t a n ) c o r r e l a t e with t o u g h
ness a n d d a m p i n g , w h i c h a r e of g r e a t i m p o r t a n c e in
e l a s t o m e r s . D e t e r m i n i n g t h e frequency a n d t e m p e r a
t u r e d e p e n d e n c e for i n t e r n a l m o t i o n s within p o l y m e r s
is v a l u a b l e in d e t e r m i n i n g t h e n a t u r e of c h a i n seg
m e n t s , crystallinity, plasticizers, a n i s o t r o p i c p r o p e r
ties a n d so o n .
T h e r m a l e x p a n s i o n is a p r o p e r t y of g r e a t t e c h n o l o
gical i m p o r t a n c e . It d e t e r m i n e s w h e t h e r p a r t s will
m a i n t a i n their a l i g n m e n t , c o n t i n u e t o a d h e r e , o r
possibly b i n d as t h e t e m p e r a t u r e shifts. A s t h e t e m
p e r a t u r e varies, c h a n g e s in length o c c u r discontin u o u s l y a t a first-order p h a s e t r a n s i t i o n o r as a
c h a n g e in t h e slope for h i g h e r - o r d e r t r a n s f o r m a t i o n s
such as t h e glass t r a n s i t i o n . T h e s h r i n k a g e of a
m a t e r i a l is o n e of t h e m o s t c o m m o n m e t h o d s for
following t h e sintering p r o c e s s .
4.2 Applications of DMA and
Thermodilatometry
C o m p o s i t e s a r e c u r r e n t l y a fertile field of study. T h e
i n t e r r e l a t i o n of time a n d t e m p e r a t u r e is evident in t h e
D M A results for t h e c u r e p r o c e s s of a g r a p h i t e
e p o x y " p r e p r e g " for m a k i n g a fiber-reinforced c o m
posite, p r e s e n t e d in F i g . 11. T h e m o d u l u s a n d reso
n a n t frequency initially decrease a s t h e t e m p e r a t u r e is
raised. T h e n , u n d e r i s o t h e r m a l c o n d i t i o n s , t h e m o d u
lus c o n t i n u e s t o rise as t h e c u r e r e a c t i o n p r o c e e d s .
T h e r m a l e x p a n s i o n h a s b e e n successful in s t u d y i n g
several aspects of L i N b 0 3 . Since t h e m a t e r i a l is used
for e l e c t r o o p t i c switching, t h e p r e s e r v a t i o n of optical
a l i g n m e n t w i t h i n t h e device p a c k a g e is crucial. Be
sides p r o v i d i n g critical e x p a n s i o n d a t a for v a r i o u s
device c o m p o n e n t s , t h e r m a l e x p a n s i o n w a s used t o
detect subtle t r a n s i t i o n s n e a r a m b i e n t t e m p e r a t u r e .
T h e Tc for a l m o s t s t o i c h i o m e t r i c m a t e r i a l , t h a t is, only
511
Thermal
Analysis:
Recent
Developments
10.0
9.0
()
8.0
7.0
6.0
5.0
<
<
600
800
1000
1000
1200
1200
T e m p e r a t u r e (C)
T e m p e r a t u r e (C)
<
200
400
600
800
1000
1200
T e m p e r a t u r e (C)
4.8
(e)
4.4
4.0
3.6
3.2
2.8
2.4
2.0|
<
<
1.6
l.2|
0.8
0.4|
400
T e m p e r a t u r e (C)
"
600
800
1000
1200
T e m p e r a t u r e (C)
Figure 9
EGA of trapped gases in thin films of sputtered TaSi2: (a) hydrogen, (b) nitrogen, (c) oxygen, (d) water vapor and
(e) argon
Thermal
Electromechanical
transducer
Analysis:
Recent
Developments
Counter
weight
S a m p l e ~|
Thermocouple
J W
JL
Flexure pivots
.c
IOH
Furnace
Driver
Frequency
display
1000
Damping
display
Programmer
Recorder
t h
Figure 70
Schematic of the Du Pont Model 981 D M A module
40
41
81
121
1400
1600
Figure 12
Sintering behavior of Ti0 2-coated A1 20 3 spheres at
50Cmin~' in air
1200
T e m p e r a t u r e (C)
161
201
Time
241
281
321
361
401
441
(min)
Figure 11
DMA results for a graphite-epoxy prepreg (courtesy of
Dupont Instruments)
in Thermal
Analysis
C o n t r o l l i n g t h e r a t e of h e a t i n g by feedback from t h e
p r o c e s s v a r i a b l e of interest p r o d u c e results closer t o
e q u i l i b r i u m (i.e., less influenced b y m a s s o r t h e r m a l
t r a n s p o r t ) . A n e x a m p l e from t h e review b y P a u l i k a n d
P a u l i k (1986) is p r e s e n t e d in F i g . 13. P o t a s s i u m
h y d r o g e n c a r b o n a t e is d e c o m p o s e d a t a h e a t i n g r a t e
_1
of 3 C m i n d u r i n g t e m p e r a t u r e r a n g e s w h e r e there
is insignificant weight loss a n d a t t h e r a t e yielding
7
_1
during the decomposition
about 3 * 1 0 ~ k g m i n
stages. C u r v e s (i) a n d (ii) s h o w t h e t e m p e r a t u r e a n d
weight, respectively, as a function of time, while curve
(iii) s h o w s t h e resulting weight vs t e m p e r a t u r e p l o t in
c o m p a r i s o n with t h e c o n v e n t i o n a l T G , c u r v e (iv).
T h e r e is greatly e n h a n c e d r e s o l u t i o n evident in t h e
" q u a s i i s o t h e r m a l " p l o t . R o u q u e r o l (1964) h a s
d e m o n s t r a t e d t h a t similar benefits c a n b e derived
b y u s i n g feedback from a p r e s s u r e sensor t o c o n t r o l
t h e r a t e of h e a t i n g . T h i s is t h e a n a l o g o u s s i t u a t i o n
based on E G A . These m e t h o d s provide a better
u n d e r s t a n d i n g of t h e t r u e processes t a k i n g place d u r
ing d e c o m p o s i t i o n .
T h i s s a m e a p p r o a c h c a n b e utilized in t e c h n o l o g y t o
p r o v i d e a b e t t e r p r o d u c t a t t h e expense of less energy.
H u c k a b e e a n d P a l m o u r (1972) d e m o n s t r a t e d " r a t e c o n t r o l l e d s i n t e r i n g " w h i c h n o t only allowed for a
d e n s e r finer-grained sintered p r o d u c t b u t also saved
energy by reducing the time-temperature needed to
obtain that superior microstructure. This was
achieved b y p r e d e t e r m i n i n g t h e o p t i m u m r a t e of
s h r i n k a g e t h a t w o u l d m a i n t a i n a n o p e n p o r o s i t y so
t h a t a m i n i m u m of t r a p p e d p o r e s w o u l d o c c u r d u r i n g
t h e early stage of sintering. T h e s e t r a p p e d p o r e s a r e
p a r t i c u l a r l y difficult t o e l i m i n a t e in t h e latter stages of
sintering. T h e t e m p e r a t u r e vs t i m e c u r v e (similar t o
c u r v e 1 in F i g . 13) t h a t p r o v i d e d this c o n t r o l l e d
s h r i n k a g e w a s r e c o r d e d in t h e p r e l i m i n a r y e x p e r i m e n t
a n d u s e d for s u b s e q u e n t p r o d u c t i o n .
513
Thermal
Analysis:
Recent
Developments
200
100
Time (min)
KHC03
0
\
3
Q-TG
20
\ t g
\
\
k
f>
2 c o 3
150
200
Temperature (C)
Figure 13
Dehydration of K H C 0 3 measured by TG under
quasi-isothermal (Q) conditions
Bibliography
Agarwal , N o h J S, Schwartz J A, Davini 1987 Effect
of surface acidity of activated carbon on hydrogen stor
age. Carbon 25: 219-26
Aylmer D, Rowe W 1982 Thermo-magneto-gravimetric
analysis of pyrite in coal and lignite. In: Miller (ed.)
1982 Proc. 7th Int. Conf. Thermal Imaging, Vol. 2. Wiley,
Chichester, UK, pp. 1270-5
Balek V 1987 Emanation thermal analysis: a status report.
Thermochim Acta 110: 222-35
Boersma S L 1955 Theory of differential analysismeasure
ment and interpretation. / . Am. Ceram. Soc. 38: 281-7
Bracconi P, Gallagher 1972 Phase diagram of a nickelzinc ferrite of composition: N i 0 6 8 Z
5 n 0 1 7F
7 e 2 1 3O
8 4 +r J. Am.
Ceram. Soc. 62: 171-6
Charles R G 1982 Thermomagnetic analysis as a means for
following corrosion reactions in sealed systems. In: Miller
(ed.) 1982 Proc. 7th Int. Conf. Thermal Imaging, Vol. 1.
Wiley, Chichester, UK, pp. 264-71
514
Thermal
Lum R 1977 Direct analysis of polymer pyrolysis using
laser microprobe techniques. Thermochim. Acta 18: 73-94
Lum R M, Feinstein L G 1981 Investigation of the molecu
lar processes controlling corrosion failure mechanisms in
plastic encapsulated semiconductor devices. Microelectron. Reliab. 21: 15-31
Mackenzie R C 1980 Differential thermal analysis and
differential scanning calorimetry. Similarities and dif
ferences. Anal. Proc. (London) 17: 217-20
Morros S A, Stewart D 1976 Automated and computerized
system for purity determination by differential scanning
calorimetry. Thermochim. Acta 14: 13-24
O'Bryan , Gallagher 1987 Characterization of
Ba 2YCu 30 Jt as a function of oxygen partial pressure. Part
II: Dependence of the O-T transition on oxygen content.
Adv. Ceram. Mater. 2: 642-8
Okamura H, Barringer A, Bowen 1986 Preparation
and sintering of monosized A1 20 3Ti0 2 composite
powder. J. Am. Ceram. Soc. 69: C22-24
Ozawa 1988 Application of thermal analysis to kinetic
study of superconducting oxide formation. Thermochim.
Acta 133: 11-16
Paulik F, Paulik J 1986 Thermoanalytical examination
under quasi-isothermal-quasi-isobaric conditions. Ther
mochim. Acta 100: 23-59
Rouquerol J 1964 Thermal analysis under low pressure and
constant rate of decomposition. Bull. Soc. Chim. Fr. 1964:
31-2
Rowe R, Gallagher , Gyorgy 1983 Establishing
the absence of any influence by an external analysis field
upon the intrinsic rate of reduction of magnetite by
hydrogen. / . Chem. Phys. 79: 353-6
Schubart B, Knothe 1972 A new thermogravimetric
instrument for chemical analysis with weighing com
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Progress in Vacuum Microbalance Techniques, Vol. 1.
Heyden, Norwich, UK, pp. 207-15
Warne S S, Gallagher 1987 Thermomagnetometry.
Thermochim. Acta 110: 269-79
Wendlandt W W, Gallagher 1981 Instrumentation. In:
Turi A (ed.) 1981 Thermal Characterization of Poly
meric Materials. Academic Press, New York, Chap. 1
P. K. Gallagher
[Ohio S t a t e University, C o l u m b u s ,
Ohio, USA]
Wave
Imaging
7. The Temperature
Field in a Uniform
Layered
Solid
T o illustrate t h e general characteristics of t h e r m a l
wave imaging, consider the temperature distribution
p r o d u c e d b y a spatially u n i f o r m optical s o u r c e of
intensity I0 () w h i c h is a m p l i t u d e m o d u l a t e d a t a n
a n g u l a r frequency cwm. T h e r a t e of h e a t d e p o s i t i o n in a
layered solid w i t h a n u p p e r layer of thickness is
(,)
= - ( \ - R)I0 exp[j(o> -
c o m) i ] F e x p ( - z )
w h e r e is t h e d e p t h in t h e s a m p l e , R t h e reflectivity,
t h e a b s o r p t i o n coefficient a n d F t h e fraction of t h e
a b s o r b e d energy t h a t is c o n v e r t e d t o h e a t . G i v e n these
c o n d i t i o n s , t h e specimen t e m p e r a t u r e a t d e p t h c a n
b e d e t e r m i n e d using t h e o n e - d i m e n s i o n a l t h e r m a l
diffusion e q u a t i o n
2
d T,
.ldT/
H(z,t)
x
(z,r)-a
' _ ( * , , ) = - - ^
515
Thermal
Wave
Imaging
w h e r e is t h e t h e r m a l diffusivity, t h e t h e r m a l
c o n d u c t i v i t y a n d C t h e specific h e a t . T h e surface
t e m p e r a t u r e is ( M u r p h y et al. 1992):
,) =
0 ( 1 " R)FI0(a>)
{
2
\- \
2 e x p ( - L/(5 0)cosh(z/<5 0)
1 - T e x p ( - 2 L / ( 5 0)
r e x p ( - L / J 0)
\1+/Si0
= (/ Mn) '
a
0 5
1 - M
)]|
0)
w h e r e 0
is t h e t h e r m a l diffusion l e n g t h
a n d is a n interlayer t h e r m a l m i s m a t c h factor.
Several i m p o r t a n t p r o p e r t i e s of t h e r m a l w a v e
m e t h o d s a r e c o n t a i n e d in E q n . (1).
1.1 Thermal Depth
Profiling
T(Q,co,com) is a p h a s o r possessing m a g n i t u d e a n d
p h a s e a t t r i b u t e s . If L / < 5 0> 1 , t h e n | ( 0 , , ) | a n d
[,,^],
t h e p h a s e of , , ^ , b e c o m e insen
sitive t o t h e presence of t h e lower layer while if
L/S0< 1, b o t h reflect t h e p r e s e n c e of t h e l o w e r layer.
T h i s c o n d i t i o n allows t h e r m a l d e p t h profiling of b u r
ied s t r u c t u r e s t h r o u g h t h e d e p e n d e n c e of | ( 0 , , ) |
a n d | T ( 0 , c o , G ) m) ] o n co m a n d h e n c e o n 0.
[T(0,co,com)] offers s o m e s u b s t a n t i a l a d v a n t a g e s in
T W I since it is insensitive t o c h a n g e s in s a m p l e
reflectivity. S u b s u r f a c e s t r u c t u r e s w h i c h m o d i f y t h e
flow of h e a t in t h e s p e c i m e n c a n b e i m a g e d a n d t h e i r
d e p t h d e t e r m i n e d t h r o u g h t h e d e p e n d e n c e of t h e r m a l
images o n com. A p p l i c a t i o n s i n c l u d e i m a g i n g of v o i d s ,
interfaces a n d regions w h e r e i n t e r l a m i n a r d i s b o n d i n g
o c c u r s in c o m p o s i t e m a t e r i a l s .
1.2 Thermal
Spectroscopy
516
2.
Imaging
A d e s c r i p t i o n of t h e T W I of m a t e r i a l s requires t h a t
E q n . (1) b e modified t o i n c l u d e spatially d i s t r i b u t e d
s o u r c e s a n d t h r e e - d i m e n s i o n a l h e a t flow in t h e speci
m e n . H o w e v e r , t h e r m a l d e p t h profiling, s p e c t r o s c o p y
a n d s o u r c e - d e p e n d e n t i m a g e c o n t r a s t a r e still p r e s e n t .
T w o g e n e r a l i m a g i n g f o r m a t s exist: spatially localized
h e a t i n g a n d spatially localized d e t e c t i o n . O f c o u r s e ,
b o t h m a y b e p r e s e n t s i m u l t a n e o u s l y (Tarn 1986).
2.1 Localized
Source
Imaging
A localized s o u r c e c r e a t e s a r e g i o n of excess t e m p e r a t
u r e w h o s e size is d e t e r m i n e d b y t h e spatial e x t e n t of
t h e s o u r c e a n d b y t h e r m a l diffusion. I m a g e s a r e
formed by scanning the source over the sample and
r e c o n s t r u c t i n g t h e t e m p e r a t u r e field from s t o r e d d a t a .
B o t h localized d e t e c t i o n , w h i c h m o n i t o r s (0,,) in a
small r e g i o n n e a r t h e s o u r c e , a n d n o n l o c a l i z e d detec
t i o n , w h i c h m o n i t o r s 3 ( 0 , ) a v e r a g e d o v e r t h e s a m
ple, c a n b e u s e d . H o w e v e r , in t h e first case b o t h
t e m p e r a t u r e a n d h e a t flow c a n b e d e t e r m i n e d b y
varying the separation distance between source a n d
d e t e c t o r . T h e lateral spatial r e s o l u t i o n for t h e i m a g i n g
of a b u r i e d feature is d e t e r m i n e d b y t h e r a t i o s SJRQ
a n d SJL w h e r e
is t h e size of t h e s o u r c e ( a s s u m e d
G a u s s i a n ) a n d L is t h e d i s t a n c e b e t w e e n d e t e c t o r a n d
s a m p l e feature. F o r i m a g i n g w h i c h m o n i t o r s t h e
surface t e m p e r a t u r e of t h e s p e c i m e n , L is t h e d e p t h of
t h e feature in t h e s a m p l e . F o r small L t h e r e s o l u t i o n is
a p p r o x i m a t e l y e q u a l t o RQ while for larger L t h e
r e s o l u t i o n is d e t e r m i n e d b y t h e g r e a t e r of S0 a n d RQ,
p r o v i d e d SJL > 1. A r e s o l u t i o n of t h e o r d e r of m i c
r o m e t e r s c a n b e achieved for n e a r - s u r f a c e features
w h e n a focused laser o r particle b e a m s o u r c e is used.
2.2 Generalized
Source
Imaging
A n o n u n i f o r m d i s t r i b u t i o n of h e a t c a n b e p r o d u c e d
b y u n i f o r m i l l u m i n a t i o n in a h e t e r o g e n e o u s s a m p l e
via spatially v a r y i n g a b s o r p t i o n o r s u b s e q u e n t ther
m a l diffusion. I m a g e f o r m a t i o n r e q u i r e s t h a t t h e
t e m p e r a t u r e b e m e a s u r e d u s i n g a localized d e t e c t o r o r
a d e t e c t o r a r r a y . F r o m t h e v i e w p o i n t of t h e t e m p e r a t
u r e field, t h e spatial r e s o l u t i o n w h i c h c a n b e achieved
is d e s c r i b e d b y t h e analysis in Sect. 2.1 a n d d e p e n d s
Thermal
o n ratios of t h e r m a l a n d physical lengths. T h e i m a g e
resolution, h o w e v e r , also d e p e n d s o n t h e d e t e c t i o n
m e t h o d selected as described in Sect. 3.
3. Detection
Methods
All m e t h o d s o f detecting t e m p e r a t u r e m o n i t o r a
physical p r o p e r t y of t h e s a m p l e o r its e n v i r o n m e n t .
T h e m o s t i m p o r t a n t p r o p e r t i e s in use for T W I a r e
infrared (ir) e m i t t a n c e , reflectivity, surface o r v o l u m e
strain, index o f refraction of t h e specimen o r a fluid in
t h e r m a l c o n t a c t w i t h t h e specimen a n d h e a t transfer
to a thin pyroelectric film sensor a t t a c h e d t o t h e
sample. T h e distinctive a s p e c t s o f several m e t h o d s a r e
s u m m a r i z e d in Sects. 3.1-3.2. T h e choice of m e t h o d is
i n t e n d e d t o illustrate h o w i m a g e c o n t r a s t a n d its
i n f o r m a t i o n c o n t e n t c a n c h a n g e with d e t e c t i o n
method.
3.1 Photothermal Radiometric
Methods
R a d i o m e t r i c T W I m o n i t o r s c h a n g e s in m o d u l a t e d ir
emission c a u s e d by t e m p e r a t u r e increases in local
regions of a n externally h e a t e d s a m p l e . T h e S t e f a n B o l t z m a n n law describes t h e t o t a l r a d i a n t e m i t t a n c e
4
Woi a b o d y a t t e m p e r a t u r e as W= w h e r e is
12
- 2
the S t e f a n - B o l t z m a n n c o n s t a n t (5.67 1 0 " W c m
4
K " ) a n d is t h e emissivity. A c h a n g e in s a m p l e
t e m p e r a t u r e p r o d u c e s a c h a n g e in r a d i a n t emit
3
tance \=4
ST w h e r e is t h e a m b i e n t t e m
p e r a t u r e of t h e specimen a n d W h a s been i n t e g r a t e d
3
over ir wavelength. T h e presence of t h e t e r m
implies t h a t this m e t h o d is potentially i m p o r t a n t for
h i g h - t e m p e r a t u r e i m a g i n g . Since d e t e c t i o n is typically
based o n H g C d T e , I n S b a n d o t h e r n a r r o w b a n d g a p
s e m i c o n d u c t o r s , o n l y a restricted b a n d of t h e e m i t t e d
wavelengths is actually detected. It is i m p o r t a n t t h a t
the emission d e p t h of t h e ir r a d i a t i o n in this d e t e c t i o n
b a n d be k n o w n for q u a n t i t a t i v e studies. A significant
a d v a n t a g e of this m e t h o d is t h e availability o f
infrared d e t e c t o r a r r a y s o r s c a n n e d d e t e c t i o n systems
which facilitate t h e i m a g i n g of large a r e a s . H o w e v e r ,
the spatial r e s o l u t i o n w h i c h c a n b e realized b y this
m e t h o d is limited by t h e d e t e c t i o n m e t h o d itself. F o r
ir imaging, t w o lateral spatial features s e p a r a t e d b y a
length d c a n be resolved only w h e n /d < 1 w h e r e is
the ir wavelength. Spatially v a r y i n g s a m p l e emissivity
c a n present a n o t h e r p r o b l e m for i m a g i n g since it c a n
a p p e a r as a noise b a c k g r o u n d . I n T W I t h e effect of
this v a r i a t i o n in s a m p l e emissivity c a n b e m i n i m i z e d
by t a k i n g r a t i o s of i m a g e s o b t a i n e d a t t w o t e m p e r a t
ures o r a t t w o closely spaced w a v e l e n g t h s p r o v i d e d
t h a t t h e emissivity is i n d e p e n d e n t of t e m p e r a t u r e over
the r a n g e o f t e m p e r a t u r e s used a n d t h a t n o localized
absorption bands are near the detection wavelengths.
3.2 Laser Detection Methods: Reflection and
Refraction
Laser detection m e t h o d s c a n m o n i t o r t e m p e r a t u r e -
Wave
Imaging
d e p e n d e n t c h a n g e s in s a m p l e reflectivity, index of
refraction a n d surface d e f o r m a t i o n , as well as index
c h a n g e s in a fluid in t h e r m a l c o n t a c t with t h e s a m p l e .
In laser thermoreflectance, t h e reflected intensity of a
p r o b e laser b e a m from a s a m p l e region h e a t e d by a
source is m e a s u r e d as a function of a n d r, the
distance b e t w e e n t h e s o u r c e a n d p r o b e b e a m centers,
h e r e a s s u m e d G a u s s i a n . T h i s intensity is modified b y
t e m p e r a t u r e - i n d u c e d c h a n g e s in t h e reflectivity a n d ,
in t h e case of s e m i c o n d u c t o r s , b y reflectivity c h a n g e s
induced by a photogenerated electron-hole plasma.
I m a g e f o r m a t i o n a n d i m a g e resolution a r e influenced
b y t h e t e m p e r a t u r e field, a s described previously, a n d
by carrier t r a n s p o r t a n d diffusion. A c o m p e t i t i o n
b e t w e e n t h e r m a l a n d p l a s m a effects m a y exist in s o m e
f r e q u e n c y - t i m e regimes ( F o u r n i e r et al. 1986). T o
analyze these effects, a n electron diffusion length
05
= [ y / J / c o J , w h e r e D is t h e diffusion coefficient,
m u s t b e i n t r o d u c e d . Special cases classified by the
r a t i o of t o a physical length in t h e s a m p l e a r e found.
A similar classification w a s described in Sect. 2 . 1 . T h e
resulting images c a n be selected t o exhibit principally
t e m p e r a t u r e d i s t r i b u t i o n effects, t h e e l e c t r o n - h o l e
p l a s m a d i s t r i b u t i o n effects o r effects associated with
the t e m p e r a t u r e d i s t r i b u t i o n derived from e l e c t r o n hole r e c o m b i n a t i o n . T h e spatial resolution for detec
tion using these laser m e t h o d s is d e t e r m i n e d by the
d i a m e t e r s of t h e s o u r c e a n d p r o b e b e a m s a n d surface
features s e p a r a t e d b y d > 1 p m c a n b e resolved.
W h e n t h e index of refraction is used for detection,
the index g r a d i e n t field p r o d u c e d by t h e source devi
ates a p r o b e b e a m . F o r o p a q u e s a m p l e s this field is in
the air a b o v e t h e s a m p l e a n d q u a n t i t a t i v e m e a s u r e
m e n t s of t h e s a m p l e t e m p e r a t u r e c h a n g e s c a n be m a d e
since t h e v a r i a t i o n of t h e index of refraction with
t e m p e r a t u r e is k n o w n . T h e t h e r m a l diffusivity c a n b e
d e t e r m i n e d in a local m e a s u r e m e n t ( K u o et al. 1989).
F o r t r a n s p a r e n t s a m p l e s , t h e index g r a d i e n t field of
t h e s a m p l e c a n be used as t h e deflecting agency a n d
t h e internal t e m p e r a t u r e d i s t r i b u t i o n a n d h e a t flow
measured. Thermal, plasma and other nonthermal
factors c a n c o n t r i b u t e t o t h e i m a g e s o b t a i n e d .
Surface strain as a p a r a m e t e r for t h e r m a l w a v e
d e t e c t i o n i n t r o d u c e s a d d i t i o n a l elements t o image
f o r m a t i o n a n d c o n t r a s t . First, surface strain c a n b e
monitored near the heating location or at a remote
l o c a t i o n via t h e elastic r e s p o n s e of t h e specimen. N e a r
the h e a t i n g l o c a t i o n , t h e r m a l e x p a n s i o n associated
with h e a t i n g n o r m a l l y causes a local bulge in the
surface of a p l a n a r s a m p l e w h i c h c a n b e detected by
interferometry o r b y d e v i a t i o n of a p r o b e b e a m .
D e t e c t i o n a t a r e m o t e l o c a t i o n o c c u r s t h r o u g h ultra
sonic w a v e p r o p a g a t i o n a t high co m o r t h r o u g h
q u a s i s t a t i c d e f o r m a t i o n a t low co m. D e t e c t i o n is b y a
piezoelectric t r a n s d u c e r c o n n e c t e d t o t h e specimen o r
by optical i n t e r f e r o m e t r y o r related techniques. In this
case, t h e elastic p r o p e r t i e s of t h e specimen c o n t r i b u t e
to the image contrast. As an example, granular mater
ials, including m e t a l s , s h o w e n h a n c e d g r a i n - b o u n d a r y
517
Thermal
Wave
Imaging
20
60
100
20
60
160
180
40
80
160
200
()
(/xm)
100
!20
140
180
x {))
20
60
100
140
180
()
Figure 1
Thermal wave images of closed vertical cracks in a single region of an aluminum sample: (a) magnitude and (b) phase
images obtained using transverse beam deflection; (c) magnitude image from normal beam deflection; and (d) magnitude
image from piezoelectric detection. The same focused, scanned laser source was used to obtain all four images. The
sample contained inclusions which appear as closed level contours in the images and a tightly closed vertical crack. The
inclusions labelled A allow different images to be correlated. The crack is evident in (a) and (b) but absent in (c) and (d).
Piezoelectric images obtained at higher modulation frequencies also show the crack. This set demonstrates how the
information content of a thermal wave image depends on the specific method used
c o n t r a s t w h e n t h e r m o e l a s t i c d e t e c t i o n is used, w h i c h
is n o t seen in t h e p u r e l y t h e r m a l case.
F i g u r e 1 s h o w s images of a c r a c k e d a l u m i n u m
s a m p l e o b t a i n w i t h different d e t e c t i o n m e t h o d s a n d
demonstrates how information content depends on
the detection method.
4. Particle
Sources
518
p a r a m e t e r s . T h e y also exhibit n o n t h e r m a l i m a g e c o n
t r a s t effects w h e n u s i n g a n y of t h e T W I m e t h o d s
described previously. E l e c t r o n b e a m s were o n e of t h e
earliest of t h e T W I sources d e v e l o p e d a n d w h e n used
with elastic w a v e d e t e c t i o n , in a m e t h o d t e r m e d
s c a n n i n g electron a c o u s t i c m i c r o s c o p y ( S E A M ) , give
h i g h - r e s o l u t i o n i m a g e s of t h e p r o p e r t i e s of m a t e r i a l s .
A p p l i c a t i o n s include visualization of t h e grain struc
t u r e in t h e heat-affected z o n e of welds a n d i m a g i n g of
t h e d i s t r i b u t i o n of d o p a n t ions in s e m i c o n d u c t o r s .
H o w e v e r , a satisfactory q u a n t i t a t i v e t h e o r y of i m a g e
Thermal
Wave
Imaging
Figure 2
Electron source TWI of subsurface structure: (a) SEM and (b) SEAM at beam voltages of 5 kV showing the surface of an
integrated circuit; (c) SEM at 30 kV continues to image the surface features whereas (d) SEAM at 30 kV images structures
located below the specimen surface
f o r m a t i o n u s i n g elastic w a v e d e t e c t i o n h a s n o t yet
been d e v e l o p e d a n d t h e m e t h o d is limited t o q u a l i t a
tive investigations of m a t e r i a l s p r o p e r t i e s . R e c e n t l y ,
b o t h r a d i o m e t r i c a n d laser deflection m e t h o d s h a v e
been a p p l i e d t o t h e s t u d y of electron b e a m - m a t e r i a l s
interactions. These thermal m e t h o d s can provide
q u a n t i t a t i v e i n f o r m a t i o n a b o u t a specimen.
4.1 Electron Injection and
Thermalization
Time-resolved m e a s u r e m e n t s of electron injection,
internal i o n i z a t i o n a n d t h e r m a l i z a t i o n h a v e b e e n
o b t a i n e d for s e m i c o n d u c t o r s , u s i n g r a p i d l y m o d u
lated b e a m s of e l e c t r o n s . T h e specimen r e s p o n s e is
m o n i t o r e d b y t h e deflection of a p r o b e laser b e a m
w h o s e p o s i t i o n is s c a n n e d t h r o u g h t h e i n t e r n a l index
g r a d i e n t field f o r m e d b y b o t h electron density a n d
t h e r m a l g r a d i e n t s . T h e results a r e i n t e r p r e t e d using a
modified version of E q n . (1) t o d e t e r m i n e t h e electron
d i s t r i b u t i o n inside t h e specimen, t h e t h e r m a l distribu
t i o n function H(r, i) a n d t h e r e l a x a t i o n times. D y n a
m i c i m a g e s h a v e been m a d e .
F i g u r e 2 c o m p a r e s surface a n d subsurface i m a g e s
519
Thermal
Wave
Imaging
5.
Summary
T W I offers a m e n u of o p p o r t u n i t i e s for m a t e r i a l s
c h a r a c t e r i z a t i o n . T h e c o n t r a s t m e c h a n i s m s available
for i m a g e f o r m a t i o n include: (a) a specific i n t e r a c t i o n
between s o u r c e a n d specimen w h i c h p e r m i t s c o n t r a s t
o n the basis of c o m p o s i t i o n o r t h e energy d e p o s i t i o n
with d e p t h in t h e s a m p l e ; (b) t h e r m a l c o n t r a s t , w h i c h
is b a s e d o n t h e t h e r m a l diffusion length o r time w h i c h
d e p e n d s o n the t h e r m a l p a r a m e t e r s of t h e specimen
and on the separation distance between thermal
source a n d object; a n d (c) d e t e c t o r c o n t r a s t , w h i c h
d e p e n d s o n t h e physical p a r a m e t e r selected t o be a
m e a s u r e of specimen t e m p e r a t u r e . E x a m p l e s of detec
t o r c o n t r a s t factors include the t h e r m a l l y driven local
elastic r e s p o n s e of a specimen w h i c h is p r e s e n t w h e n
surface d e f o r m a t i o n of t h e s a m p l e is m o n i t o r e d , t h e
infrared a b s o r p t i o n s p e c t r u m of t h e s a m p l e in t h e
spectral region used for d e t e c t i o n w h e n ir e m i t t a n c e is
t h e p r o p e r t y m o n i t o r e d a n d t h e electron d i s t r i b u t i o n
w h e n several of the laser d e t e c t i o n m e t h o d s a r e used.
In conclusion, w h e n e v e r T W I is used for c h a r a c t e r i z a
tion, selection of a family m e m b e r a p p r o p r i a t e t o t h e
i n t e n d e d a p p l i c a t i o n is essential.
See also: Stress Distribution: Analysis Using Thermoelastic
Effect
Bibliography
Fournier D, Boccara C, Skumanich A, Amer 1986
Photothermal investigation of transport in semiconduc
torstheory and experiment. / . Appl. Phys. 59: 787-95
Kuo , Favro L D, Thomas R L 1989 Mirage detection of
thermal waves In: Sell J A (ed.) 1989 Photothermal
Investigations of Solids and Liquids. Academic Press, New
York, pp. 191-212
Murphy J C, Spicer J W M, Aamodt L C 1986 Image
contrast processes in thermal and thermoacoustic imag
ing. IEEE Trans. Ultrason. Ferroelec. Frequency Control
33: 529-41
Murphy J C, Spicer J W M, Aamodt L C 1992 Principles of
photothermal detection in solids. In: Mandelis A (ed.)
1992 Photothermal and Photoacoustic Science and Tech
nology, Vol. 1. Elsevier, Amsterdam, pp. 41-94
Sawada T, Kasai 1987 Nondestructive inspection of
stacking faults and dislocations of semiconductor wafers
by photoacoustic microscopy (PAM) and photothermal
beam deflection. In: Mandelis A (ed.) 1987 Photoacoustic
and Thermal Wave Phenomena in Semiconductors. NorthHolland, Amsterdam, pp. 5-26
Tarn A C 1986 Applications of photoacoustic sensing tech
niques. Rev. Mod. Phys. 58: 384-131
J. C. M u r p h y
[ J o h n s H o p k i n s University, L a u r e l ,
Maryland, USA]
520
(1)
w h e r e p{ is t h e p a r t i a l p r e s s u r e of i exerted by t h e
s o l u t i o n o r c o m p o u n d a n d p? is t h e s a t u r a t e d v a p o r
p r e s s u r e of p u r e / a t t h e s a m e t e m p e r a t u r e .
A l t h o u g h activities a r e t h e r m o d y n a m i c functions
of state, their m a g n i t u d e s a n d v a r i a t i o n s a r e deter
mined by the interactions a m o n g the constituent
particles of t h e system, w h i c h , in t u r n , d e t e r m i n e
b o n d energies a n d influence t h e spatial configurations
a s s u m e d by t h e particles. T h u s , m e a s u r e m e n t of a c
tivities within a class of similar simple systems c a n be
expected t o p r o v i d e , a t best, s o m e f u n d a m e n t a l
u n d e r s t a n d i n g of t h e n a t u r e s of these i n t e r a c t i o n s , or,
at least, a basis for c o r r e l a t i o n of t h e b e h a v i o r , which
c a n t h e n be used for e x t r a p o l a t i o n of the b e h a v i o r of
m o r e c o m p l e x systems.
T h e m o l a r free energy of f o r m a t i o n of a s o l u t i o n o r
c o m p o u n d from its p u r e c o m p o n e n t s is o b t a i n e d from
M
t h e activities of t h e c o m p o n e n t s as AG = RT Nt In
at, w h e r e TV, is t h e m o l e fraction of t h e c o m p o n e n t /.
A s t h e v a r i o u s p h a s e equilibria o c c u r r i n g in a m a t e r
ials system a r e d e t e r m i n e d by t h e v a r i a t i o n s , with
c o m p o s i t i o n , t e m p e r a t u r e a n d p r e s s u r e , of t h e relative
free energies of t h e v a r i o u s p h a s e s , such equilibria c a n
be m o s t precisely d e t e r m i n e d by a c c u r a t e m e a s u r e
m e n t of activity. A l s o , t h e activity of a c o m p o n e n t in
a s o l u t i o n is a m e a s u r e of t h e m i n i m u m free energy
r e q u i r e d t o c o n v e r t t h e c o m p o n e n t from its state in
s o l u t i o n t o t h e p u r e state in a n y p r o p o s e d e x t r a c t i o n
o r refining p r o c e s s .
I n a d d i t i o n t o t h e d e t e r m i n a t i o n of activities b y
a p p l i c a t i o n of E q n . (1) t o t h e m e a s u r e m e n t of v a p o r
p r e s s u r e , activities h a v e been d e t e r m i n e d from t h e
e s t a b l i s h m e n t of e q u i l i b r i u m in chemical r e a c t i o n
systems a n d b y m e a s u r e m e n t of t h e e l e c t r o m o t i v e
forces of reversible galvanic cells.
I n t h e m a j o r i t y of t h e e x p e r i m e n t a l m e t h o d s t h e
activity of only o n e c o m p o n e n t is m e a s u r e d . In such
cases t h e activities of t h e o t h e r c o m p o n e n t s c a n be
o b t a i n e d by i n t e g r a t i o n of t h e G i b b s - D u h e m e q u a
tion. F o r c o n s t a n t t e m p e r a t u r e a n d t o t a l p r e s s u r e this
expression is TV, d(\n a) = 0 or, in a m o r e c o n v e n i e n t
form, Ni d(\n ) = 0, w h e r e y, = aJNt is t h e activity
coefficient of /. A p p l i e d t o t h e b i n a r y system A - B in
which t h e v a r i a t i o n of is k n o w n a c r o s s t h e entire
r a n g e of c o m p o s i t i o n ,
In y B( a U V B) = -
'
(NA /NB)
d(\n y A )
(2)
Thermodynamic
1. Activity
Measurement
Determination
of Vapor
by
Experimental
Pressure
T h e choice of e x p e r i m e n t a l t e c h n i q u e for t h e
m e a s u r e m e n t of v a p o r p r e s s u r e is d e t e r m i n e d b y t h e
m a g n i t u d e of the p r e s s u r e t o be m e a s u r e d . T h e
various techniques that have been developed can be
classified as a b s o l u t e m e t h o d s (direct a n d indirect
static m e t h o d s ) a n d indirect m e t h o d s (effusion a n d
t r a n s p i r a t i o n m e t h o d s ) . T h e earlier activity m e a s u r e
m e n t s were m a d e o n b i n a r y alloys of m e r c u r y w i t h
zinc, gold, silver a n d t h a l l i u m a t t e m p e r a t u r e s n e a r
the boiling p o i n t of m e r c u r y . T h e p a r t i a l p r e s s u r e of
m e r c u r y exerted b y a n a m a l g a m is so m u c h g r e a t e r
t h a n the p a r t i a l p r e s s u r e of t h e o t h e r c o m p o n e n t t h a t
the former c a n be e q u a t e d w i t h t h e t o t a l v a p o r
pressure of t h e a m a l g a m . In t h e first investigations t h e
alloy w a s used as t h e sealing liquid in a U - t u b e nullp o i n t m a n o m e t e r . T h e v a p o r in e q u i l i b r i u m w i t h t h e
alloy is c o n t a i n e d in t h e closed a r m of t h e m a n o m e t e r ,
a n d h y d r o g e n , the p r e s s u r e of w h i c h is m e a s u r e d a t a
second m a n o m e t e r , is i n t r o d u c e d i n t o t h e o t h e r a r m
until t h e meniscuses in b o t h a r m s a r e a t t h e s a m e
level. T h e v a p o r p r e s s u r e s of a m a l g a m s a t lower
t e m p e r a t u r e s h a v e been m e a s u r e d using v a r i o u s d e
vices such as m e m b r a n e m a n o m e t e r s , q u a r t z spiral
manometers and ionization gauges.
T h e p a r t i a l p r e s s u r e s of zinc a n d c a d m i u m o v e r aA g - Z n - C d alloys a n d zinc over -brasses h a v e b e e n
m e a s u r e d by r e s o n a n c e a b s o r p t i o n s p e c t r o s c o p y . I n
s t u d y i n g t h e zinc alloys, light p r o d u c e d b y a s p a r k
between zinc electrodes is p a s s e d t h r o u g h a s a m p l e of
v a p o r in e q u i l i b r i u m w i t h t h e alloy a n d t h e a b s o r p
tion of the 307.6 n m r e s o n a n c e line is m e a s u r e d . A s
the 303.5 n m r e s o n a n c e line is n o t a b s o r b e d , it is
used as a n i n t e r n a l s t a n d a r d , a n d t h e v a p o r p r e s s u r e
of zinc o b t a i n e d from Beer's law a s l n ( / 3 07 J
Im5)
= Kapd/T, w h e r e / is t h e intensity of t h e t r a n s
m i t t e d light, Ka is t h e a b s o r p t i o n coefficient, is t h e
a b s o l u t e t e m p e r a t u r e a n d d is t h e d i s t a n c e travelled b y
the light t h r o u g h t h e s a m p l e of v a p o r .
T h e d e w - p o i n t m e t h o d is well suited t o systems
c o n t a i n i n g a distinctly volatile c o m p o n e n t , a n d h a s
been applied t o m e a s u r e m e n t of t h e activity of zinc in
b i n a r y alloys c o n t a i n i n g c o p p e r , a l u m i n u m , silver,
gold, z i r c o n i u m , t h o r i u m , u r a n i u m a n d y t t r i u m a n d
of t h e activity of c a d m i u m in s i l v e r - c a d m i u m alloys.
E x p e r i m e n t a l l y , t h e alloy is placed a t o n e e n d of a
long, initially e v a c u a t e d t u b e w h i c h is h e a t e d t o t h e
desired t e m p e r a t u r e Tx. T h e t e m p e r a t u r e of t h e o t h e r
e n d of t h e t u b e is l o w e r e d until c o n d e n s a t i o n of t h e
volatile c o m p o n e n t is o b s e r v e d a t t h e t e m p e r a t u r e T2.
A s t h e p r e s s u r e within t h e t u b e is u n i f o r m , t h e p a r t i a l
pressure of t h e volatile c o m p o n e n t exerted b y t h e
alloy a t Tx e q u a l s t h e s a t u r a t e d v a p o r p r e s s u r e of t h e
p u r e volatile c o m p o n e n t a t T2. T h e use of fused silica
t u b e s , w h i c h p e r m i t s visual o b s e r v a t i o n of c o n d e n s a
tion at the c oole r e n d , h a s limited t h e t e m p e r a t u r e t o
less t h a n 1 1 0 0 C a n d , generally, m e a s u r e m e n t s h a v e
Activity:
Measurement
b e e n m a d e in t h e r a n g e 4 0 0 - 9 0 0 C. In a similar
isopiestic t e c h n i q u e , t h e p u r e volatile c o m p o n e n t is
p l a c e d in t h e cool e n d of a n initially e v a c u a t e d t u b e
m a i n t a i n e d in a k n o w n t e m p e r a t u r e g r a d i e n t a n d
weighed q u a n t i t i e s of t h e p u r e s e c o n d c o m p o n e n t a r e
t h e n p l a c e d a t intervals a l o n g t h e t e m p e r a t u r e g r a d i
ent. T h e volatile c o m p o n e n t is transferred from the
v a p o r p h a s e t o t h e specimens of n o n v o l a t i l e c o m
p o n e n t until t h e alloys in e q u i l i b r i u m w i t h t h e prevail
ing p r e s s u r e of t h e volatile c o m p o n e n t a r e f o r m e d . In
this t e c h n i q u e , w h i c h h a s been a p p l i e d t o m e a s u r e
m e n t of t h e activities of a l u m i n u m in solid A l - F e a n d
A l - N i alloys, t h e c o m p o s i t i o n s of t h e e q u i l i b r i u m
alloys a r e d e t e r m i n e d gravimetrically. A p p l i c a t i o n of
t h e d e w - p o i n t a n d isopiestic t e c h n i q u e s t o the
m e a s u r e m e n t of activity r e q u i r e s k n o w l e d g e of the
t e m p e r a t u r e d e p e n d e n c e of t h e s a t u r a t e d v a p o r pres
sure of t h e volatile c o m p o n e n t .
I n t h e t r a n s p i r a t i o n t e c h n i q u e a n inert carrier gas is
p a s s e d o v e r a s a m p l e a t a flow r a t e t h a t p e r m i t s
e v a p o r a t i o n of t h e alloy t o o c c u r t o t h e extent neces
sary t o s a t u r a t e t h e car r i er gas. T h i s t e c h n i q u e h a s
b e e n used t o m e a s u r e t h e activities in liquid F e - C u
a n d F e - N i alloys. T h e m a t e r i a l e v a p o r a t e d from the
s a m p l e is c o n d e n s e d d o w n s t r e a m a n d is chemically
a n a l y z e d . T h e t o t a l a m o u n t of e v a p o r a t i o n i n t o u n i t
v o l u m e of t h e car r i er gas a t t h e t o t a l p r e s s u r e is
d e t e r m i n e d b y m e a s u r i n g t h e weight loss of the s a m
ple o r b y q u a n t i t a t i v e analysis of t h e a m o u n t of
c o n d e n s a t e r eco v er ed from a k n o w n v o l u m e of gas. If
Fe, nCu a n d nHe a r e t h e n u m b e r s of m o l e s of i r o n ,
c o p p e r a n d h e l i u m carrier g a s in t h e s a m p l e d v o l u m e ,
respectively, t h e n t h e p a r t i a l p r e s s u r e of i r o n is cal
c u l a t e d from t h e ideal-gas law as pFe = PnFJ(nFe
+
nCu + nHe). A n a d v a n t a g e of this t e c h n i q u e is t h a t the
activities of b o t h c o m p o n e n t s a r e m e a s u r e d a n d hence
i n t e r n a l consistency of t h e results c a n b e checked
u s i n g t h e G i b b s - D u h e m e q u a t i o n . H o w e v e r , in o r d e r
t h a t surface d e p l e t i o n of t h e m o r e volatile c o m p o n e n t
be a v o i d e d , t h e r a t e s of diffusion in t h e alloy m u s t be
faster t h a n t h e r a t e s of e v a p o r a t i o n .
I n t h e effusion t e c h n i q u e t h e alloy t o be studied is
p l a c e d in a K n u d s e n cell (a sealed crucible c o n t a i n i n g
a small orifice in its lid) a n d t h e crucible is h e a t e d in
v a c u u m t o t h e desired t e m p e r a t u r e . P h a s e e q u i l i b r i u m
is established b e t w e e n t h e v a p o r p h a s e a n d t h e c o n
d e n s e d p h a s e in t h e cell a n d , if t h e d i m e n s i o n s of t h e
orifice a r e small in c o m p a r i s o n w i t h t h e m e a n free
p a t h of t h e v a p o r species, t h e p a s s a g e of v a p o r species
t h r o u g h t h e orifice is n o t d i s t u r b e d b y collisions.
T h u s , t h e rates of effusion of t h e v a p o r species are
p r o p o r t i o n a l t o their v a p o r p r e s s u r e s within the cell.
F r o m t h e kinetic t h e o r y of gases, t h e n u m b e r of
particles in a v a p o r p h a s e striking u n i t a r e a of the
c o n t a i n i n g wall in u n i t t i m e is 0.25 nc, w h e r e is the
112
is
density of t h e v a p o r species a n d c = (SRT/)
t h e a v e r a g e speed of t h e particles (M is m o l a r m a s s ) .
T h u s , t h e weight loss W d u e t o effusion t h r o u g h a n
l/2
orifice of a r e a A in time / is W = pAt/(2nMRT)
and
521
Thermodynamic
Activity:
Measurement
(3)
w h e r e t h e c o n s t a n t K{ is d e t e r m i n e d b y t h e i o n i z a t i o n
cross section of t h e ion, t h e d e t e c t o r sensitivity a n d
t h e g e o m e t r y of the K n u d s e n - c e l l ion s o u r c e . T h e
a p p l i c a t i o n of the t e c h n i q u e t o m e a s u r e m e n t of activi
ties in b i n a r y systems w a s greatly facilitated b y a
m a n i p u l a t i o n of t h e G i b b s - D u h e m e q u a t i o n w h i c h
allows the v a r i a t i o n s with c o m p o s i t i o n of t h e activity
coefficients of the individual c o m p o n e n t s t o b e
o b t a i n e d from the c o r r e s p o n d i n g m e a s u r e d r a t i o of
the activity coefficients:
= - j " V
In y B ( a t NB)
d[\n(yA/yB)]
(4)
F r o m E q n . (3),
'A
/B
Pa
OC
pb
_?*
OC
77-
y* *
s u b s t i t u t i o n of w h i c h i n t o E q n . (4) gives
In )> B(at7V B) = - J %
v a n a d i u m , c h r o m i u m , iron, c o b a l t , nickel, c o p p e r ,
silver, gold, a l u m i n u m , t h a l l i u m , lead, tin, b i s m u t h ,
antimony and indium.
2. Activity Determination
by
Heterogeneous
Equilibrium
Establishing
d[\n(lX //+ )
K =
5 PcolPco2 c
()
and
-\n(NA/NB)]
U s e of a m a s s s p e c t r o m e t e r requires t h a t a p r e s s u r e of
8
less t h a n 1 0 ~ a t m be m a i n t a i n e d in t h e a r e a s of t h e
ion s o u r c e , a n a l y z e r a n d d e t e c t o r . T h i s t e c h n i q u e h a s
been applied t o m e a s u r e m e n t of activities in a large
n u m b e r of b i n a r y a n d t e r n a r y systems c o n t a i n i n g
522
6=Pco2/PcoPo2
(6)
T h u s , a t a fixed t e m p e r a t u r e , w h i c h d e t e r m i n e s t h e
values of K5 a n d K6, a C O - C 0 2 , gas m i x t u r e of k n o w n
Pco a n d PCQ2 h a s a n activity of c a r b o n given b y E q n .
(5) a n d a p a r t i a l p r e s s u r e of o x y g e n given b y E q n . (6).
Similarly,
by
virtue
of
the
equilibrium
Thermodynamic
H 2 + ^ 0 2 ^ H 2 0 , a n H 2 - H 2 0 m i x t u r e of k n o w n pH2
a n d pH20 exerts a u n i q u e p a r t i a l p r e s s u r e of o x y g e n a t
a n y t e m p e r a t u r e . By virtue of t h e e q u i l i b r i u m
H 2 + ^ S 2 ^ H 2 S , a n H 2 - H 2 S m i x t u r e of k n o w n pH2 a n d
pHlS exerts a u n i q u e p a r t i a l p r e s s u r e of sulfur a t a n y
t e m p e r a t u r e , a n d , b y virtue of t h e e q u i l i b r i u m C ( g r a p. h
and
i t e) + 2 H 2 ^ C H 4 , a C H 4 - H 2 m i x t u r e of k n o w n pCH2
pH2 h a s a u n i q u e activity of c a r b o n a t a n y t e m p e r a
ture. C o n s e q u e n t l y , C O - C 0 2 a n d C H 4 - H 2 m i x t u r e s
c a n be used as gas p h a s e s of fixed activity of c a r b o n
for use in t h e e s t a b l i s h m e n t of h e t e r o g e n e o u s equili
bria b e t w e e n a gas p h a s e a n d a c o n d e n s e d p h a s e .
Similarly, C O - C 0 2 a n d H 2 - H 2 0 m i x t u r e s c a n b e used
as gas p h a s e s of fixed oxygen p r e s s u r e a n d H 2 - H 2 S
m i x t u r e s c a n be used as gas p h a s e s of fixed sulfur
pressure.
T h e activities of c a r b o n in liquid a n d solid i r o n
h a v e been d e t e r m i n e d b y e q u i l i b r a t i n g i r o n with C O C 0 2 and C H 4 - H 2 mixtures a n d measuring the equi
librium c a r b o n c o n t e n t of t h e m e t a l p h a s e , a n d t h e
activities of oxygen a n d sulfur in liquid i r o n h a v e b e e n
d e t e r m i n e d b y e q u i l i b r a t i n g i r o n with H 2 0 - H 2 a n d
H 2 S - H 2 m i x t u r e s , respectively. I n simpler g a s - m e t a l
equilibria, t h e activities of h y d r o g e n a n d n i t r o g e n in
iron h a v e been d e t e r m i n e d b y m e a s u r i n g t h e solubili
ties of the gases a s functions of gas p r e s s u r e . Activities
in t h e system F e - F e 2 0 3 h a v e b e e n d e t e r m i n e d b y
e x p e r i m e n t a l o b s e r v a t i o n of t h e v a r i a t i o n of t h e c o m
p o s i t i o n of small s a m p l e s of c o n d e n s e d p h a s e s w i t h
temperature and oxygen pressure imposed by an
equilibrating gas p h a s e . T h e v a r i a t i o n , with c o m p o s i
tion, of the activity of i r o n in t h e system is d e t e r m i n e d
by G i b b s - D u h e m i n t e g r a t i o n of t h e c o r r e s p o n d i n g
m e a s u r e d v a r i a t i o n of t h e e q u i l i b r i u m p a r t i a l p r e s s u r e
of oxygen. T h e oxygen c o n t e n t of liquid i r o n in
e q u i l i b r i u m with p u r e liquid F e O a t 1600 C is
0.23 w t % . If t h e oxide of a less n o b l e m e t a l t h a n i r o n
is dissolved in t h e liquid F e O , t h e activity of F e O , a n d
hence t h e e q u i l i b r i u m oxygen c o n t e n t of t h e liquid
iron, is decreased. If t h e latter is JC w t % , t h e activity of
F e O , relative t o p u r e i r o n - s a t u r a t e d F e O as t h e s t a n
d a r d state, in t h e oxide s o l u t i o n is x / 0 . 2 3 . T h i s tech
n i q u e h a s been used t o d e t e r m i n e t h e activity of F e O
in C a O - F e O a n d C a O - F e O - S i 0 2 melts s a t u r a t e d
with liquid i r o n .
O n e step m o r e c o m p l e x is t h e e s t a b l i s h m e n t of
e q u i l i b r i u m b e t w e e n a gas p h a s e a n d t w o c o n
densed p h a s e s . T h e e q u i l i b r i u m b e t w e e n m a n g a n e s e ,
M n O a n d a C O - C 0 2 m i x t u r e , expressed
as
M n + C 0 2 ^ M n O + C O , requires t h a t
K
()
T h u s , a t a given t e m p e r a t u r e , t h e e q u i l i b r i u m b e t w e e n
p u r e m a n g a n e s e (at u n i t activity) a n d m a n g a n e s e s a t u r a t e d p u r e M n O (at u n i t activity) o c c u r s a t a
y en
u n i q u e value of t h e r a t i o pCo/Pco2 g i
b y E q n . (7). If
a m e t a l m o r e n o b l e t h a n m a n g a n e s e is e m b e d d e d in
a n excess of M n O a n d subjected t o a lower
pco/Pco2
r a t i o , m a n g a n e s e is transferred from t h e M n O t o t h e
Activity:
Measurement
m e t a l p h a s e until t h e activity of m a n g a n e s e r e q u i r e d
s
b y E q n . (7) a n d b y t h e i m p o s e d pColPco2
* estab
lished. T h e m a n g a n e s e c o n t e n t of t h e alloy c o r r e s
p o n d i n g t o t h e i m p o s e d activity is d e t e r m i n e d b y
chemical analysis. T h e o t h e r c o m p o n e n t of t h e alloy
m u s t be sufficiently m o r e n o b l e t h a n m a n g a n e s e t h a t
f o r m a t i o n a n d s o l u t i o n of its o x i d e in t h e M n O p h a s e
is negligible. T h e activity of m a n g a n e s e in M n - P t
alloys h a s been d e t e r m i n e d in this m a n n e r . T h e a c
tivity of M n O in o x i d e m e l t s c o n t a i n i n g oxides m o r e
stable t h a n M n O c a n s u b s e q u e n t l y b e f o u n d b y
e q u i l i b r a t i n g a small s a m p l e of p l a t i n u m with a n
excess of o x i d e m e l t a n d a C O - C 0 2 g a s m i x t u r e .
A g a i n , as m a n g a n e s e is d i s t r i b u t e d b e t w e e n t h e P t M n alloy a n d t h e oxide m e l t in a c c o r d a n c e w i t h E q n .
(7) a n d t h e i m p o s e d PcolPco? c h e m i c a l analysis of t h e
e q u i l i b r a t e d P t - M n alloy yields aMn a n d h e n c e , from
E q n . (7), t h e value of aMnQ in t h e o x i d e melt. I n this
a p p l i c a t i o n , t h e o t h e r oxide c o m p o n e n t m u s t be of a
m e t a l w h i c h is sufficiently less n o b l e t h a n m a n g a n e s e
t h a t t h e e x t e n t of its s o l u t i o n in t h e P t - M n p h a s e is
negligible. T h i s t e c h n i q u e h a s b e e n used t o d e t e r m i n e
t h e activity of M n O in systems s u c h as M n O - S i 0 2 ,
M n O - T i 0 2, M n O - A l 20 3, M n O - B 20 3 and M n O C a O - S i 0 2.
O t h e r e x a m p l e s of d e t e r m i n a t i o n of activities b y
establishing e q u i l i b r i u m b e t w e e n a b i n a r y alloy, a
n o n m e t a l l i c p h a s e of k n o w n c o m p o s i t i o n a n d a gas
p h a s e include:
Fe(in F e - N i alloys) + H 2 0 ; = F e O + H 2
2Cr(in C r - N i alloys) + 3 H 2 0 ^ C r 2 0 3 + 3 H 2
3 M n ( i n M n - C u alloys) + C H 4 ^ M n 3 C + 2 H 2
2 C u ( i n C u - A u alloys) + H 2 S ^ C u 2 S + H 2
3Si(in S i - A g alloys) + N 2 ( i n N 2 - H 2 m i x t u r e s )
^ S i 3N 4
(8)
523
Thermodynamic
Activity:
Measurement
wherein =
flMnflFe0/aFeaMn0.
F r o m chemical analysis
of t h e e q u i l i b r a t e d F e - M n alloy a n d k n o w l e d g e of t h e
activities in t h e system F e - M n , t h e r a t i o yFe0/yMn0
in
the e q u i l i b r a t i n g oxide s o l u t i o n is o b t a i n e d as
OVeo/yMno) = ^ F e
^MnO l Mn
FcO
a n d G i b b s - D u h e m i n t e g r a t i o n of t h e v a r i a t i o n of this
r a t i o with c o m p o s i t i o n in the o x i d e s o l u t i o n a c c o r d
ing t o E q n . (4) yields t h e i n d i v i d u a l activity coeffi
cients, a n d hence activities, of t h e c o m p o n e n t s of t h e
oxide s o l u t i o n . T h i s t e c h n i q u e h a s b e e n used t o deter
m i n e activities in t h e systems F e 2 S i 0 4 - C o 2 S i 0 4 a n d
F e 2S i 0 4- M n 2S i 0 4.
Activities h a v e been d e t e r m i n e d b y establishing
e q u i l i b r i u m a m o n g three c o n d e n s e d p h a s e s a n d a g a s
p h a s e . A s a n e x a m p l e , t h e activity of S i 0 2 in C a O M g 0 - A l 2 0 3 - S i 0 2 melts has been determined by
establishing t h e e q u i l i b r i u m
S i 0 2 + 2C;=Si + 2 C O
(9)
(10)
3. Electrochemical
Measurement
of
ionic c o n d u c t o r c o n t a i n i n g
ions of metal A of valence z A
alloy A - B
524
Al(l)| A l
3 +
(in K C l - N a C l ) | A l - A g ( l )
Similarly, t h e activities of c a d m i u m in C d - P b , C d - B i ,
C d - S b a n d C d - S n alloys a n d t h e activities of c o p p e r
in C u - A u m e l t s a n d silver in A g - A u m e l t s h a v e b e e n
d e t e r m i n e d from c o n c e n t r a t i o n cells w i t h liquid chlor
ide electrolytes.
T h e cell
M g ( l ) | M g C l 2( l ) | C l 2( g , l a t m )
is a f o r m a t i o n cell in w h i c h t h e cell r e a c t i o n is
M g + Cl 2;=MgCl 2. W i t h p u r e liquid m a g n e s i u m p u r e
liquid M g C l 2 a n d C l 2 a t 1 a t m p r e s s u r e , t h e freeenergy c h a n g e is t h e s t a n d a r d free-energy c h a n g e
0
A G a n d t h e e m f is t h e s t a n d a r d e m f E= - AG2F.
Alloying t h e a n o d e w i t h a m o r e n o b l e m e t a l s u c h as
a l u m i n u m alters t h e free-energy c h a n g e for t h e cell
0
r e a c t i o n t o AG = A G - RT In aMg (in t h e alloy) a n d
h e n c e t h e cell e m f t o
= E + (RT/2F)\n
aMg(m
t h e alloy)
(11)
E q n . (11) h a s b e e n u s e d t o d e t e r m i n e t h e activities of
m a g n e s i u m in M g - A l m e l t s from e m f m e a s u r e m e n t s
in t h e r a n g e 7 0 0 - 8 8 0 C.
Similarly, t h e f o r m a t i o n cell
P b ( l ) | P b O ( l ) | 0 2( g , l a t m )
Activity
h a s a s t a n d a r d e m f = - AG/2F. A l l o y i n g t h e P b O
electrolyte w i t h t h e o x i d e of a less n o b l e m e t a l , such as
S i 0 2 , c h a n g e s t h e cell e m f t o
E=E-
(RT/2F)\n
aPbo(m
P b O - S i 0 2)
CaO-Zr02
0 2( g , a t
p r e s s u r e P 2) , P t
in w h i c h t h e cell r e a c t i o n is 0 2 ( g , a t p r e s s u r e
Px)
Thermoluminescence
a F e( i n t h e alloy)
(12)
T h i s m e t h o d is similar t o t h a t discussed in c o n n e c t i o n
with E q n . (8). In t h e chemical e q u i l i b r a t i o n t e c h n i q u e
the oxygen p r e s s u r e is i m p o s e d a n d t h e F e - N i alloy in
e q u i l i b r i u m w i t h F e O a n d t h e i m p o s e d oxygen p r e s
sure is p r o d u c e d in t h e e x p e r i m e n t a l a p p a r a t u s . I n t h e
emf t e c h n i q u e t h e o x y g e n p r e s s u r e in e q u i l i b r i u m with
a given F e - N i alloy a n d F e O is m e a s u r e d . E q n . (12)
h a s been used as t h e basis for electrochemical deter
m i n a t i o n of t h e activities in a large n u m b e r of solid
a n d liquid b i n a r y alloy systems, t h e m a j o r i t y of w h i c h
h a v e c o n t a i n e d i r o n , c o b a l t , nickel o r c o p p e r as t h e
less n o b l e m e t a l . T h e activity of silicon in F e - S i alloys
at 1 5 5 0 C a n d 1600 C h a s been d e t e r m i n e d with
electrodes of c h r o m i u m , C r 2 0 3 a n d S i 0 2 , F e - S i , a n d
activities in t h e systems T a - W a n d T a - M o h a v e b e e n
d e t e r m i n e d with a Y 2 0 3 - T h 0 2 electrolyte a n d t a n t a
l u m , T a 2 0 5 a n d T a - X , T a 2 O s electrodes. T h e activities
of S n O in S n O - S i 0 2 melts a n d P b O in P b O - S i 0 2
melts h a v e b e e n d e t e r m i n e d from cells of t h e t y p e M ,
M O | C a O - Z r 0 2l M , M O - S i 0 2.
O t h e r solid electrolytes w h i c h h a v e been used in
clude b e t a - a l u m i n a a n d soft s o d a glass for m e a s u r e
m e n t of the activity of s o d i u m in alloys, a n d glasses
+
+
a n d A g for s t u d y , respectively, of
containing K
p o t a s s i u m a n d silver alloys. It c a n b e expected t h a t , as
new solid-state electrolytes a r e d e v e l o p e d for possible
use in fuel cells, they will be a p p l i e d t o t h e d e t e r m i
n a t i o n of activities b y e m f m e a s u r e m e n t s .
See also: Phase Diagrams and Phase Stability: Calculations
Bibliography
Belton G R, Fruehan R J 1971 The determination of
activities by mass-spectrometry: some additional
methods. Metall. Trans. 2: 291-6
Chandrasekharaiah S, Sreedharan , Chattopadhyay
G 1980 Thermodynamic studies of alloys and intermetallic compounds. In: Subbarao C (ed.) 1980 Solid Electro
lytes and their Applications. Plenum, New York, pp. 9 9 126
Elliott J F 1981 Physical chemistry of liquid metal solutions.
In: Tien J K, Elliott J F (eds.) 1981 Metallurgical Trea
tises. The Metallurgical Society (AIME), Warrendale,
PA, pp. 41-58
Elliott J F, Gleiser M, Ramakrishna V 1963 Thermo
chemistry for Steelmaking. Addison-Wesley, Reading,
MA
Thermoluminescence
T h e r m o l u m i n e s c e n c e ( T L ) is a p r o c e s s in w h i c h a
m a t e r i a l , previously subjected t o ionizing r a d i a t i o n , is
h e a t e d so t h a t s o m e of t h e s t o r e d energy is released in
t h e f o r m of light. M a n y i n s u l a t o r a n d s e m i c o n d u c t o r
m a t e r i a l s exhibit this p r o p e r t y . A few i n s u l a t o r m a t e r
ials with t h e m o s t f a v o r a b l e t h e r m o l u m i n e s c e n t
p r o p e r t i e s a r e used for r a d i a t i o n d o s i m e t r y ; t h e light
o u t p u t allows a m e a s u r e of t h e received d o s e . Simi
larly, t h e r m o l u m i n e s c e n c e is used in a r c h e o l o g y for
t h e d a t i n g of c e r a m i c objects w h i c h h a v e been irra
d i a t e d b y n a t u r a l r a d i a t i o n d u r i n g their lifetime. T h e
s a m e m e t h o d c a n be used for t h e d a t i n g of geological
formations.
T h e r m o l u m i n e s c e n c e is of interest as a physical
p r o c e s s n o w recognized a s b e i n g p a r t of a larger
g r o u p of processes k n o w n as t h e r m a l l y s t i m u l a t e d
r e l a x a t i o n s in solids ( B r a u n l i c h 1979). It h a s b e c o m e
a n i m p o r t a n t t e c h n i q u e for s t u d y i n g t h e t r a p p i n g
of electrons a n d holes a t p o i n t a n d line defects in
crystals.
1.
Apparatus
A p p a r a t u s used for m e a s u r i n g t h e r m o l u m i n e s c e n c e
usually consists of: (a) a h e a t i n g e l e m e n t which h e a t s
t h e specimen, usually a t a linear h e a t i n g r a t e g o v e r n e d
by a t e m p e r a t u r e c o n t r o l l e r a n d p r o g r a m m e r ; (b) a
photomultiplier tube and power supply to measure
t h e intensity of t h e e m i t t e d light; (c) a system t o
m e a s u r e t h e p h o t o m u l t i p l i e r signal; a n d (d) a n x-y
p l o t t e r t o display t h e t h e r m o l u m i n e s c e n t intensity as a
c u r r e n t versus t e m p e r a t u r e p l o t , called a glow curve
(Fig. 1). A n optical filter c a n be e m p l o y e d t o r e d u c e
t h e infrared r a d i a t i o n from t h e h e a t e r e n t e r i n g t h e
p h o t o m u l t i p l i e r t u b e w h i c h typically b e c o m e s signi
ficant a b o v e 400 C. T h e light d e t e c t i o n system is
completely enclosed a n d a n a t m o s p h e r e of n i t r o g e n
m a y be used w i t h p o w d e r s a m p l e s t o minimize a
s p u r i o u s b a c k g r o u n d emission k n o w n as t r i b o l u m i nescence. R a p i d r e a d o u t rates a r e s o m e t i m e s favored
525
Thermoluminescence
h e a t e d , t h e electron m a y b e t h e r m a l l y released from
its t r a p b y a t t a i n i n g t h e a c t i v a t i o n energy t o j u m p
into the conduction band, and then migrate to a
t r a p p e d h o l e a n d r e c o m b i n e w i t h t h e emission of light
(Fig. 2b). If t h e electrons a t t e m p t t o leave t h e t r a p a t a
frequency 5 , t h e n t h e p r o b a b i l i t y of escape P, a s s u m
ing a B o l t z m a n n d i s t r i b u t i o n of energies, is
dc
ammeter
High - v o l t a g e
dc s u p p l y
Photomultiplier
tube
100
150
Temperature
Infrared
Thermocouple
filter
I Programmer
L i g h t - t i g h t seal
Thermoluminescent
sample
Temperature
controller
Resistance
heater
= S e x p ( - E/kT)
200
C O
Power
(1)
T h e simplest m o d e l for t h e r m o l u m i n e s c e n c e is t h e
first-order-kinetics m o d e l in w h i c h it is a s s u m e d t h a t
t h e intensity of light e m i t t e d , 7, is p r o p o r t i o n a l t o t h e
r a t e of release of electrons from their t r a p s , w h i c h is in
t u r n p r o p o r t i o n a l t o t h e n u m b e r of t r a p p e d electrons.
T h e b a c k r e a c t i o n , t h e r e t r a p p i n g of electrons, is
a s s u m e d t o b e negligible. If t h e r e a r e t r a p p e d
electrons ( a n d t r a p p e d holes) t h e r a t e of release of
electrons is
- dn/dt = nP
(2)
Figure 1
Apparatus for the measurement of thermoluminescence
w h e r e is t h e p r o b a b i l i t y of a n electron being
released f r o m its t r a p p e r u n i t t i m e . T h e t h e r m o l u m i
nescent intensity c a n t h e n b e expressed as
w h e r e c is a c o n s t a n t . It is possible t o i n t e g r a t e this
e q u a t i o n for t h e case of a linear h e a t i n g r a t e
b e t w e e n t e m p e r a t u r e 0 , w h e n n0 electrons a r e
t r a p p e d , for e x a m p l e , after i r r a d i a t i o n , a n d T, t o
d e t e r m i n e t h e intensity / as a function of t e m p e r a t u r e .
1=
^Conduction
e J
E/kT)
band
Electron
trap
h
\
^
(3)
Hole
trap
Valence band
(a)
2. Atomic
Processes
in
Thermoluminescence
526
Conduction
band
e
Light
emitted
Valence
band
( b )
Figure 2
Band model for (a) the formation of electrons and holes
by ionizing radiation, and their trapping, and (b) the
release of electrons from their traps, the recombination
with holes and the emission of light, as a result of heating
the sample
Thermoluminescence
T h e solution is:
I=cn0S
x f
5.
exp( -
E/kT)exp
exp(-E/kT)dT
(-s/)
(4)
F i g u r e 3a r e p r e s e n t s t h e v a r i a t i o n of t h e n u m b e r of
t r a p p e d electrons with t e m p e r a t u r e for a c o n s t a n t
h e a t i n g r a t e . F i g u r e 3b s h o w s t h e associated light
o u t p u t as a function of t e m p e r a t u r e (i.e., t h e glow
p e a k ) a n d is described b y E q n . (4). V a r i o u s m e t h o d s
h a v e been devised t o a n a l y z e e x p e r i m e n t a l glow p e a k s
to o b t a i n t h e a c t i v a t i o n energies a n d t h e p r e e x p o nential factors S ( C h e n a n d K i r s c h 1981). In p r a c t i c e ,
m o r e t h a n o n e glow p e a k is generally f o u n d a n d
frequently these p e a k s o v e r l a p , w h i c h m a y m a k e t h e m
difficult t o analyze. S o m e t i m e s t h e p e a k s c a n b e
s e p a r a t e d b y r e a d i n g t h e m o u t successively, t h a t is,
partially r e a d i n g o u t a p e a k , d r o p p i n g t h e t e m p e r a
t u r e a n d t h e n r e r e a d i n g t h e p e a k . T h e single p e a k m a y
t h e n be a n a l y z e d t o give a n d S values. T h i s is called
p e a k cleaning. Alternatively, c o m p u t e r m e t h o d s of
curve fitting m a y be used t o a n a l y z e t h e individual
p e a k s m a k i n g u p a glow curve. A d j u s t a b l e p a r a m e t e r s
in these fitting p r o c e d u r e s a r e t h e a c t i v a t i o n energy E,
t h e p r e e x p o n e n t i a l S a n d t h e o r d e r of t h e kinetics.
A n alternative m o d e l for alkali halide crystals h a s
been p r o p o s e d ( A u s i n a n d A l v a r e z - R i v a s 1972) in
which t h e activated p r o c e s s for d e t r a p p i n g is associ
a t e d with t h e liberation of interstitial a t o m s , r a t h e r
t h a n electrons a n d holes.
Temperature
Figure 3
A plot of (a) the variation in the number of trapped
electrons in a previously irradiated sample with
temperature increasing with time, and (b) the resultant
glow peak arising from the release of electrons and their
recombination with holes
Dosimetry
527
Thermoluminescence
4.
Dating
T h e r m o l u m i n e s c e n c e h a s been a p r i m a r y t e c h n i q u e
for d a t i n g in a r c h e o l o g y . It d e p e n d s o n t h e fact t h a t in
the p a s t s o m e c e r a m i c objects were fired d u r i n g their
m a n u f a c t u r e , t o t e m p e r a t u r e s a b o v e 500 C. T h i s
firing t r e a t m e n t e m p t i e d the t h e r m o l u m i n e s c e n t t r a p s
in the materials, for e x a m p l e , in q u a r t z particles, so
t h a t only t h e r a d i a t i o n t h a t w a s received s u b s e q u e n t l y
from n a t u r a l r a d i a t i o n c o n t r i b u t e d t o their t h e r m o l u
minescence. T h i s being so, a k n o w l e d g e of the d o s e
rate received by t h e object e n a b l e s t h e d a t e of its
m a n u f a c t u r e t o be calculated:
_ d o s e a c q u i r e d since firing
annual dose rate
_ t h e r m o l u m i n e s c e n c e x r a d s p e r unit of T L
r a d s per year
T h e t e r m " r a d s p e r unit of T L " m u s t be d e t e r m i n e d
from a l a b o r a t o r y c a l i b r a t i o n p l o t m a d e with the
same m a t e r i a l . S o m e difficulties m a y arise from
the fact t h a t h e a t i n g u p the s a m p l e t o r e a d o u t the
t h e r m o l u m i n e s c e n c e m a y t h e n affect its sensitivity t o
a calibrating d o s e . O t h e r c o m p l i c a t i o n s arise from the
fact t h a t different forms of r a d i a t i o n h a v e different
p e n e t r a t i o n d e p t h s . F o r e x a m p l e , particles p e n e t r a t e
d e p t h s of m i c r o m e t e r s , electrons millimeters a n d y
rays centimeters. Particles of q u a r t z will c o n s e q u e n t l y
receive different a n n u a l doses, d e p e n d e n t o n their
size, from their s u r r o u n d i n g s . Sophisticated p r o c e d
ures h a v e been developed t o c i r c u m v e n t these p r o b
lems (Aitken 1974). T h e n a t u r a l d o s e r a t e arising from
radioactive u r a n i u m , t h o r i u m , p o t a s s i u m a n d cosmic
rays c a n be d e t e r m i n e d from a c o m b i n a t i o n of c h e m
ical analysis, c o u n t i n g a n d t h e r m o l u m i n e s c e n c e
dosimetry. Since t h e half-lives of r a d i o a c t i v e u r a n i u m ,
t h o r i u m a n d p o t a s s i u m a r e very m u c h longer t h a n the
5
age of a n y m a n - m a d e ceramics (less t h a n 10 years),
the dose received is n o r m a l l y r e g a r d e d as being c o n
s t a n t with time.
It s h o u l d be m a d e clear t h a t only fractions of a
g r a m of material are necessary for t h e r m o l u m i n e s
cence a n d this c a n be r e m o v e d u n o b t r u s i v e l y from
ancient objects. T h e t e c h n i q u e w h e n carefully applied
c a n give a n a c c u r a c y of d a t i n g t o 1 0 % . In recent
years it h a s b e c o m e a powerful tool in t h e detection of
a r t forgeries ( F l e m i n g 1975).
T h e s a m e principles a p p l y t o t h e d a t i n g of geolo
gical rocks. Q u a r t z in the e a r t h ' s crust h a s received so
m u c h ionizing r a d a t i o n t h a t the t r a p s h a v e b e c o m e
s a t u r a t e d . H o w e v e r , w h e r e t h e r o c k s h a v e been
h e a t e d sufficiently, for e x a m p l e , by t h e flow of lava
from v o l c a n o s , t h e p r e v i o u s r a d i a t i o n effects a r e
erased. It t h e n b e c o m e s possible by m e a n s of t h e r m o
luminescence, t o establish the d a t e at which they were
last h e a t e d intensively. T h e r e is a n u p p e r limit of
528
a b o u t 10 years for t h e d a t i n g of r o c k s b y t h e r m o
luminescence, because over longer p e r i o d s t h e n a t u r a l
r a d i a t i o n s a t u r a t e s t h e t r a p s t h a t give rise t o t h e glow
p e a k s used in d a t i n g . T h e lower limit of d a t i n g
d e p e n d s o n t h e t h e r m o l u m i n e s c e n t sensitivity of a
m a t e r i a l b u t is typically a few years.
5. Material
Identification
Bibliography
Aitken J 1974 Physics and Archaeology. Clarendon,
Oxford
Ausin V, Alvarez-Rivas J L 1972 Thermoluminescence and
annealing of F centers in KC1 y-radiated at toom temper
ature. J. Phys. C 5: 82-96
Becker 1973 Solid State Dosimetry. CRC, Cleveland, OH
Braunlich (ed.) 1979 Thermally stimulated relaxations in
solids. Top. Appl. Phys. 37: Springer, Berlin
Cameron J R, Suntharalingam N, Kenny G 1968 Thermo
luminescent Dosimetry. University of Wisconsin Press,
Madison, WI
Chen R, Kirsch Y 1981 Analysis of Thermally Stimulated
Processes. Pergamon, Oxford
Douglas G, Morency M, McDougall D J 1970 Detection of
strain in rocks using an intrinsic "semini-insulator" char
acteristic of some materials. Mod. Geol. 1: 211-17
Fairchild R G, Mattern L, Lengweiler K, Levey W 1978
Thermoluminescence of LiF TLD 100: emission-spectra
measurements. J. Appl. Phys. 49: 4512-22
Fleming S J 1975 Authenticity in Art: The Scientific Detec
tion of Forgery. Institute of Physics, London, pp. 73-97
Fleming S J 1979 Thermoluminescence Techniques in Archae
ology. Oxford University Press, New York
Kriegseis W, Scharman A 1980 Toxicity determination of
quartz and coal mine dust by thermoluminescence. Nucl.
Instr. Meth. 175: 239-40
McKeever S W S 1984 Thermoluminescence. Cambridge
University Press, Cambridge
McKinlay A F 1981 Thermoluminescence Dosimetry. Hilger,
London
Taylor G C, Lilley 1978 The analysis of thermolumines
cent glow peaks in LiF (TLD-100). J. Phys. D 11: 567-81
E. Lilley
[Norton, Northboro, Massachusetts, USA]
Thermophysical
Thermophysical Measurements,
Subsecond
U s i n g s u b s e c o n d pulse h e a t i n g t e c h n i q u e s it is p o s
sible t o reach t e m p e r a t u r e regions t h a t a r e n o t access
ible t o s t e a d y - s t a t e e x p e r i m e n t s , w h i c h a r e limited t o
t e m p e r a t u r e s below a b o u t 2000 K . T h i s article p r e
sents a description a n d general survey of s u b s e c o n d
t h e r m o p h y s i c s research including b o t h r a p i d resistive
h e a t i n g (volume) a n d pulse laser h e a t i n g (surface)
techniques. T h e e m p h a s i s will b e o n m e a s u r e m e n t s a t
very high t e m p e r a t u r e s . Pulse h e a t i n g t e c h n i q u e s a r e
used for t h e d e t e r m i n a t i o n of t h e t h e r m o p h y s i c a l
p r o p e r t i e s of m a t t e r for t e m p e r a t u r e s from a b o u t
1500 u p t o a b o u t 10 000 K . T h e time regime
12
covered is 1 - 1 0 " s. T h e s e investigations e n a b l e t h e
s t u d y of t h e b e h a v i o r of m a t t e r u n d e r c o n d i t i o n s b o t h
n e a r t o a n d far from t h e r m o d y n a m i c e q u i l i b r i u m .
1. Advantages
of Pulse Heating
Techniques
T r a d i t i o n a l static s t e a d y - s t a t e t e c h n i q u e s for t h e
m e a s u r e m e n t of t h e r m o p h y s i c a l p r o p e r t i e s a r e
generally limited t o t e m p e r a t u r e s below a b o u t
2000 K . T h i s limitation is a result of t h e chemical
i n t e r a c t i o n of t h e specimens with t h e c o n t a i n e r s , t h e
loss of m e c h a n i c a l s t r e n g t h , a n d p r o b l e m s with h e a t
transfer, e v a p o r a t i o n a n d electrical i n s u l a t i o n while
the s a m p l e a n d its e n v i r o n m e n t a r e k e p t for p e r i o d s of
u p t o h o u r s a t high t e m p e r a t u r e s . F a s t d y n a m i c
m e t h o d s h a v e been d e v e l o p e d t o a v o i d these difficult
ies a n d t o p e r m i t t h e e x t e n s i o n of t h e m e a s u r e m e n t s
to higher t e m p e r a t u r e s . T h e p r o p e r t i e s of m a t t e r a t
high t e m p e r a t u r e s a r e useful for h i g h - t e m p e r a t u r e
technologies s u c h a s a e r o s p a c e , n u c l e a r energy a n d
the e s t a b l i s h m e n t of t e m p e r a t u r e reference p o i n t s ,
including a p p l i c a t i o n s which a r e subjected t o hight e m p e r a t u r e / h i g h - p r e s s u r e c o n d i t i o n s , as well as for
m o d e l l i n g a n d basic t h e o r y .
Such pulse h e a t i n g e x p e r i m e n t s p e r f o r m t h e entire
m e a s u r e m e n t in less t h a n 1 s. T h e h e a t i n g rates used
4
_1
1 0
_1
and 1 0 K s
a n d require
vary b e t w e e n 1 0 K s
r e c o r d i n g e q u i p m e n t with s h o r t r e s p o n s e times. T h e
scope of this article is restricted t o resistive selfh e a t i n g m e t h o d s a n d t o laser h e a t i n g t e c h n i q u e s .
O t h e r t e c h n i q u e s for p r o p e r t y m e a s u r e m e n t s u p t o
5 0 0 0 - 1 0 000 K , such as chemical flames, s h o c k waves,
solar h e a t i n g , fission/fusion a n d high-energy electron
o r n e u t r o n h e a t i n g , will n o t b e t a k e n i n t o c o n s i d e r a
tion here.
2. Resistive
Pulse
Heating
2.1
Experimental
R a p i d v o l u m e h e a t i n g m e t h o d s a r e limited t o electri
cally c o n d u c t i n g m a t e r i a l s a n d involve resistive selfh e a t i n g of t h e specimen b y passing a n electrical
c u r r e n t pulse t h r o u g h it. S t a r t i n g a t r o o m t e m p e r a
Measurements,
Subsecond
t u r e , t h e m e a s u r e m e n t s c a n b e p e r f o r m e d far i n t o t h e
liquid p h a s e of t h e investigated m a t e r i a l . D e p e n d i n g
o n t h e h e a t i n g r a t e r e q u i r e d , t h e energy is s t o r e d in a
b a t t e r y b a n k (slow) o r in a c a p a c i t o r b a n k (fast). T h e
m e t a l s a m p l e s u s u a l l y wires, foils o r t u b e s a r e
c o n t a i n e d in a c o n t r o l l e d e n v i r o n m e n t c h a m b e r .
M e a s u r e m e n t s c a n be p e r f o r m e d in v a c u u m o r u n d e r
a m b i e n t pressures u p t o 5 k b a r u n d e r nearly isobaric
c o n d i t i o n s , t h e pressurized m e d i u m n o r m a l l y being
argon or water.
A functional d i a g r a m of a typical resistive pulse
h e a t i n g system is given in F i g . 1; t h e details of t h e
c o m p o n e n t s vary with t h e time scale of t h e m e a s u r e
m e n t . T h e discharge circuit typically consists of the
energy s t o r a g e , t h e m a i n switch (e.g., high-voltage
m e r c u r y v a p o r ignition t u b e ) a n d t h e specimen
c h a m b e r with w i n d o w s for optical diagnostics,
t o g e t h e r with t h e pressure c o n t r o l . A d d i t i o n a l re
q u i r e m e n t s a r e a c r o w b a r switch t o s t o p t h e experi
m e n t a t a n y desired m o m e n t a n d t h e c h a r g i n g unit.
The measured quantities are the current through
t h e s a m p l e , t h e voltage a c r o s s t h e s a m p l e , t h e t e m p e r
a t u r e of t h e s a m p l e , which is d e t e r m i n e d using optical
p y r o m e t e r s , a n d o t h e r optical m e a s u r e m e n t s (e.g.,
s a m p l e v o l u m e , velocity of s o u n d , see T a b l e 1), as well
as t h e a m b i e n t p r e s s u r e . T h e r e c o r d i n g e q u i p m e n t is
n o r m a l l y placed in a shielded r o o m : t h e faster t h e rise
time of a n e x p e r i m e n t , t h e b e t t e r t h e shielding h a s t o
be. T h e r e c o r d e d d a t a a r e e v a l u a t e d after t h e experi
m e n t with t h e aid of a c o m p u t e r .
D u r i n g t h e c o u r s e of o n e fast pulse e x p e r i m e n t , it is
possible t o o b t a i n d a t a for, for e x a m p l e , e n t h a l p y ,
t e m p e r a t u r e , specific electric resistivity, specific
v o l u m e as a function of time (while t h e specimen
rapidly passes t h r o u g h a wide r a n g e of states) a n d
s o u n d velocity a t a desired t e m p e r a t u r e (as well as
o t h e r q u a n t i t i e s , as cited in T a b l e 1) reaching far i n t o
the liquid p h a s e of t h e investigated m a t e r i a l . F r o m
these q u a n t i t i e s it is possible t o calculate, for liquid
m e t a l s , t h e specific h e a t a t c o n s t a n t p r e s s u r e , the
t h e r m a l e x p a n s i o n coefficient, G r u n e i s e n ' s y, a d i a b a tic a n d i s o t h e r m a l b u l k m o d u l i i a n d compressibilities,
specific h e a t a t c o n s t a n t p r e s s u r e a n d specific h e a t a t
constant volume.
F o r t h e solid m a t e r i a l , d a t a for t h e r m o p h y s i c a l
p r o p e r t i e s , such a s solid-solid t r a n s i t i o n t e m p e r a t u r e s
a n d energies, n o r m a l spectral e m i t t a n c e , h e m i s p h e r i
cal t o t a l e m i t t a n c e a n d t h e r m a l c o n d u c t i v i t y (see
T a b l e 1), c a n be o b t a i n e d by slower pulse experi
m e n t s . E x a c t f o r m u l a e for t h e calculation of these
t h e r m o p h y s i c a l p r o p e r t i e s s h o u l d be t a k e n from t h e
review articles of G a t h e r s (1986) a n d of Cezairliyan
(1988).
T h e pulse h e a t i n g t e c h n i q u e s described here a r e
usually classified u n d e r three categories, d e p e n d i n g o n
t h e r e q u i r e d time resolution of t h e m e a s u r i n g e q u i p
m e n t : millisecond resolution systems, m i c r o s e c o n d
r e s o l u t i o n systems a n d s u b m i c r o s e c o n d resolution
systems.
529
Thermophysical
Measurements,
Subsecond
Circuit
inductivity
Circuit
resistivity
Shielded
Pressure(
control
diiCharging
Crowbar
unit
switch
Temperature
<
measurement
.
room
<
hi
Voltage
measurement
Current
Current
probe
measurement
Start
Main
switch
Figure 1
A typical resistive pulse heating system
530
Thermophysical
Measurements,
Subsecond
Table 1
Thermophysical properties that may be measured by dynamic (subsecond) heating methods
Heating method
Time
resolution
Resistive heating
ms
Laser heating
Solids
Liquids
heat capacity
thermal expansion
electrical resistivity
hemispherical total emittance
normal spectral emittance
phase transitions
solid-solid transformation temperature
solid-solid transformation energy
melting temperature
apparent temperature at melting point
deduced from radiance
thermal conductivity
mechanical properties"
8
velocity of sound
surface tension8
heat of fusion8
heat capacity
8
electrical resistivity
8
hemispherical total emittance
phase transitions
heat of fusion
heat capacity
electrical resistivity
thermal expansion
velocity of sound
melting temperature
phase transitions
apparent temperature at melting point
deduced from radiance
8
thermal conductivity
8
normal spectral emittance
heat of fusion
heat capacity
cv
electrical resistivity
thermal expansion
velocity of sound
melting temperature
phase transitions
apparent temperature at melting point
deduced from radiance
Gruneisen
adiabatic bulk modulus
isothermal bulk modulus
adiabatic compressibility
isothermal compressibility
8
thermal conductivity
8
normal spectral
emittance
8
heat of fission 8
surface tension
heat of fusion
heat capacity
thermal expansion
normal spectral emittance
melting temperature
vapor pressure
partial pressures
reflectivity
phase transitions
hemispherical total emittance
transmission
thermal conductivity
heat of fusion
heat capacity
thermal expansion
normal spectral emittance
melting temperature
vapor pressure
partial pressures
reflectivity
phase transitions
8
surface tension
8
viscosity
ns
phase transitions
reflectivity
transmission
thermal conductivity
phase transitions
reflectivity
ps
phase transitions
reflectivity
transmission
velocity of sound
phase transitions
reflectivity
a in development stage
531
Thermophysical
Measurements,
Subsecond
e x p e r i m e n t s is set by the o n s e t of c o m p l e x g e o m e t r y .
7
T h e h e a t i n g rates a r e typically in t h e r a n g e 1 0 8
_ 1
1 0 K s . M o r e o v e r , t o achieve high t e m p e r a t u r e s ,
high pressures h a v e t o be applied, r a n g i n g u p t o
5 kbar.
M i c r o s e c o n d t e c h n i q u e s h a v e r e a c h e d a high level
of d e v e l o p m e n t a n d achieve a c c u r a t e m e a s u r e m e n t s
o n liquid m e t a l s . T h e uncertainties a r e b e t w e e n 2 %
a n d 7 % . T h e c u r r e n t t h r o u g h t h e s a m p l e is m e a s u r e d
using a high-precision c u r r e n t p r o b e a n d the voltage
a l o n g the s a m p l e is m e a s u r e d by knife-edge p r o b e s o r
with o h m i c voltage dividers.
T h e surface r a d i a n c e of t h e h o t surface is detected
b y fast p y r o m e t e r s w i t h silicon p h o t o d i o d e s c o m b i n e d
with interference niters. T h e c o n s t a n t r a d i a t i o n of t h e
melting s a m p l e is used as a fixed p o i n t of t h e t e m p e r
a t u r e calculations, using the K i r c h h o f f - P l a n c k law.
T e m p e r a t u r e s a r e calculated from m e a s u r e d intensit
ies by f o r m i n g ratios of t h e intensity a t a r b i t r a r y
p o i n t s to t h e intensity a t melt. T h i s is carried o u t
u n d e r the a s s u m p t i o n t h a t , b e c a u s e of t h e lack of
emissivity d a t a for this region, t h e emissivity a t t h e
melting p o i n t e(X9Tm) is e q u a l t o the emissivity in t h e
liquid p h a s e (,).
V o l u m e s a r e m e a s u r e d with s h a d o w g r a p h systems
by backlighting t h e s a m p l e , t h e s a m e m e a s u r e m e n t s
p r o v i n g t h e stability of t h e specimen. S o m e systems
a r e also able t o m e a s u r e s o u n d velocities in t h e pulse
h e a t e d samples a t different t e m p e r a t u r e s .
T h e e x p e r i m e n t a l q u a n t i t i e s a r e r e c o r d e d every
100 ns with digital d a t a acquisition systems. T h e
t h e r m o p h y s i c a l p r o p e r t i e s o b t a i n e d with m i c r o s e c o n d
time resolution a r e listed in T a b l e 1.
T h e well-equipped a p p a r a t u s described previously
is t h a t of R . S. H i x s o n a n d c o - w o r k e r s a t t h e L o s
A l a m o s N a t i o n a l L a b o r a t o r y , N e w M e x i c o , U S A . By
m e a s u r i n g t h e speed of s o u n d in liquid m e t a l s they a r e
able t o calculate all the t h e r m o p h y s i c a l p r o p e r t i e s
cited for fast pulse h e a t i n g systems in Sect. 2 . 1 . O t h e r
o p e r a t i o n a l systems will n o w be discussed.
A t the N a t i o n a l Institute of S t a n d a r d s a n d T e c h
nology in G a i t h e r s b u r g , M a r y l a n d , U S A , a m i c r o
second r e s o l u t i o n system w a s recently established b y
J. L. M c C l u r e a n d c o - w o r k e r s . T h e w h o l e e x p e r i m e n
tal s e t u p is h o u s e d in a shielded r o o m , with all the
recording equipment outside.
In E u r o p e , at t h e C o m m i s s a r i a t a l'Energie A t o m i q u e in Paris, A . B e r t h a u l t a n d c o - w o r k e r s h a v e e s t a b
lished nearly the s a m e system as t h a t in L o s A l a m o s .
T h i s i n s t r u m e n t a t i o n is n o w being o p e r a t e d by T .
T h e v e n i n . T h e i r results, m a i n l y o n t r a n s u r a n i u m ele
m e n t s , a r e confidential.
E. K a s c h n i t z a n d G . P o t t l a c h e r a t t h e Institut fur
Experimentalphysik der Technischen
Universitat
G r a z , A u s t r i a , h a v e also b e g u n t o establish a m i c r o
second resolution system similar t o t h e o n e in L o s
A l a m o s . T h i s system is still u n d e r c o n s t r u c t i o n , b u t
they h a v e a l r e a d y been able t o r e p o r t s o m e i m p r o v e
m e n t s , such as a fast p y r o m e t e r sensitive d o w n t o t h e
532
m e l t i n g t e m p e r a t u r e of c o p p e r , m e a s u r e m e n t s of
s o u n d velocity in solid m e t a l s a n d the first results o n
t h e emissivity of liquid m e t a l s .
M . A . Scheindlin a n d c o - w o r k e r s a t t h e Institute of
H i g h T e m p e r a t u r e s , I V T A N , M o s c o w , o p e r a t e a sys
7
l
t e m with h e a t i n g rates of 10 s ~ . T h e onset of their
p y r o m e t e r is a t 2500 K . T h i s g r o u p also p e r f o r m s
e x p e r i m e n t s with laser pulse h e a t i n g a n d c o n n e c t s t h e
results o b t a i n e d b y b o t h m e t h o d s .
A n o t h e r pulse h e a t i n g system is o p e r a t e d by M .
M a r t y n y u k a n d c o - w o r k e r s at t h e Patrice L u m u m b a
P e o p l e ' s F r i e n d s h i p University, M o s c o w . T h e m a i n
interest of this g r o u p is in t h e investigation of p h a s e
transitions.
2.4 Experiments
Resolution
with Submicrosecond
Time
T h e t e m p e r a t u r e r a n g e covered in s u b m i c r o s e c o n d
time r e s o l u t i o n e x p e r i m e n t s is from a b o u t 2000 u p
t o m o r e t h a n 10 000 K , a g a i n d e p e n d i n g o n t h e m a t e r
ial investigated. I n this k i n d of e x p e r i m e n t , the reach
ing of t h e s p i n o d a l line in t h e V p l a n e of t h e classical
v a n d e r W a a l s e q u a t i o n of state is t h e stability limit.
F u r t h e r h e a t i n g will p r o d u c e r a p i d v o l u m e e x p a n s i o n ;
t h e so-called " w i r e e x p l o s i o n " will t a k e place a n d
i n t e r r u p t electrical c o n d u c t i v i t y . T h e h e a t i n g rates
9
_ 1
applied a r e m o r e t h a n 1 0 K s . T h e s e high h e a t i n g
rates also allow investigations a t 1 b a r , b u t m o r e
a c c u r a t e results a r e o b t a i n e d a t a m b i e n t pressures u p
to 5 kbar.
S u b m i c r o s e c o n d t e c h n i q u e s allow t h e investigation
of liquid m e t a l s u p t o t h e e n d of their liquid p h a s e .
Because of t h e time regime ( s a m p l i n g r a t e e a c h 10 ns
o r less) a n d t h e wide t e m p e r a t u r e r a n g e , the uncer
tainties will increase from 5 % t o 1 5 % . G e n e r a l l y , the
o b t a i n e d results a r e in g o o d a g r e e m e n t with the
results from m i c r o s e c o n d t e c h n i q u e s .
T h e a c h i e v e m e n t of h e a t i n g rates g r e a t e r t h a n
9
_1
requires a very low inductivity for t h e dis
10 Ks
c h a r g e circuit a n d a very g o o d shielding of the
m e a s u r e d signals. T h i s calls for a coaxially m o u n t e d
discharge system with d o u b l e coaxially shielded m e a
suring lines leading t o a screened r o o m which includes
the recording equipment.
E x p e r i m e n t s with s u b m i c r o s e c o n d time resolution
a r e p e r f o r m e d a t t h e I n s t i t u t fur E x p e r i m e n t a l p h y s i k
d e r T e c h n i s c h e n U n i v e r s i t a t G r a z , A u s t r i a . T h e only
difference from t h e m i c r o s e c o n d m e a s u r e m e n t s is the
m e a s u r e m e n t of c u r r e n t , w h i c h is carried o u t with t h e
aid of a n i n d u c t i o n coil a n d s u b s e q u e n t electrical RC
i n t e g r a t i o n of t h e i n d u c e d signal. Besides the d e t e r m i
n a t i o n of t h e r m o p h y s i c a l p r o p e r t i e s u p t o very high
t e m p e r a t u r e s , e x p e r i m e n t s h a v e also b e e n m a d e o n
o b t a i n i n g critical p o i n t d a t a for m e t a l s by investiga
tions a t elevated pressures. T h e first results o n lead
h a v e been r e p o r t e d b y P o t t l a c h e r a n d J a g e r (1990).
A t t h e I n s t i t u t e of H i g h T e m p e r a t u r e s , I V T A N ,
M o s c o w , Savvatimskii a n d c o - w o r k e r s a r e interested
in e x p l o d i n g wires p h e n o m e n a a n d they a r e also
Thermophysical
determining
metals.
3. Laser
thermophysical
Pulse
properties
of
liquid
Heating
3.1
Experimental
T h e m a i n a d v a n t a g e of laser pulse h e a t i n g is t h a t it
c a n be used for t h e investigation of all k i n d s of
m a t e r i a l s in a d d i t i o n t o m e t a l s such as c e r a m i c s , fuel
m a t e r i a l s a n d n o n m e t a l s . T h e energy is delivered t o
the s a m p l e in a localized w a y so t h a t efficient h e a t i n g
results a n d small specimens c a n be used. T h e use of
u l t r a s h o r t laser pulses results in very fast h e a t i n g ;
t h u s , extremely high t e m p e r a t u r e s m a y be achieved.
By using this t e c h n i q u e t h e a m o u n t of m a t t e r being
h e a t e d is c o n s i d e r a b l y smaller, b u t t h e m a i n d i s a d v a n
tage is, in m o s t cases, t h a t t h e laser energy d e p o s i t i o n
r a t e c a n n o t be assessed precisely.
I n this k i n d of e x p e r i m e n t , a s h o r t pulse of laser
r a d i a t i o n h e a t s small p a r t s of t h e surface of a plain
s a m p l e or, w i t h o u t c o n t a i n m e n t , t h e full v o l u m e of a
small levitating s p h e r e ( 5 0 0 - 1 0 0 0 p m d i a m e t e r ) from
r o o m t e m p e r a t u r e u p t o t h e liquid p h a s e . A g a i n , t h e
samples a r e inside a c o n t r o l l e d e n v i r o n m e n t c h a m b e r
a n d the m e a s u r e m e n t s c a n b e p e r f o r m e d in v a c u u m
(laser h e a t i n g , v a c u u m ( L H V ) ) o r u n d e r a m b i e n t
pressures u p t o 2 k b a r (laser h e a t i n g , p r e s s u r e ( L H P ) ) .
T h e pressurized m e d i u m is inert gas.
A s c h e m a t i c display of t h e e x p e r i m e n t a l t e c h n i q u e
a n d s o m e m a i n items of i n s t r u m e n t a t i o n of a laser
pulse h e a t i n g system a r e s h o w n in F i g . 2. T h e details
of the c o m p o n e n t s v a r y for different m e a s u r e m e n t s
a n d for different t e c h n i q u e s .
T h e e x p e r i m e n t a l s e t u p for p e r f o r m i n g laser h e a t
ing m e a s u r e m e n t s is c e n t e r e d o n a pulsed laser s o u r c e ,
Mass
spectrometer
Figure 2
A laser pulse heating system
aquisition
Measurements,
Subsecond
usually a n N d : Y A G m o d e - l o c k e d laser. T h e o u t p u t
r a d i a t i o n ( r e c t a n g u l a r laser pulse, = 1.06 p m , 90 fs
t o 1 m s pulse d u r a t i o n , G a u s s i a n spatial p o w e r
7
2
profile, p o w e r densities u p t o 1 0 W c m ) m a y be
frequency c o n v e r t e d b y h a r m o n i c g e n e r a t i o n in n o n
linear crystals, r e a c h i n g visible a n d ultraviolet w a v e
lengths. T h e laser pulse is focused o n t h e polished
surface of t h e s a m p l e a n d p r o v i d e s t h e excitation u p
t o t e m p e r a t u r e s of 5 0 0 0 - 1 0 000 K. T h e h e a t e d a r e a of
the t a r g e t r a n g e s from 1 m m t o 3 m m in d i a m e t e r . T h e
s a m p l e itself is inside a c o n t r o l l e d e n v i r o n m e n t
c h a m b e r ( n o t indicated in Fig. 2).
T h e light e m i t t e d from t h e centre of the target is
detected optically by a high-speed p y r o m e t e r ; the
c a l c u l a t i o n of t h e t e m p e r a t u r e of t h e target surface
b e c o m e s possible o n certain a s s u m p t i o n s ; the s a m e is
t r u e for the d e t e r m i n a t i o n of spectral a n d t o t a l emit
t a n c e a n d for ultrafast p h a s e t r a n s i t i o n s . M e a s u r e
m e n t s of v o l u m e p r o p e r t i e s o n acoustically levitating
spheres such as density, t h e r m a l e x p a n s i o n , e n t h a l p y
a n d h e a t c a p a c i t y rely o n t h e a c h i e v e m e n t of t e m p e r
a t u r e u n i f o r m i t y o r t h e a c c u r a t e k n o w l e d g e of t h e
t e m p e r a t u r e profile t h r o u g h o u t t h e s a m p l e . A s in
m o s t cases t h e laser energy d e p o s i t i o n r a t e c a n n o t be
assessed precisely, t h e c o o l i n g tail of the levitation
e x p e r i m e n t s is used preferentially (e.g., for t h e deter
m i n a t i o n of Cp(X), from t h e g r a p h of t e m p e r a t u r e vs
time).
A m a s s s p e c t r o m e t e r is used t o d e t e r m i n e the
p a r t i a l pressures of t h e v a r i o u s n e u t r a l a n d ionized
g a s e o u s species of t h e v a p o r jet. S p e c t r o s c o p i c t e m
p e r a t u r e m e a s u r e m e n t s a n d high-speed p h o t o g r a p h y
of t h e e v a p o r a t i n g j e t a r e r e q u i r e d as i n p u t d a t a t o
investigate t h e gas d y n a m i c e x p a n s i o n m e c h a n i s m a t
e x t r e m e rates of e v a p o r a t i o n a n d t o estimate b a c k scattering effects.
A p r o b i n g laser b e a m c a n be focused o n t h e center
of the h e a t e d a r e a of t h e s a m p l e a n d t h e reflected a n d /
o r t r a n s m i t t e d b e a m energies a r e m e a s u r e d by light
d e t e c t o r s . T h e s e signals, o n c e n o r m a l i z e d , p r o v i d e
reflectivity a n d / o r t r a n s m i s s i o n d a t a for t h e p r o b e d
w a v e l e n g t h a t a certain p o i n t in time. F r o m the
i n s t a n t a n e o u s values of reflectivity a n d t r a n s m i s s i o n ,
it is possible to d e d u c e the c o m p l e x index of refraction
of t h e m a t e r i a l d u r i n g t h e i n t e r a c t i o n .
O t h e r investigation m e t h o d s a r e also used, b u t a r e
n o t i n d i c a t e d in Fig. 2, such as x-ray investigations of
t h e s a m p l e s (levitated spheres) t o o b t a i n v o l u m e d a t a
as well as density.
After r e c o r d i n g t h e m e a s u r e m e n t s with fast digital
e q u i p m e n t , this difficult t e c h n i q u e needs a lot of
theoretical b a c k g r o u n d i n f o r m a t i o n a b o u t optical
p y r o m e t r y , t h e energy b a l a n c e of the s a m p l e , Fresnel
f o r m u l a e a n d so o n in o r d e r t o calculate from the
m e a s u r e d d a t a p r o p e r t i e s such as t e m p e r a t u r e , emissi
vity, C p , t h e c o m p l e x index of refraction a n d so o n .
O w i n g t o t h e c o m p l e x c a l i b r a t i o n a n d analytical
p r o c e d u r e s , the u n c e r t a i n t y of the o b t a i n e d t h e r m o
physical p r o p e r t i e s increases strongly a n d their inter-
533
Thermophysical
Measurements,
Subsecond
534
N a n o s e c o n d laser-induced p h a s e t r a n s i t i o n s a n d
m e t a s t a b l e p h a s e s q u e n c h i n g a r e being investigated a t
t h e D i p a r t i m e n t o di Fisica of t h e University of C a t a
nia, Italy, b y P . Baeri. T h e m e a s u r e m e n t s allow t h e
d e t e r m i n a t i o n of m e l t i n g p o i n t s a n d t h e e v a l u a t i o n of
heat capacity and thermal conductivity.
A t t h e Physics D e p a r t m e n t of t h e G e n e r a l M o t o r s
Research Laboratories, Warren, Michigan, USA, G.
Eesley h a s used a n optical t r a n s i e n t reflectance tech
n i q u e with p i c o s e c o n d laser pulses t o c h a r a c t e r i z e
b o t h t h e t h e r m a l a n d a c o u s t i c t r a n s p o r t d y n a m i c s of
thin m e t a l films. T h e t r a n s i e n t thermoreflectance a n d
piezoreflectance m e a s u r e m e n t s c a n be e x t e n d e d i n t o
t h e f e m t o s e c o n d time d o m a i n t o investigate t h e d y n a
mics of energy t r a n s p o r t u n d e r n o n e q u i l i b r i u m elec
t r o n lattice t e m p e r a t u r e differences.
M . Malvezzi a t t h e D i p a r t i m e n t o di E l e t t r o n i c a of
t h e U n i v e r s i t y of P a v i a , Italy, h a s built u p a very
m a t u r e system for p i c o s e c o n d laser pulses (30 p s ,
1.06 ) t o m e a s u r e time-resolved reflectivity a n d / o r
t r a n s m i s s i o n values, p h a s e t r a n s i t i o n s a n d timeresolved ellipsometry. I n f o r m a t i o n o n t h e optical
dielectric function of t h e m a t e r i a l u n d e r t h e c o n
d i t i o n s of t h e e x p e r i m e n t c a n be o b t a i n e d .
(c) Femtosecond heating pulses. T h e u l t i m a t e regime
in t h e surface h e a t i n g of solids o c c u r s with femto
s e c o n d pulses. H e r e , t h e laser pulse d u r a t i o n s r e a c h
t h e characteristic times for energy r e l a x a t i o n of t h e
p h o t o e x c i t e d electron gas t o t h e lattice. T h e h e a t is
d e p o s i t e d in s u c h a s h o r t t i m e t h a t the h e a t c o n d u c
tion o u t of t h e l i g h t - a b s o r b i n g v o l u m e d o e s n o t o c c u r
within t h e laser pulse d u r a t i o n . E x t r e m e l y high t e m
p e r a t u r e s a r e g e n e r a t e d in a shallow layer w h i c h is still
in a quiescent s t a t e a n d c a n b e o b s e r v e d before m a t t e r
escapes t h e i r r a d i a t e d a r e a b y e v a p o r a t i o n o r a b l a
tion. T h e field of t h e r m o p h y s i c s is still in its infancy
h e r e , a l t h o u g h these c i r c u m s t a n c e s a r e extremely at
tractive in t h e s t u d y of h i g h - t e m p e r a t u r e regimes of
c o n d e n s e d m a t t e r a n d they o p e n n e w possibilities in
t h e field of t h e r m o p h y s i c a l m e a s u r e m e n t s .
Time-resolved optical reflectivity m e a s u r e m e n t s
a n d t h e d e t e c t i o n of ultrafast p h a s e t r a n s i t i o n s with
t h e aid of f e m t o s e c o n d laser pulses (90 fs, 0.62 )
h a v e b e e n p e r f o r m e d a t t h e University of T e x a s a t
Austin, U S A , by M . D o w n e r and co-workers.
A t t h e I n s t i t u t fur L a s e r u n d P l a s m a p h y s i k ,
U n i v e r s i t a t Essen, G e r m a n y , D . v o n d e r L i n d e h a s
1 4
_1
o b t a i n e d h e a t i n g rates of 1 0 K s w i t h laser pulses
of 20 p s d u r a t i o n . T h i s results in d y n a m i c a l super
h e a t i n g of t h e solid p h a s e a n d allows t h e s t u d y of melt
front velocities in s u p e r h e a t e d s a m p l e s .
F e m t o s e c o n d e x p e r i m e n t s h a v e also been per
f o r m e d a t t h e N a t i o n a l C o u n c i l of C a n a d a , O t t a w a ,
C a n a d a , b y P . C o r k u m . H i s research is also c o n c e n
t r a t e d o n t h e physics t h a t is implied b y t h e fast t i m e
scales a n d t h e high intensities available.
A t t h e U n i v e r s i t y of C h i c a g o , U S A , N . Scherer h a s
used u l t r a s h o r t laser pulses t o s t u d y a n d investigate
Thermophysical
the ultrafast s p e c t r o s c o p y of c o n d e n s e d p h a s e d y n a
mics a n d f e m t o s e c o n d chemistry.
4. Future
Developments
Bibliography
Baeri 1990 Nanosecond laser-induced phase transitions
and metastable phases quenching. Philos. Mag. B. 61:
587-600
Berthault A, Aries L, Matricon J 1986 High-pressure hightemperature thermophysical measurements on tantalum
and tungsten. Int. J. Thermophys. 7: 167-79
Cezairliyan A 1988 Pulse calorimetry. In: Ho C Y (ed.) 1988
Specific Heat of Solids, CINDAS Data Series on Material
Properties, Vols. 1, 2. Hemisphere Publishing, New York,
pp. 323-53.
Cezairliyan A, Gathers G R, Malvezzi A M, Miiller A P,
Righini F, Shaner J W 1990 Issues and future directions in
subsecond thermophysics research. Int. J. Thermophys.
11: 819-33
Measurements,
Subsecond
535
Thermophysical
Measurements,
Subsecond
Reflection
of X
Rays
=1--
(1)
where
2 2
o = (X e /2nmc )ZNi(Zi+fi)
(2)
and
2
/? = / 2 ^ ) 7 / 7 )
536
(3)
+,
(4)
where
2A
+ 4 / ? ] ' + ( - \)
+ 4 >
= [( - ])
1 2
(5)
(6)
and
2
IB
= [( - ,)
+ ( - \)
O n e of the m o s t i m p o r t a n t p o i n t s t o n o t e is t h a t the
p e n e t r a t i o n of the rays i n t o the surface for < (pc
d o e s n o t d r o p t o zero. A n evanescent w a v e effectively
p r o b e s a few n a n o m e t e r s i n t o the s a m p l e surface. T h e
p e n e t r a t i o n d e p t h z 1 / e, defined as t h e d e p t h at which
the electric field h a s d r o p p e d t o 1 /e of its value at the
s a m p l e surface, is d e p e n d e n t o n a n d for small , is
given by
(7)
' *~4
Finally, it is interesting t o calculate the evanescent
w a v e intensity at t h e surface. T h i s is given by the
p r o d u c t of the electric field a n d its c o m p l e x conju
gate, a n d its d e p e n d e n c e o n is described by
EE*(<p) ^
1. Specular
= (Z +,
41<p
( + Af
(8)
w h e r e I is t h e incident b e a m intensity.
C u r v e s of ( ^ ) , zlle(<p) a n d \) are s h o w n in Fig.
1. It is i m m e d i a t e l y a p p a r e n t t h a t by v a r y i n g t h e
incident angle of a b e a m of rays o n a s m o o t h surface
the d e p t h of p e n e t r a t i o n c a n be controlled in a r a n g e
from a few n a n o m e t e r s t o m a n y m i c r o m e t e r s . T h i s is
the basis for t h e v a r i o u s thin-film analysis m e t h o d s
discussed in the following sections.
I n t h e o r y , a perfectly s m o o t h flat surface for which
t h e a b s o r p t i o n coefficient for r a y s is zero will h a v e a
reflection coefficient R(q>) of unity for all values of
from zero t o the critical angle 0, a b o v e which R(<p)
Thin Films:
0
Incident
2
angle
Figure 1
Typical curves of reflectivity (R), penetration depth ( z l / e)
and evanescent wave intensity (EE*) as a function of
incident angle () for rays incident on a smooth flat
surface
where is t h e a n g u l a r p o s i t i o n of t h e m t h m a x i m u m
a n d d is t h e film thickness. T h e s e " K i e s s i g fringes"
c a n be u n d e r s t o o d as a n effect arising from t h e
interference b e t w e e n t h e b e a m reflected from t h e
surface of the film a n d from t h e film-substrate inter
face. A s c a n be seen from E q n . (9), analysis of Kiessig
fringes c a n yield i n f o r m a t i o n o n t h e film thickness
a n d electronic density. Surface a n d interface r o u g h
ness m a y also b e c o n s i d e r e d in theoretical m o d e l s a n d
experimentally a p p e a r s as a r e d u c t i o n in fringe c o n
trast from the theoretical c a l c u l a t i o n for perfectly
s m o o t h interfaces. M o d e r n c o m p u t e r s a n d c o m p u t a
tional m e t h o d s m a y be used t o a n a l y z e t h e reflectivity
curves of surfaces with several d e p o s i t e d layers. A n
elegant illustration of this g r a z i n g x-ray reflectometry
( G X R R ) t e c h n i q u e is described by Le Boite et al.
(1988) w h o c o m p a r e it with R u t h e r f o r d b a c k s c a t t e r
ing as a n analysis t e c h n i q u e for thin-film mixing b y
ion b e a m s . H o w e v e r , the t e c h n i q u e is certainly n o t
w i t h o u t its limitations: systems giving p o o r fringe
c o n t r a s t d u e t o different densities b e t w e e n layers a r e
Characterization
by X
Rays
u n s u i t a b l e for G X R R , a n d t h e s a m p l e m u s t be fairly
large (for a c c u r a t e a l i g n m e n t ) , very s m o o t h a n d flat.
O n e further t e c h n i q u e for thin-film c h a r a c t e r i z a
tion m a y be m e n t i o n e d a t this p o i n t : total-reflection
x-ray fluorescence ( T X R F ) . T h i s is a simple modifica
tion of t h e s t a n d a r d t e c h n i q u e for c o m p o s i t i o n a l
analysis, w h e r e b y t h e surface is illuminated w i t h a n xr a y b e a m a n d t h e resulting x-ray fluorescence spec
t r u m yields i n f o r m a t i o n o n t h e a t o m i c species present.
In t h e glancing angle g e o m e t r y , a fine slit is used t o
collimate t h e b e a m , e n a b l i n g a c c u r a t e c o n t r o l of t h e
incident angle. D e p t h profiling of c o m p o s i t i o n is t h u s ,
in principle, feasible t h o u g h t h e t e c h n i q u e is n o r m a l l y
o n l y used for identifying a n d q u a n t i f y i n g surface
species. T X R F w a s originally d e v e l o p e d for c o m
p o s i t i o n a l analysis of trace elements d e p o s i t e d (e.g.,
from s o l u t i o n ) o n t o a n optically flat x-ray reflecting
surface, b u t its a p p l i c a t i o n t o thin-film a n d surface
analysis is o b v i o u s . Identification of interfacial a t o m i c
species is also possible.
2. Glancing
Angle
X-Ray
Diffraction
537
Thin Films:
Characterization
by X
Rays
Detector
SLit
Sample
Figure 2
GIAB surface diffraction geometry
538
Detector
Figure 3
GIXS surface diffraction geometry
3. Surface
X-Ray
Absorption
Spectroscopy
X - r a y a b s o r p t i o n s p e c t r o s c o p y ( X A S ) is a wellk n o w n t e c h n i q u e for s t r u c t u r a l c h a r a c t e r i z a t i o n t h a t
h a s d e v e l o p e d rapidly d u e t o t h e increased availability
of high-intensity s y n c h r o t r o n x-ray sources. X A S is
generally divided i n t o t w o regimes: x-ray a b s o r p t i o n
n e a r edge s t r u c t u r e ( X A N E S ) a n d e x t e n d e d x-ray
a b s o r p t i o n fine s t r u c t u r e ( E X A F S ) . X A N E S deals
with the s t r u c t u r e in the a b s o r p t i o n coefficient close t o
a n inner shell a b s o r p t i o n edge of t h e p a r t i c u l a r a t o m i c
species u n d e r investigation in the s a m p l e , while
E X A F S is c o n c e r n e d with t h e oscillations observed in
the a b s o r p t i o n coefficient u p t o several h u n d r e d elec
t r o n volts a b o v e t h e a b s o r p t i o n edge. B o t h furnish
i n f o r m a t i o n a b o u t t h e local s t r u c t u r e a r o u n d the
a b s o r b i n g a t o m i c species a n d a r e t h u s p a r t i c u l a r l y
useful in t h e s t u d y of a m o r p h o u s solids o r dilute
species in h o s t e n v i r o n m e n t s , w h e r e x-ray diffraction
is of limited use, X A N E S also gives the valence state
of the a b s o r b i n g species.
T h e subject of interest is h o w t o a p p l y X A S t o the
s t u d y of thin films o r surfaces. T h e first surfacesensitive X A S t e c h n i q u e , k n o w n as surface E X A F S
Thin Films:
(or S E X A F S ) , w a s p r o p o s e d a n d d e v e l o p e d in t h e late
1970s. T h e basis o f this m e t h o d is t h a t t h e surface
p h o t o e l e c t r o n yield is closely related t o t h e surface xr a y a b s o r p t i o n coefficient. T h e small escape d e p t h of
t h e p h o t o e l e c t r o n s (a few n a n o m e t e r s ) e n s u r e s surface
sensitivity, so t h a t S E X A F S is only of use in s t u d y i n g
surfaces (e.g., a b s o r b e d a t o m s o r m o n o l a y e r s ) o r very
thin films.
By e m p l o y i n g t h e glancing angle g e o m e t r y d e
scribed previously a n o t h e r r a n g e of surface a n d inter
face t e c h n i q u e s b e c o m e s possible. Reflection E X A F S ,
o r R e f l E X A F S , w a s first r e p o r t e d b y B a r c h e w i t z et al.
(1978). T h i s m e t h o d (see F i g . 4) consists of reflecting
a n x-ray b e a m off t h e s a m p l e surface a n d m e a s u r i n g
t h e r a t i o of reflected t o incident intensity ( / r / / 0) a s a
function of t h e x-ray energy ( ) . T h e surface a b s o r p
tion s p e c t r u m m a y t h u s b e f o u n d , w i t h a n effective
p e n e t r a t i o n d e p t h of a few n a n o m e t e r s . T h e possibili
ties of this t e c h n i q u e d o n o t , h o w e v e r , s t o p h e r e . F o r
surfaces with thin d e p o s i t e d films it is often possible
t o reflect t h e incident b e a m off t h e
film-substrate
interface. R e f l E X A F S in this case will b e sensitive t o
t h e c o m p l e t e d e p t h of t h e film, p l u s a few n a n o m e t e r s
of t h e s u b s t r a t e . Since X A S is " a t o m specific," t h e
possibilities for s t u d y i n g t h e interfacial region a r e
immediately a p p a r e n t . T h e signal-to-noise r a t i o of
such a surface-sensitive X A S t e c h n i q u e m a y often b e
c o n s i d e r a b l y e n h a n c e d b y m o n i t o r i n g t h e x-ray fluor
escence from t h e s a m p l e surface ( / F d e t e c t o r ) i n s t e a d
of t h e reflected b e a m intensity (see F i g . 4). Solidstate d e t e c t o r s m a y b e u s e d h e r e w i t h c o n s i d e r a b l e
effect t o further r e d u c e u n w a n t e d b a c k g r o u n d signal.
Fluorescence-detected E X A F S ( o r F L E X A F S ) a t
glancing angle is p a r t i c u l a r l y suitable w h e n s t u d y i n g
the e n v i r o n m e n t s of a t o m s with low c o n c e n t r a t i o n
a n d in c o n t r a s t w i t h R e f l E X A F S m a y b e e m p l o y e d a t
incident angles a b o v e ^ c , m a k i n g it m o r e versatile.
4. Current
Situation
Detector
slit
"Knife edge"
Figure 4
Experimental arrangement for ReflEXAFS and glancing
angle FLEXAFS
Characterization
by X
Rays
Bibliography
Aiginger H, Wobrauschek 1985 Total reflectance x-ray
spectrometry. In: Barrett C S, Predecki , Leyden D
(eds.) 1985 Advances in X-Ray Analysis, Vol. 28. Plenum,
New York, pp. 1-10
Barchewitz R, Cremonese-Visicato M, Onori G 1978 X-ray
photoabsorption of solids by specular reflection. J. Phys.
C 11: 4439^15
Born M, Wolf 1980 Principles of Optics. Pergamon,
Oxford
Compton A 1923 The total reflection of x-rays. Philos.
Mag. 45: 1121-31
Doerner F, Brennan S 1988 Strain distribution in thin
aluminum films using x-ray depth profiling. J. Appl. Phys.
63(1): 126-31
Eisenberger P, Citrin P, Hewitt R, Kincaid 1981
SEXAFS: new horizons in surface structure determi
nation. CRC Crit. Rev. Solid State Mater. Sci. 10(2): 191207
Fox R, Gurman S J 1980 EXAFS and surface EXAFS from
measurements of x-ray reflectivity. J. Phys. C 13: L249-53
Heald S M, Keller E, Stern A 1984 Fluorescence detection
of surface EXAFS. Phys. Lett. A 103(3): 155-8
Huang C, Toney F, Brennan S, Rek 1987 Analysis of
cobalt-doped iron oxide thin films by synchrotron radia
tion. Thin Solid Films 154: 439-45
Kiessig 1931a Interference of Rontgen rays on thin layers.
Ann. Physik 10: 769-88
Kiessig 1931b Investigation of the total reflection of
Rontgen rays. Ann. Physik 10: 715-68
539
by X
Rays
540
O f t h e v a r i o u s microdiffraction t e c h n i q u e s , o n e
c o n v e r g e n t - b e a m diffractionhas
become
more
widely used t h a n the o t h e r s , a n d this article will
c o n c e n t r a t e o n it.
/.
Basic
Ideas
2. Experimental
Details
Transmission
Electron
Microscopy:
Convergent-Beam
and
Microdiffraction
Figure 1
Schematic diagram to show the formation of
convergent-beam electron diffraction patterns
b e a m a n d o n e for e a c h B r a g g reflected b e a m . F i g u r e 2
s h o w s a n e x a m p l e of a c o n v e r g e n t - b e a m p a t t e r n . T h e
v a r i a t i o n of intensity w i t h i n e a c h disk is a m a p of t h e
w a y intensity varies a s a function of t h e angle b e t w e e n
the incident b e a m a n d t h e crystal s t r u c t u r e . E a c h
p o i n t in t h e disk relates t o electrons incident a t a
distinct o r i e n t a t i o n . It is this intensity v a r i a t i o n w i t h i n
t h e disks o f t h e c o n v e r g e n t - b e a m p a t t e r n t h a t m a k e s
such p a t t e r n s so m u c h m o r e i n f o r m a t i v e t h a n o t h e r
diffraction t e c h n i q u e s .
I n m o s t m o d e r n t r a n s m i s s i o n electron m i c r o s c o p e s ,
it is easy t o o b t a i n such p a t t e r n s ; t h e only r e q u i r e m e n t
is t o be able t o tilt t h e s a m p l e t o line u p t h e c h o s e n
o r i e n t a t i o n of t h e crystal with t h e axis of i l l u m i n a t i o n .
Earlier m i c r o s c o p e s c o u l d n o t p r o d u c e such p a t t e r n s
because they lacked t h e electron optical s t r u c t u r e t o
form the focused p r o b e a n d b e c a u s e c o n t a m i n a t i o n
levels were t o o high.
F u r t h e r details of t h e m i c r o s c o p e o p e r a t i o n t o f o r m
c o n v e r g e n t - b e a m p a t t e r n s c a n be f o u n d in t h e Biblio
graphy.
3.
Applications
3.1 Film-Thickness
Determination
T h e r e a r e m a n y a p p l i c a t i o n s for w h i c h it is necessary
t o k n o w t h e local thickness of t h e a r e a u n d e r o b s e r v a
tion in a n electron m i c r o s c o p e . I n t h e case of crystal
line s a m p l e s , c o n v e r g e n t - b e a m diffraction p r o v i d e s
541
Transmission
Electron
Microscopy:
Convergent-Beam
and
Microdiffraction
Figure 2
An example of a convergent-beam electron diffraction pattern at a zone-axis orientation: the pattern is from V 3Si at the
[110] zone axis taken at an electron-beam energy of 80 kV (courtesy of D. Konitzer)
Figure 3
Convergent-beam pattern from V 3Si at the [111] zone axis at 80 kV taken at a short camera length to show both the
zero-layer reflections and the outer ring that form the first-order Laue zone: note that the zero-layer reflections, near the
center of the pattern, have sixfold symmetry while the first-order ring shows only threefold (courtesy of D. Konitzer)
542
Transmission
Electron
p a t t e r n d i s t o r t i o n s a r e d i s l o c a t i o n s , p l a n a r faults a n d
large v a r i a t i o n s in thickness within t h e electron p r o b e .
Since it frequently h a p p e n s t h a t p h a s e identification is
s o u g h t for small particles of a w k w a r d s h a p e (e.g.,
precipitates in g r a i n b o u n d a r i e s o r grains in a finely
dispersed s t r u c t u r e ) , it m a y n o t b e possible t o o b t a i n
g o o d c o n v e r g e n t - b e a m p a t t e r n s from t h e specimen.
In this case, t h e a p p r o p r i a t e a p p r o a c h is t o p r e p a r e
special s a m p l e s , with large g r a i n s of g o o d crystal, of
those p h a s e s w h o s e presence is suspected. T h e s e
special s a m p l e s c a n b e used t o o b t a i n " s t a n d a r d s e t s "
of z a p s . It is t h e n often possible t o o b t a i n t h e identifi
c a t i o n of t h e p h a s e s b y c o m p a r i n g t h e d i s t o r t e d
p a t t e r n s from t h e specimen with t h e ( u n d i s t o r t e d )
s t a n d a r d sets.
T h i s m e t h o d of identifying p h a s e s is a n i m p o r t a n t
a d d i t i o n t o t h e m o r e u s u a l m e t h o d s of identification
by unit-cell analysis o r by E D X s p e c t r o s c o p y . B o t h of
these latter m e t h o d s a r e subject t o e r r o r a n d a m
biguity. T h e r e a r e m a n y p h a s e s t h a t h a v e similar
lattice p a r a m e t e r s o r lattice p a r a m e t e r s t h a t v a r y w i t h
c o m p o s i t i o n . E D X analysis c a n also be misleading,
especially w h e n t h e particle is e m b e d d e d in a m a t r i x ;
b o t h t h e m a t r i x a n d local c o m p o s i t i o n v a r i a t i o n a t t h e
surface of t h e specimen c a n c o n t r i b u t e t o results t h a t
lead t o e r r o r . F o r these r e a s o n s , t h e initial identifica
tion of a p h a s e , n o t previously seen, s h o u l d b e m a d e
with g r e a t care, using, w h e n e v e r possible, a large
perfect g r a i n o r a g r a i n o n a n e x t r a c t i o n replica r a t h e r
t h a n o n e e m b e d d e d in a m a t r i x . H o w e v e r , o n c e t h e
identification is m a d e , these p r o b l e m s b e c o m e irrele
vant; the c o n v e r g e n t - b e a m p a t t e r n will m a k e a direct
identification.
3.3 Symmetry
Determination
T h e value of k n o w i n g t h e s y m m e t r y of a crystal is n o t
limited t o t h e w a y in w h i c h limiting a search t o o n e
o u t of 230 space g r o u p s aids t h e identification of a
crystal p h a s e . M a n y physical p h e n o m e n a a n d p r o
cesses a r e subject t o c o n s t r a i n t s related t o s y m m e t r y .
T h e n u m b e r of t w i n n i n g m o d e s , t h e n u m b e r of over
g r o w t h v a r i a n t s , t h e m o d e s of p h a s e t r a n s f o r m a t i o n
a n d t h e presence o r a b s e n c e of piezoelectric a n d
pyroelectric effects, for e x a m p l e , all d e p e n d o n t h e
s y m m e t r y of t h e crystal.
Historically, crystal s y m m e t r y h a s been d e t e r m i n e d
by x-ray diffraction b u t this m e t h o d suffers from t w o
limitations: e r r o n e o u s results c a n b e o b t a i n e d if t h e
crystal in q u e s t i o n is f o u n d with a high density of
faults o r twins; a n d n o result a t all c a n be o b t a i n e d if
only a small s a m p l e is available. E l e c t r o n diffraction
o v e r c o m e s these p r o b l e m s . A n electron diffraction
p a t t e r n c a n be o b t a i n e d from a single g r a i n d o w n t o a
few u n i t cells in size a n d , if a crystal h a s faults o r
twins, t h e i m a g e of t h e s a m p l e f o r m e d in t h e i m a g e
m o d e of t h e m i c r o s c o p e allows a defect-free region t o
be c h o s e n t o f o r m t h e diffraction p a t t e r n .
T h e s y m m e t r y of a c o n v e r g e n t - b e a m p a t t e r n a t a
z o n e axis reflects t h e s y m m e t r y of t h e specimen.
Microscopy:
Convergent-Beam
and
Microdiffraction
543
Transmission
Electron
Microscopy:
Convergent-Beam
544
and
Microdiffraction
Transmission
Electron
m e a n s for d e t e r m i n i n g t h e u n i t cell of t h e s t r u c t u r e
from a single p a t t e r n .
A l t h o u g h specimens for t r a n s m i s s i o n electron
m i c r o s c o p y a r e never m o r e t h a n a few h u n d r e d n a n o
m e t e r s thick a n d h e n c e all t r a n s m i s s i o n electron
m i c r o s c o p y uses s a m p l e s in which surface c h a r a c t e r i s
tics are i m p o r t a n t , m o s t studies a r e c o n c e r n e d with
characterizing the " b u l k " material. Convergent-beam
techniques, in p a r t i c u l a r , a r e c o n c e r n e d with t h e
crystal s t r u c t u r e ( a n d its defects) of the infinite crystal
from which t h e s a m p l e is cut.
O n the o t h e r h a n d , as t h e q u a l i t y of t h e v a c u u m in
the i n s t r u m e n t h a s i m p r o v e d , electron m i c r o s c o p y h a s
b e c o m e m o r e a n d m o r e involved in surface studies.
Specimens t h a t h a v e a t o m i c a l l y s m o o t h surfaces c a n
s h o w a n o m a l o u s diffraction effects if their thickness
d o e s n o t c o r r e s p o n d t o a n integer n u m b e r of u n i t cells
(or the w r o n g integer n u m b e r of cells in s o m e cases).
T h e s e effects c a n be used t o i m a g e surface steps, for
example.
N e w h i g h - r e s o l u t i o n electron m i c r o s c o p e s h a v e
m a d e d r a m a t i c c o n t r i b u t i o n s t o surface studies b y
direct i m a g i n g of surfaces seen edge o n . N e w (or
newly revived) reflection surface i m a g i n g t e c h n i q u e s
h a v e s h o w n s p e c t a c u l a r i m a g e s of surface steps,
surface-reconstruction p h a s e t r a n s f o r m a t i o n s a n d
surface defects.
C o n v e r g e n t - b e a m diffraction, t o o , c a n be carried
o u t in a reflection m o d e from surfaces t h a t a r e a t o m i
cally s m o o t h (or nearly so). R e c e n t results suggest
t h a t , as in t r a n s m i s s i o n , surface c o n v e r g e n t - b e a m
p a t t e r n s will p r o v e a powerful tool t h a t is c o m p l e m e n
t a r y t o t h e o t h e r m e t h o d s of surface c h a r a c t e r i z a t i o n
in the electron m i c r o s c o p e .
4.
Conclusion
C o n v e r g e n t - b e a m diffraction is a t e c h n i q u e t h a t h a s
m a n y virtues. It is e x p e r i m e n t a l l y r a t h e r simple a n d
c a n be u n d e r t a k e n o n m o s t m o d e r n m i c r o s c o p e s
w i t h o u t i n s t r u m e n t a l modification. T h e i n f o r m a t i o n
is o b t a i n e d from very small regions of the specimen.
T h e p a t t e r n s a r e very rich in i n f o r m a t i o n . T h e princi
pal a p p l i c a t i o n s (fingerprinting, s y m m e t r y d e t e r m i
n a t i o n , m e a s u r e m e n t of lattice p a r a m e t e r v a r i a t i o n ,
thickness d e t e r m i n a t i o n ) require m i n i m a l , if a n y ,
c o m p u t i n g . Finally, the p a t t e r n s a r e a g r e e a b l e t o
w o r k with b e c a u s e they a r e visually interesting a n d
often beautiful.
cknowledgement
This w o r k w a s s u p p o r t e d by t h e U S D e p a r t m e n t of
Energy. T h i s e n t r y is a revision of a n article in Applied
Surface Science t o w h o m a c k n o w l e d g e m e n t is m a d e .
See also: Electron
Analytical
Diffraction;
Electron
Microscopy,
Microscopy:
Convergent-Beam
and
Microdiffraction
Bibliography
Chemelle P, Ribes A, Portier R, Thomas J 1983 Introduc
tion to some applications of convergent beam electron
diffraction (in French). J. Microsc. Spectrose. Electron. 8:
401-18
Convergent Beam Electron Diffraction of Alloy Phases 1984
by the Bristol Group, compiled by John Mansfield.
Hilger, Bristol, UK
Fraser L 1983 Applications of convergent-beam electron
diffraction to nickel-base superalloys. J. Microsc. Spectrosc. Electron. 8: 431-41
Fung , McKernan S, Steeds J W, Wilson J A 1981
Broken hexagonal symmetry in the locked-in state of
2Ha-TeSe 2, and the discommensurate microstructure of
its incommensurate CDW states. / . Phys. C 14: 5417-32
Goodman P, Olsen A, Whitfield J 1985 Mirror-symmetric
and non-mirror-symmetric glide planes in CuAs-Se, _xSx,l:
a convergent beam electron diffraction study. Ultramic
roscopy 16: 227-32
Jones , Rackham G M, Steeds J W 1977 Higher order
Laue zone effects in electron diffraction and their use in
lattice parameter determination. Proc. R. Soc. London,
Ser. A 354: 197-222
Kaufman J, Fraser L 1984 Characterization of meta
stable crystalline phases in the Al-Ge alloy system. Acta
Metall. 33: 191-203
Kelly , Jostsons A, Blake R G, Napier J G 1975 The
determination of foil thickness by scanning transmission
electron microscopy. Phys. Status Solidi A 31: 771-80
Porter A J, Ecob R C, Ricks R A 1983 Coherency strain
fields: magnitude and symmetry. J. Microsc. 129: 327-36
Spence J C H, Carpenter R W 1986 Electron microdiffrac
tion. In: Joy D C, Romig A D Jr, Goldstein J (eds.)
1986 Principles of Analytical Electron
Microscopy.
Plenum, New York
Steeds J W 1979 Convergent beam electron diffraction. In:
Hren J J, Goldstein J I, Joy D C (eds.) 1979 Introduction
to Analytical Electron Microscopy. Plenum, New York,
pp. 387-422
Steeds J W 1984 Electron crystallography. In: Chapman J
N, Craven A J (eds.) 1984 Quantitative Electron Micros
copy, Scottish Universities Summer School in Physics,
Edinburgh, pp. 49-96
Tanaka M, Saito R, Watanabe D 1980 Symmetry determi
nation of the room-temperature form of L n N b 0 4
(Ln = La, Nd) by convergent-beam electron diffraction.
Acta Crystallogr., Sect. A 36: 350-2
Tanaka M, Sekii H, Nagasawa 1983 Space-groups deter
mination by dynamic extinction in convergent-beam elec
tron diffraction. Acta Crystallogr., Sect. A 39: 825-37
Tanaka M, Terauchi 1985 Convergent-Beam Electron
Diffraction. JEOL, Tokyo
Thomas J, Portier R, Gandais 1983 Introduction to the
theory and practice of convergent beam electron diffrac
tion (in French). J. Microsc. Spectrosc. Electron. 8: 34399
Vincent R, Bird D M, Steeds J W 1984 Structure of AuGeAs
determined by convergent-beam electron diffraction: I,
derivation of basic structure; II, refinement of structural
parameters. Philos. Mag. A 50: 745-86
J. A . E a d e s
[University of Illinois, U r b a n a ,
Illinois, U S A ]
545
Vibrothermography
V i b r o t h e r m o g r a p h y is a n o n d e s t r u c t i v e e v a l u a t i o n
( N D E ) t e c h n i q u e t h a t c a n be used t o locate a n d
identify regions of discontinuities in a variety of
m a t e r i a l s . T h e m e t h o d uses real-time video t h e r m o g
r a p h y t o detect t h e r m a l g r a d i e n t s resulting from t h e
t r a n s f o r m a t i o n of m e c h a n i c a l v i b r a t i o n a l energy i n t o
h e a t . T h e r m o g r a p h y refers t o t h e d e t e c t i o n a n d m a p
p i n g of i s o t h e r m a l c o n t o u r lines o n t h e surface of a
b o d y . R e a l - t i m e video t h e r m o g r a p h y refers t o t h e
detection of infrared r a d i a t i o n from t h e surface, t h e
electronic c o n d i t i o n i n g of t h e received e l e c t r o m a g n e
tic signals a n d t h e display of these as i s o t h e r m a l
c o n t o u r lines o n a c a t h o d e r a y t u b e . V i b r o t h e r m o
g r a p h y is especially useful for t h e d e t e c t i o n of d e l a m i n a t i o n s o r d e l a m i n a t i o n - l i k e d a m a g e in a d v a n c e d
c o m p o s i t e m a t e r i a l s (see Composite Materials:
Non
destructive Evaluation). It h a s , h o w e v e r , s h o w n itself
to be a d a p t a b l e t o h o m o g e n e o u s m a t e r i a l s as well.
T h e m e c h a n i c a l v i b r a t i o n a l energy w h i c h is a p p l i e d
to the material to develop the thermal gradient pat
terns is a m a j o r a t t r i b u t e of t h e t e c h n i q u e . T h e r e a r e
o t h e r w a y s of using t h e r m o g r a p h y t o detect local
thermal conductivity inhomogeneities. F o r example,
the b o d y c a n be h e a t e d externally. T h e r m o g r a p h y will
t h e n detect h o t a n d cold regions c a u s e d b y t h e local
v a r i a t i o n s in t h e r m a l conductivities. H o w e v e r , these
t h e r m a l c o n d u c t i v i t y v a r i a t i o n s m a y b e c a u s e d by a
n u m b e r of effects, such as p h a s e segregation, w h i c h
m a y n o t be related t o d a m a g e d e v e l o p e d b y in-service
l o a d s . T h e benefit of a p p l y i n g m e c h a n i c a l v i b r a t i o n a l
energy t o t h e specimen is t h a t this energy will i n t e r a c t
with localized regions of d a m a g e , c a u s i n g preferential
t r a n s f o r m a t i o n of h e a t w h i c h is d e t e c t a b l e by t h e r m o
g r a p h y . Since t h e m e c h a n i c a l s t r e n g t h , stiffness a n d
life of a n y s t r u c t u r a l c o m p o n e n t a r e ultimately affec
ted by t h e stress state existing inside t h e b o d y , a n
N D E m e t h o d w h i c h c a n directly o r indirectly react t o
the internal stress s t a t e will be m o r e responsive t o t h e
m e c h a n i c a l state of t h e m a t e r i a l . I n o t h e r w o r d s ,
v i b r o t h e r m o g r a p h y is a n N D E m e t h o d w h i c h is dir
ectly responsive t o t h e stress state in t h e m a t e r i a l
while o t h e r t e c h n i q u e s for establishing t h e r m a l g r a d i
ents a r e n o t .
1. Description
of
Technique
V i b r o t h e r m o g r a p h y is a n active N D E m e t h o d . T h a t
is, s o m e external s o u r c e of energy m u s t be a p p l i e d t o
t h e b o d y in o r d e r for t h e N D E t e c h n i q u e t o be able t o
detect the d a m a g e d o r flawed regions existing in t h e
m a t e r i a l . S u c h t e c h n i q u e s a r e distinguished from p a s
Vibrothermography
548
2.
Applications
V i b r o t h e r m o g r a p h y h a s been applied t o t h e d e t e c t i o n
of d a m a g e in b o t h h o m o g e n e o u s a n d c o m p o s i t e
m a t e r i a l s . T h i s is a u n i q u e t h e r m o g r a p h i c t e c h n i q u e
in t h a t t h e h e a t o b s e r v e d is p r o d u c e d b y the specimen
r a t h e r t h a n b y a n o u t s i d e source. T h e h e a t so p r o
d u c e d is p r o p o r t i o n a l t o t h e m e c h a n i c a l energy dissi
p a t e d b y t h e m a t e r i a l a t e a c h p o i n t . T h e energy
dissipated, in t u r n , is p r o p o r t i o n a l t o t h e level of
stress a t t h a t p o i n t . I n a d d i t i o n , it s h o u l d b e n o t e d
t h a t t h e h e a t d e v e l o p m e n t will d e p e n d o n t h e inte
g r a t e d , o r c o m p l e t e , state of d a m a g e in t h e m a t e r i a l .
H e n c e , it s h o u l d b e possible t o o b s e r v e t h e severity
a n d d i s t r i b u t i o n of d a m a g e in a b o d y b y observing t h e
severity a n d d i s t r i b u t i o n of stress indicated by t h e
heat pattern.
A s a n illustration of this, o n e m i g h t n o t e t h a t m a n y
real m a t e r i a l s h a v e n o b o u n d a r i e s of m a t e r i a l p h a s e s
w h i c h exist o n a scale large e n o u g h t o influence
significantly engineering b e h a v i o r . H e n c e it is r e a s o n
able t o call these m a t e r i a l s h o m o g e n e o u s o n t h e
m a c r o s c o p i c level. A l t h o u g h these m a t e r i a l s m a y h a v e
p h a s e b o u n d a r i e s a t t h e m i c r o level, u n d e r v i b r a t o r y
excitation, t h e m a c r o s c o p i c h e a t p a t t e r n p r o d u c e d in
a n unflawed, h o m o g e n e o u s plate is u n i f o r m a n d cor
r e s p o n d s t o w h a t is called a h o m o g e n e o u s state of
stress. W h e n a d i s c o n t i n u i t y such a s a hole, n o t c h o r
c r a c k is p r e s e n t , t h e stress field also b e c o m e s n o n u n i
f o r m a n d t h e o b s e r v e d h e a t p a t t e r n indicates t h e s a m e
t y p e of c h a n g e . F i g u r e 1 s h o w s t h e d i s t r i b u t i o n of
h y d r o s t a t i c stress a r o u n d a circular h o l e in a finite
p l a t e ; F i g . 2 is t h e c o r r e s p o n d i n g d i a g r a m for inp l a n e s h e a r stress. A v i b r o t h e r m o g r a p h i c p i c t u r e w a s
o b t a i n e d for a m e t h y l m e t h a c r y l a t e p l a t e , 25 m m wide
by 175 m m l o n g b y 6.25 m m thick with a 6.25 m m
center h o l e . T h i s p l a t e w a s l o a d e d in a s e r v o h y d r a u l i c
testing frame a t a m a x i m u m of 5 0 % of the u l t i m a t e
l o a d a n d a t a frequency of 30 H z . T h e i s o t h e r m
p a t t e r n t r a c e d from t h e t h e r m o g r a p h i c p i c t u r e is
s h o w n in Fig. 3. A c o m p a r i s o n of Figs. 1 a n d 2 with 3
strongly suggests t h a t t h e h e a t p a t t e r n is r e p r e s e n t a
tive of t h e stress d i s t r i b u t i o n in t h e plate. T h e very
close similarity b e t w e e n Figs. 2 a n d 3 especially
suggests t h a t t h e s h e a r stress in this case is m o r e
i m p o r t a n t in g e n e r a t i n g t h e h e a t energy t h a n is the
hydrostatic component.
V i b r o t h e r m o g r a p h y h a s b e e n applied t o c o m p o s i t e
m a t e r i a l s with excellent results. T h e m e t h o d h a s
p r o v e d itself t o be m o s t useful in detecting the early
f o r m a t i o n of d a m a g e d u r i n g t h e fatigue testing of
c o m p o s i t e s a n d in detecting
delamination-like
d a m a g e in c o m p o s i t e s w h e n t h e l o w - a m p l i t u d e , highfrequency excitation m e t h o d is e m p l o y e d . T h e basic
m e c h a n i s m s of fatigue d a m a g e in a d v a n c e d c o m p o
site m a t e r i a l s a r e q u i t e different from t h a t in h o m o
g e n e o u s m a t e r i a l s . I n s t e a d of t h e initiation of a
fatigue c r a c k a n d its p r o p a g a t i o n in a self-similar
fashion, as o c c u r s in h o m o g e n e o u s m a t e r i a l s , fatigue
Vibrothermography
Figure 3
Isothermal contours traced from thermographic picture of
methyl methacrylate plate fatigue loaded at 30 Hz
Figure 1
Distribution of hydrostatic stress component around a
hole in a finite-sized plate
Figure 2
Distribution of in-plane shear stress component around a
hole in a finite-sized plate (after Talug et al. 1979)
d a m a g e in c o m p o s i t e s consists of v a r i o u s c o m
b i n a t i o n s of m a t r i x c r a c k i n g , fiber m a t r i x d e b o n d i n g ,
d e l a m i n a t i o n , void g r o w t h a n d local fiber b r e a k a g e . A
t e c h n i q u e t o detect a n d m o n i t o r nondestructively
d a m a g e d e v e l o p m e n t in c o m p o s i t e s m u s t be c a p a b l e
of assessing t h e c o m b i n e d effect of t h e n u m e r o u s
d a m a g e m o d e s w h i c h f o r m t h e d a m a g e state. T h e
v i b r o t h e r m o g r a p h i c t e c h n i q u e h a s p r o v e d itself t o be
directly a p p l i c a b l e t o detecting d a m a g e initiation a n d
t o m o n i t o r i n g d a m a g e g r o w t h in c o m p o s i t e s since a
large p e r c e n t a g e of t h e energy released d u r i n g the
d a m a g e processes is c o n v e r t e d t o h e a t . In b o r o n
e p o x y c o m p o s i t e m a t e r i a l , for e x a m p l e , v i b r o
t h e r m o g r a p h y detected, q u i t e early in t h e fatigue test,
local h o t s p o t s in t h e b o d y ( M a r c u s a n d S t i n c h c o m b
1975). W h e n t h e test w a s m o m e n t a r i l y h a l t e d , n o
evidence of d a m a g e c o u l d b e f o u n d by o t h e r m e a n s .
O n r e s t a r t i n g t h e fatigue test, t h e h o t s p o t s r e a p
p e a r e d a n d after m a n y m o r e a d d i t i o n a l l o a d cycles,
o n e w a s finally able t o detect d e v e l o p i n g d a m a g e in
t h e s a m e l o c a t i o n s as t h e h o t regions. O t h e r w o r k , in
graphite epoxy material, has shown that vibrothermo
g r a p h y c a n be used t o m e a s u r e d a m a g e g r o w t h rates
in real t i m e ( H e n n e k e et al. 1979). In this instance, t h e
local h o t s p o t s d e v e l o p e d a r o u n d a n o t c h t h a t w a s
m a c h i n e d in t h e specimen initially, a n d m o v e d with
t h e d a m a g e a s it p r o g r e s s e d a n d grew a w a y from the
notch.
F o r t h e d e t e c t i o n of d a m a g e t h a t a l r e a d y exists in a
specimen d u e t o m a n u f a c t u r i n g defects o r p r e v i o u s
l o a d i n g h i s t o r y , t h e l o w - a m p l i t u d e , high-frequency
m o d e of excitation h a s p r o v e d t o b e very g o o d in
locating delaminations or delamination-like damage
in c o m p o s i t e s . T h i s m o d e of excitation, as n o t e d
earlier, d o e s n o t a d d t o t h e m e c h a n i c a l d a m a g e
a l r e a d y existing in t h e b o d y . A n interesting effect of
549
Vibrothermography
t h e t h r e e w h i t e s p o t s a c r o s s t h e w i d t h of t h e specimen
j u s t b e l o w t h e h o r i z o n t a l center line of the p i c t u r e .
T h e h o l e itself is barely visible as t h e gray region j u s t
b e l o w t h e line of t h e t h r e e w h i t e s p o t s . T h e interesting
t h i n g a b o u t this t h e r m o g r a p h is t h e large h o t region,
i n d i c a t e d b y t h e large w h i t e a r e a o n t h e u p p e r righth a n d side of t h e specimen. T h i s region d e l a m i n a t e d
internally as a result of t h e l o a d i n g applied t o the
specimen. W h i l e t h e m a t c h s t i c k fracture w a s visible t o
t h e eye, this d e l a m i n a t e d region w a s n o t , a n d if it were
n o t for t h e v i b r o t h e r m o g r a p h y t e c h n i q u e , this w o u l d
have gone unnoticed.
T h e v i b r o t h e r m o g r a p h y t e c h n i q u e is also appli
cable t o m o r e c o m p l e x specimen geometries t h a n the
plates previously discussed. T h e t e c h n i q u e h a s been
applied t o full-size helicopter r o t o r blades m a d e from
c o m p o s i t e m a t e r i a l s , m u l t i b l a d e d r o t o r s used in air
c o m p r e s s o r s , a n d a u t o m o b i l e d o o r s . I n e a c h case,
t h e r m a l g r a d i e n t s d e v e l o p e d in regions w h e r e stress
c o n c e n t r a t i o n s existed d u e t o i n t e r n a l defects, d a m a g e
o r o t h e r stress raisers. H e n c e , it a p p e a r s t h a t t h e
v i b r o t h e r m o g r a p h y t e c h n i q u e will lend itself t o field
use as well as t o l a b o r a t o r y investigations.
See also: Stress Distribution: Analysis Using Thermoelastic
Effect
Bibliography
Figure 4
Thermograph of boron epoxy composite plate
550
w
Wood: Acoustic Emission and
Acousto-UItrasonic Characteristics
A c o u s t i c emission ( A E ) a n d a c o u s t o - u l t r a s o n i c s ( A U )
a r e useful t e c h n i q u e s for d e t e r m i n i n g t h e integrity of
w o o d a n d w o o d - b a s e d m a t e r i a l s . A c o u s t i c emission
arises from m a t e r i a l u n d e r stress a n d c a n b e sensed
with piezoelectric t r a n s d u c e r s , usually c o u p l e d t o t h e
surface of t h e m a t e r i a l . M a t e r i a l s c o n t a i n i n g flaws o r
w e a k a r e a s g e n e r a t e A E a t lower stress levels t h a n
t h o s e of g r e a t e r integrity. A U c o m b i n e s t h e sensitivity
of A E t r a n s d u c e r s w i t h u l t r a s o n i c t r a n s m i t t e r s t o
e v a l u a t e t h e c h a n g e in energy c o n t e n t of a signal a s it
passes t h r o u g h t h e m a t e r i a l . I n general, a decrease in
energy c o n t e n t signifies less m a t e r i a l integrity. A E h a s
been used w i t h w o o d - b a s e d m a t e r i a l s since t h e 1960s;
A U , w h i c h h a s b e e n in f o r m a l existence since t h e late
1970s, h a s only recently b e e n used. T h e a p p l i c a t i o n of
A E and A U to wood-based materials has been sub
stantially a i d e d b y d e v e l o p m e n t s in assessing t h e
integrity of fiber-reinforced plastics ( F R P s ) , w h i c h
h a v e m a n y characteristics similar t o t h o s e of w o o d .
F R P s , like w o o d , r e q u i r e special t e c h n i q u e s t o detect
i n t e r n a l flaws, in c o n t r a s t t o m e t a l s w h e r e x-ray
t e c h n i q u e s a r e usually sufficient.
W o o d - b a s e d m a t e r i a l s h a v e A E characteristics
similar t o t h o s e of fiber-reinforced c o m p o s i t e s . S o m e
indications of w e a k e r ( o r w e a k e n e d ) m a t e r i a l o r s t r u c
t u r e a r e emissions a t low stress levels, a n d increased
n u m b e r s a n d / o r r a t e s of events. A n o t h e r i n d i c a t o r of
w e a k e n e d m a t e r i a l is a low Felicity r a t i o , w h i c h is
d e t e r m i n e d f r o m a s e q u e n c e of l o a d / u n l o a d cycles
d u r i n g w h i c h A E is m o n i t o r e d . I n s o m e m a t e r i a l s , n o
A E o c c u r s d u r i n g r e l o a d i n g until t h e p r e v i o u s stress is
r e a c h e d , giving a l o a d r a t i o (Felicity r a t i o ) of u n i t y
(this is referred t o as t h e K a i s e r effect). H o w e v e r ,
m a n y m a t e r i a l s , such a s c o m p o s i t e s , h a v e a Felicity
r a t i o of less t h a n u n i t y , n o t o b e y i n g t h e K a i s e r effect.
A c o u s t o - u l t r a s o n i c s differs f r o m A E in t h a t a n
active pulser is used t o inject stress w a v e s t h a t a r e
received b y c o n v e n t i o n a l A E sensors, a n d t h e result
ing w a v e f o r m is a n a l y z e d t o d e t e r m i n e t h e c h a n g e
in signal c o n t e n t from p u l s e r t o sensor. A U differs
from c o n v e n t i o n a l u l t r a s o n i c t e c h n i q u e s in t h a t m o r e
subtle flaws, such as p o o r - q u a l i t y b o n d i n g , c a n b e
detected. I n m o s t a p p l i c a t i o n s , t h e p u l s i n g e l e m e n t is
also a c o n v e n t i o n a l A E sensor t h a t is energized w i t h a
n a r r o w , h i g h - v o l t a g e pulse, b u t o t h e r m e a n s of sur
face s t i m u l a t i o n c a n b e used, i n c l u d i n g m e c h a n i c a l
i m p a c t , laser b u r s t s a n d electrical discharges.
1. Acoustic
Properties
1
Typical u l t r a s o n i c velocities a r e 1 k r n s " a c r o s s t h e
_1
grain and 5 k m s
a l o n g t h e g r a i n for l u m b e r a n d
veneer. R e c o n s t i t u t e d m a t e r i a l s s u c h a s c o m p o s i t e
p a n e l s h a v e velocities similar t o solid w o o d a c r o s s t h e
g r a i n . W o o d - b a s e d m a t e r i a l s a r e a b o u t a n o r d e r of
m a g n i t u d e g r e a t e r in a t t e n u a t i o n t h a n geological
m a t e r i a l s a n d t w o o r d e r s of m a g n i t u d e g r e a t e r t h a n
m e t a l s . A t t e n u a t i o n in w o o d is m u c h g r e a t e r across
t h a n a l o n g t h e g r a i n . Because of these differences, A E
s e n s o r p o s i t i o n i n g is critical, p a r t i c u l a r l y for solid
w o o d w h e r e t h e g r a i n direction is well defined.
Since a t t e n u a t i o n increases e x p o n e n t i a l l y w i t h fre
q u e n c y , t h e u s a b l e u p p e r frequency level for sensors
o n w o o d - b a s e d m a t e r i a l s is a b o u t 100-200 k H z . I n
this frequency r a n g e , a t t e n u a t i o n a l o n g a n d a c r o s s t h e
_1
1
a n d 200 d B m , respect
g r a i n is a b o u t 3 0 d B m
ively. T h e effects of w o o d density a n d m o i s t u r e c o n
t e n t o n a t t e n u a t i o n h a v e n o t b e e n clearly d e t e r m i n e d ,
b u t a p p e a r t o b e of lower o r d e r as c o m p a r e d with
g r a i n angle. O b v i o u s l y , t h e m o r e a t t e n u a t i n g t h e
m a t e r i a l , t h e g r e a t e r t h e limit o n sensitivity. H o w e v e r ,
t h e m o r e a t t e n u a t i n g m a t e r i a l s h a v e a n a d v a n t a g e in
d a m p i n g o u t e x t e r n a l u n w a n t e d signals, p e r m i t t i n g
t h e use of higher gains t o o b t a i n t h e n e e d e d sensiti
vity. A t t e n u a t i o n also results f r o m g e o m e t r i c s p r e a d
ing of t h e signal as it travels t h r o u g h t h e m a t e r i a l ; for
p l a n a r m a t e r i a l s , a t t e n u a t i o n is p r o p o r t i o n a l t o the
d i s t a n c e f r o m t h e s o u r c e , a n d for b u l k m a t e r i a l s , t o
t h e s q u a r e of t h e d i s t a n c e . F o r w o o d - b a s e d m a t e r i a l s ,
t h e g e o m e t r i c s p r e a d i n g m a y b e a n i s o t r o p i c because
of t h e g r a i n direction effect.
2. Coupling
of Transducers
to
Wood-Based
Materials
A c o u s t i c i m p e d a n c e (the p r o d u c t of velocity a n d
d e n s i t y ) is t h e d e t e r m i n i n g p a r a m e t e r for acoustic
c o u p l i n g of o n e m a t e r i a l t o a n o t h e r . F o r w o o d a l o n g
t h e g r a i n , a c o u s t i c i m p e d a n c e is similar t o t h a t of
m e t a l s ; a c r o s s t h e g r a i n it is c o m p a r a b l e t o plastics
a n d w a t e r . C o u p l i n g p r e s e n t s t h e greatest source of
variability a n d t h e m a j o r i m p e d i m e n t t o on-line
i m p l e m e n t a t i o n of A E o r A U in processing w o o d b a s e d m a t e r i a l s . F o r A E l a b o r a t o r y studies, c o u p l i n g
is generally effected u s i n g either a c o u p l a n t (grease
type) o r b y b o n d i n g t h e sensor t o t h e m a t e r i a l . Special
p r o b l e m s in c o u p l i n g t o w o o d - b a s e d m a t e r i a l s include
p o r o s i t y a n d r o u g h n e s s of t h e surface. Because of this,
grease-type c o u p l a n t s a r e very difficult t o use w i t h o u t
t h e m b e i n g forced i n t o t h e m a t e r i a l ; this c h a n g e s t h e
p r e s s u r e a t t h e face of t h e sensor. B o n d e d c o u p l i n g
w i t h c o n t a c t o r h o t m e l t adhesives c a n b e used t o
o v e r c o m e such p r o b l e m s . B o n d e d c o u p l i n g will
usually give a b o u t a 3 d B increase in efficiency over
551
Wood:
Acoustic
Emission
and Acousto-Ultrasonic
c o u p l a n t s because of transfer of t h e s h e a r - w a v e c o m
p o n e n t . B o n d i n g m u s t be used c a u t i o u s l y since differ
ential e x p a n s i o n of t h e b o n d e d interfaces c a n c a u s e
failure within t h e b o n d o r g e n e r a t e stresses t h a t m i g h t
cause e x t r a n e o u s A E . F o r m a n y A U a p p l i c a t i o n s , t h e
surface m u s t b e s c a n n e d , w h i c h c a n be d o n e t h r o u g h
d r y c o u p l i n g using rigid o r e l a s t o m e r i c m a t e r i a l s ,
w h e r e c o u p l i n g p r e s s u r e m u s t be high e n o u g h t o
" s q u e e z e " o u t air g a p s a n d m a i n t a i n consistent local
pressure o n t h e m a t e r i a l . F o r b o t h A E a n d A U , m o s t
on-line uses involve m a t e r i a l s t h a t a r e m o v i n g ,
generally r e q u i r i n g a d r y c o u p l i n g system a n d a d d i n g
considerable c o m p l e x i t y in s e n s o r / c o u p l i n g design.
D r y c o u p l i n g i n t r o d u c e s a loss of a b o u t 2 0 - 3 0 d B (at
7 0 k P a ) , which c a n be r e d u c e d t o a b o u t 10 d B with
increased pressure (300 k P a ) . Alternatively, b u t with
s o m e risk with h y g r o s c o p i c m a t e r i a l s , c o u p l i n g c a n b e
achieved b y using a w a t e r mist a t t h e c o n t a c t a r e a .
3. Defect
Location
L o c a t i o n of t h e origin of A E emissions c a n be a c c o m
plished by using m u l t i p l e sensors a n d m e a s u r i n g time
of arrival of the s a m e event. W i t h t w o sensors, t h e
definition of l o c a t i o n is limited t o a p l a n e p e r p e n d i c u
lar t o t h e line b e t w e e n t h e sensors. T h e a d d i t i o n of
m o r e sensors p e r m i t s m o r e precise definition of t h e
origin, a s s u m i n g t h a t t h e m a t e r i a l is r e a s o n a b l y
h o m o g e n e o u s a n d t h e event r a t e is n o t t o o high t o
distinguish b e t w e e n events. F o r solid w o o d , t h e rela
t i o n s h i p of velocity t o g r a i n o r i e n t a t i o n a n d t h e high,
a n i s o t r o p i c a t t e n u a t i o n r e q u i r e special p r e c a u t i o n s in
sensor l o c a t i o n a n d i n t e r p r e t a t i o n of time intervals.
S o m e of t h e m o r e nearly i s o t r o p i c w o o d - b a s e d c o m
posites, such as certain types of fiberboard a n d p a r t i c
l e b o a r d , p e r m i t g o o d l o c a t i o n r e s o l u t i o n . In c o n t r a s t ,
p l y w o o d presents special p r o b l e m s from b o t h t h e
grain o r i e n t a t i o n of t h e plies a n d b o u n d a r i e s b e t w e e n
plies. O r i e n t e d s t r a n d b o a r d s h o u l d b e h a v e i n t e r m e
diately b e t w e e n p a r t i c l e b o a r d a n d p l y w o o d .
4.
Applications
A l t h o u g h there a r e a limited n u m b e r of e x a m p l e s of
direct a p p l i c a t i o n of A E a n d A U in q u a l i t y assess
ment (QA) and quality control (QC), a substantial
research effort is u n d e r w a y t h a t will p r o v i d e t h e
b a c k g r o u n d for d e v e l o p m e n t of further industrial
systems for n o n d e s t r u c t i v e e v a l u a t i o n a n d testing.
T h e r e p o r t e d research in A E a n d A U for w o o d - b a s e d
m a t e r i a l s c a n be placed in four m a j o r categories:
fracture/fracture m e c h a n i c s , d r y i n g (as m o n i t o r e d b y
f o r m a t i o n of checks), decay a n d m a c h i n i n g . O n l y t h e
first c a t e g o r y lacks c u r r e n t Q C / Q A efforts. A l t h o u g h
a b o u t 5 0 % of the r e p o r t e d research h a s been in
fracture/fracture m e c h a n i c s , a m a j o r a r e a of e m p h a s i s
since 1980 h a s been in w o o d drying. T h e m o s t recent
552
Characteristics
Wood:
Acoustic
clearer s e p a r a t i o n of t h e c o n t r i b u t i n g s o u r c e t h a n if
considering only M O R . T e n s i o n fatigue h a s b e e n
observed t o c a u s e a n e x p o n e n t i a l increase of A E w i t h
cycles; the c o n t r i b u t i o n of A E from l o a d i n g a n d
u n l o a d i n g , h o w e v e r , w a s n o t eliminated.
C l e a r specimens stressed in flexure g e n e r a t e c o m
p a r a b l y little A E until n e a r t h e u l t i m a t e stress, in
c o n t r a s t t o high activity in m a t e r i a l c o n t a i n i n g d e
fects. T h e initiation a n d p r o p a g a t i o n of failures c a n
be detected by u s i n g l o c a t i o n t e c h n i q u e s w i t h t w o o r
m o r e sensors. T h e initiation of flaws in b o t h l a b o r a
t o r y a n d full-size specimens c a n b e c o r r e l a t e d with t h e
location of n a t u r a l o r artificial defects.
4.2
Composites
W o o d - b a s e d c o m p o s i t e m a t e r i a l s emit A E a t s u b s t a n
tially lower stress levels t h a n o c c u r s with solid w o o d .
F o r e x a m p l e , in static b e n d i n g tests, c o m p o s i t e m a t e r
ials begin emissions a t a b o u t 1 0 - 2 0 % of t h e u l t i m a t e
stress, w h e r e a s clear solid w o o d begins a t a b o u t 4 0 5 0 % . T h e smaller t h e c o n s t i t u e n t particle in t h e
b o a r d , the higher t h e stress level of initial emissions.
In A E m o n i t o r i n g d u r i n g i n t e r n a l b o n d (IB) tests o n
c o m p o s i t e s , a clear r e l a t i o n s h i p w a s f o u n d b e t w e e n
one-half of t h e t o t a l events a n d u l t i m a t e stress. I n
p a r t i c l e b o a r d with c o n t r o l l e d resin levels, t o t a l events
t o failure c o r r e l a t e d w i t h resin level. A l s o , A E d a t a
correlated m u c h b e t t e r w i t h I B values t h a n d i d speci
m e n density. S o m e limited d a t a indicate a high c o r r e
lation of A E w i t h A U m e a s u r e d b y t r a n s m i s s i o n . T h e
Felicity r a t i o of p a r t i c l e b o a r d a p p e a r s t o b e r e a s o n
ably c o n s t a n t (at a b o u t 0.9) u p t o failure.
A E h a s b e e n m e a s u r e d from i n t e r n a l microfailures
d u r i n g t h e thickness swelling of p a r t i c l e b o a r d a t high
relative h u m i d i t y . T h e active p e r i o d of A E coincides
with irreversible swelling ( s p r i n g b a c k ) . W o o d - f i b e r
h a r d b o a r d with c o n t r o l l e d p r e t r e a t m e n t s tested in
c o m p r e s s i o n n o r m a l t o t h e face p r o d u c e d c u m u l a t i v e
A E t h a t c o r r e l a t e d well w i t h thickness swelling from
boil-swell tests, i n d i c a t i n g t h a t c u m u l a t i v e A E m a y b e
a g o o d n o n d e s t r u c t i v e p r e d i c t o r of d i m e n s i o n a l stabi
lity. W h e n t h e s a m e t y p e of m a t e r i a l s were subjected
t o cyclic w a t e r - s o a k e x p o s u r e , stress-wave factor
( S W F ) values decreased with increasing n u m b e r s of
cycles, c o r r e s p o n d i n g t o increasing d a m a g e . H o w
ever, u n d a m a g e d b o a r d s w i t h h i g h e r S W F h a d lower
thickness swelling, suggesting t h a t S W F c o u l d p r e d i c t
the degree of d i m e n s i o n a l stability.
4.3
Machining
A E characteristics h a v e been d e t e r m i n e d for c u t t i n g
o p e r a t i o n s t h a t a p p r o x i m a t e veneer peeling. T h e
p r i m a r y s o u r c e of A E w a s f o u n d t o b e c h a n g e s in
plastic d e f o r m a t i o n in t h e s h e a r z o n e a t t h e tip of t h e
c u t t i n g t o o l . T h e A E c o u n t r a t e , while n o t well
correlated with c u t t i n g forces, w a s m o r e sensitive t o
the c u t t i n g p r o c e s s t h a n t h e r m s signal. T h e A E
output was considered potentially m o r e important to
m o n i t o r tool w e a r t h a n c u t t i n g forces. T h i s w o r k h a s
Emission
and Acousto-Ultrasonic
Characteristics
been e x t e n d e d t o p r e l i m i n a r y tests o n m o n i t o r i n g A E
from circular saw c u t t i n g , using several types of
coupling attachments to the blade.
4.4 Drying and Drying
Control
O n e of t h e m o r e p r o m i s i n g a p p l i c a t i o n s of A E is for
m o n i t o r i n g a n d c o n t r o l l i n g t h e d r y i n g process of
l u m b e r . A E h a s b e e n used t o sense t h e d e v e l o p m e n t of
surface checks in b o t h h a r d w o o d s a n d softwoods.
T h e a c t u a l fracture of t h e surface h a s been directly
o b s e r v e d s i m u l t a n e o u s l y w i t h A E emissions. By c o n
trolling t h e e n v i r o n m e n t a l c o n d i t i o n s t o p r e v e n t high
r a t e s of emissions, it is possible t o d r y faster with less
d e g r a d a t i o n . Several investigators h a v e d e m o n s t r a t e d
t h e feasibility of c o n t r o l l i n g c h e c k i n g d u r i n g h a r d
w o o d d r y i n g b y using a fixed level of A E t o c o n t r o l
d r y i n g c o n d i t i o n s . H a r d w o o d s generally check m u c h
m o r e readily t h a n s o f t w o o d s a n d c o n s e q u e n t l y h a v e
A E r a t e s a b o u t a n o r d e r of m a g n i t u d e greater. H o w
ever, a m o n g h a r d w o o d s , t h e r e d o e s n o t a p p e a r t o be a
g o o d c o r r e l a t i o n b e t w e e n p r o p e n s i t y t o check a n d A E
r a t e . A E h a s been s h o w n t o r e s p o n d r a p i d l y t o
c h a n g i n g surface R H c o n d i t i o n s , i n d e p e n d e n t of
w h e t h e r e n d grain o r side g r a i n is e x p o s e d . G e o m e t r y
c a n h a v e a large effect o n A E g e n e r a t i o n , d e p e n d i n g
o n t h e direction of m o i s t u r e m o v e m e n t a n d t h e degree
of stress d e v e l o p m e n t . T h e r e is s o m e evidence t h a t A E
d u r i n g d r y i n g also originates from fracture of w a t e r
capillaries, a n a l o g o u s t o A E from w a t e r stress in
plants.
4.5 Biological
Degradation
553
Wood: Acoustic
Emission
and Acousto-Ultrasonic
Bibliography
Ansell 1982 Acoustic emission from softwoods in
tension. Wood Sci. Technol. 16: 35-58
Beall F C 1985 Relationship of acoustic emission to internal
bond strength of wood-based composite panel materials.
J. Acoust. Emission 4(1): 19-29
Beall F C 1986 Effect of moisture conditioning on acoustic
emission from particleboard. J. Acoust. Emission 5(2): 7
554
Characteristics
X-Ray Absorption Spectroscopy:
EXAFS and XANES Techniques
X - r a y spectroscopies, in v a r i o u s forms, h a v e l o n g
been exploited for s t u d y i n g t h e electronic a n d crystallographic s t r u c t u r e of solids. M o s t extensively uti
lized, of c o u r s e , a r e diffraction t e c h n i q u e s e m p l o y e d
for the p u r p o s e of e x t r a c t i n g c r y s t a l l o g r a p h i c infor
m a t i o n . H o w e v e r , x-ray a b s o r p t i o n studies a r e cur
rently experiencing a s t r o n g surge of scientific interest
resulting from recent i m p o r t a n t a d v a n c e s , b o t h in
theoretical u n d e r s t a n d i n g a n d in e x p e r i m e n t a l c a p a
bility. E x p e r i m e n t a l l y , t h e E X A F S (extended x-ray
a b s o r p t i o n fine structure) a n d X A N E S (x-ray a b s o r p
tion near-edge fine s t r u c t u r e ) techniques a r e dis
tinguished simply b y their spectral r a n g e s ( m e a s u r e d
relative t o a n x-ray a b s o r p t i o n edge). T h e distinction
is m a d e since x-ray-induced electronic excitations in
the vicinity of t h e edge involve c o n s i d e r a t i o n s t h a t a r e
s o m e w h a t different from t h e m o r e energetic p r o
cesses. Oscillatory s t r u c t u r e in t h e x-ray a b s o r p t i o n
coefficient t h a t m a y b e o b s e r v e d in t h e higher spectral
r a n g e (40 eV ^ hv ^ 1000 eV a b o v e t h e edge) is called
E X A F S , while X A N E S refers t o t h e s t r u c t u r e in t h e
i m m e d i a t e vicinity of t h e edge (i.e., for hv ^ 50 eV
a b o v e t h e edge). T h e s e x-ray a b s o r p t i o n t e c h n i q u e s
h a v e u n i q u e capabilities a n d a r e being used t o s t u d y a
wide variety of c o m p l e x m a t e r i a l s . Studies of a m o r
p h o u s m a t e r i a l s , catalysts, biological m a t e r i a l s a n d
solutions h a v e been r e p o r t e d .
I n this article, t h e u n d e r l y i n g theoretical c o n c e p t s
of E X A F S a n d X A N E S a r e outlined a n d recent
experimental a d v a n c e s a r e discussed. A d v a n t a g e s a n d
limitations of t h e x-ray a b s o r p t i o n spectroscopies,
a n d types of p r o b l e m s m o s t suited for these tech
niques, will b e discussed. M o r e detailed discussions
are available in literature reviews, a n d t h e extensive
review b y Lee et al. (1981) is particularly r e c o m
m e n d e d t o t h e interested reader.
1. Theory
and Comparison
with
()\(/\}\ ()
*(*) = Z^jH)f(k)sm[2krj
)]
j
2
(2)
1.6,-
Experiment
W i t h i n t h e electric dipole a p p r o x i m a t i o n , t h a t p a r t of
the a b s o r p t i o n coefficient resulting from p h o t o e m i s sion from a core state is given b y
2
0.7h
0)
8500
9000
Energy
(eV)
Figure 1
The absorption coefficient (multiplied by the thickness
JC) of nickel as a function of energy at 38
555
X-Ray
Absorption
Spectroscopy:
EXAFS
and XANES
Ac
(b)
Figure 2
(a) The EXAFS spectrum, kx{k) vs k, and (b) the radial
distribution function, ^(r) vs r, for nickel at 38 K. The
numbers in parentheses are the number of atoms per shell,
indicated at the known shell distances
w h e r e r} is t h e d i s t a n c e from t h e c e n t r a l ( a b s o r b e r )
a t o m t o t h e yth shell of a t o m s , Nj is t h e n u m b e r of
a t o m s in the shell, is a D e b y e - W a l l e r - l i k e factor
which m e a s u r e s t h e a i s o r d e r of t h e a t o m s in t h e yth
shell relative t o t h e central a t o m a n d is a m e a n free
p a t h , e s t i m a t e d t o be 3.5-5 A. T h e a m p l i t u d e function
ffi) a n d t h e p h a s e function ) c a n be calculated
theoretically o r d e t e r m i n e d empirically from c o m
p o u n d s of k n o w n s t r u c t u r e . I n principle, therefore,
the p a r a m e t e r s Np rp cr, a n d c a n b e d e t e r m i n e d
for the first few n e a r - n e i g h b o r shells. I n practice,
however, there a r e limits o n t h e n u m b e r of p a r a m e t e r s
t h a t c a n be i n d e p e n d e n t l y d e t e r m i n e d a n d also o n t h e
a c c u r a c y of t h e d e t e r m i n a t i o n s . In m a n y cases, dis
tances between the central a t o m a n d t h e first shell of
s u r r o u n d i n g n e i g h b o r s in a n u n k n o w n m a t e r i a l c a n
be d e t e r m i n e d t o 0 . 0 1 A, a n d t h e n u m b e r of first
n e a r n e i g h b o r s c a n be m e a s u r e d t o b e t t e r t h a n 2 0 %
accuracy.
Analysis of E X A F S spectra is c o n s i d e r a b l y a i d e d
by calculating t h e F o u r i e r t r a n s f o r m of kx(k).
Because of the special form of E q n . (2), t h e F o u r i e r
t r a n s f o r m of kx(k) is a p a r t i c u l a r l y useful inter
p r e t a t i o n . T h e t r a n s f o r m #?(r) is a r a d i a l - d e p e n d e n t
function t h a t a p p r o x i m a t e l y m e a s u r e s the spatial dis
t r i b u t i o n of b a c k s c a t t e r i n g a t o m s relative t o t h e cen
556
Techniques
(A)
Figure 3
The uranium L-edge radial-distribution function, <p(R) vs
R, for a 0.02 molar uranium aqueous solution
X-Ray
Absorption
2. Experimental
Considerations
Spectroscopy:
EXAFS
and XANES
CaO
: V / \ ^ L o T i 0 3_
V.
;
/ / ^ \
Techniques
MnO
f.
Fe0 M
5 q Q 05
LaMn03
w / /
L
/ : ^ \
'
J*
(b)
A^CeVO^
N d/ 0 > M
5 o
At
^ l
T5 i 0
r\
_ 0
C O A I 2O 4
\ ^
Pi
NiO
.*
(a)
CoO
1 1 1 1 1 1 1 1 1
'
1
Ve
1 1 1 1 1 1
IA\
Energy
Figure 4
K-edge XANES spectra for (a) perovskites,
(b) monoxides, (c) zircon-type oxides and (d) spinels
557
X-Ray
Absorption
Spectroscopy:
EXAFS
and XANES
3. Strengths
and Weaknesses
of EXAFS
and
XANES
E X A F S is a t e c h n i q u e t h a t is p r i m a r i l y useful for
measuring crystallographic structure parameters. The
m e a s u r e m e n t is a t o m specific, p r o v i d i n g a local r a d i a l
d i s t r i b u t i o n function for t h o s e a t o m s d i s t r i b u t e d
a b o u t the central ( a b s o r b e r ) a t o m .
F o r simple systems with l o n g - r a n g e o r d e r , a c c u r a
cies in t h e s t r u c t u r a l p a r a m e t e r s achievable w i t h
E X A F S a r e inferior t o t h o s e achievable using diffrac
tion t e c h n i q u e s p r o v i d i n g t h a t t h e m a t e r i a l s a r e n o n dilute. E X A F S plays t h e m o r e i m p o r t a n t role in
o b t a i n i n g s t r u c t u r a l i n f o r m a t i o n for a m o r p h o u s
m a t e r i a l s , solutions a n d dilute systems of v a r i o u s
k i n d s (such as h e t e r o g e n e o u s catalysts, biological
m a t e r i a l s a n d i m p u r i t y a t o m s in crystalline solids).
X A N E S is a spectroscopic t o o l useful for p r o b i n g
the u n o c c u p i e d electron states within 50 eV of t h e
F e r m i level. By m o n i t o r i n g a b s o r p t i o n edges associ
a t e d with different c o r e levels, electric dipole selection
rules c a n be used t o a d v a n t a g e in identifying e m p t y
states of specific a n g u l a r m o m e n t u m c h a r a c t e r . A s a
tool for p r o b i n g these e m p t y electron states, X A N E S
c o m p l e m e n t s a n u m b e r of o t h e r spectroscopies (such
as b r e m s s t r a h l u n g i s o c h r o m a t s p e c t r o s c o p y , u l t r a
558
Techniques
violet
photoemission
and
optical
reflectivity).
X A N E S c a n b e used a s a m a t e r i a l s c h a r a c t e r i z a t i o n
t o o l . N o v a c u u m is r e q u i r e d for these m e a s u r e m e n t s
(a significant e x p e r i m e n t a l convenience) a n d , often,
m a t e r i a l s with very low c o n c e n t r a t i o n of a b s o r b e r c a n
be studied w i t h ease.
E X A F S a n d X A N E S a r e , in a certain sense, redis
covered spectroscopies. T h e p h e n o m e n a h a v e b e e n
k n o w n for d e c a d e s , b u t only recently h a v e a d v a n c e s
in theoretical u n d e r s t a n d i n g a n d i n s t r u m e n t d e v e l o p
m e n t b e e n a d e q u a t e t o d e m o n s t r a t e t h e p r o m i s e of
t h e spectroscopies for m a t e r i a l s studies.
See also: X-Ray and Neutron Diffraction Studies of Amor
phous Solids; X-Ray Powder Diffraction
Bibliography
Lee A, Citrin , Eisenberger , Kincaid 1981
Extended x-ray absorption fine structure: its strengths
and limitations as a structural tool. Rev. Mod. Phys. 53:
769-806
Maylotte D H, Wong J, St Peters R L, Lytle L W, Greegor
R 1981 X-ray absorption spectroscopic investigation of
trace vanadium sites in coal. Science 214: 554-6
Sayers D E, Stern A, Lytle F W 1971 New technique for
investigating noncrystalline structures: Fourier analysis
of the extended x-ray absorption fine structure. Phys. Rev.
Lett. 27: 1204-7
Stern A (ed.) 1980 Workshop on Laboratory EXAFS
Facilities and Their Relation to Synchroton Radiation
Sources, AIP Conference Proceedings No. 64. American
Institute of Physics, New York
G . S. K n a p p a n d B. W . Veal
[Argonne National Laboratory,
A r g o n n e , Illinois, U S A ]
X-Ray
and Neutron
Diffraction
Studies
of Amorphous
Solids
r e g e n e r a t i o n of t h e u n d e r l y i n g t h r e e - d i m e n s i o n a l
s t r u c t u r e c a n never be u n i q u e . T h u s , diffraction s t u d
ies of a m o r p h o u s solid s t r u c t u r e s fall n a t u r a l l y i n t o
t w o stages: t h e a c t u a l e x p e r i m e n t c u l m i n a t i n g in t h e
d e r i v a t i o n of a real-space c o r r e l a t i o n function, a n d
the i n t e r p r e t a t i o n of this c o r r e l a t i o n function in t e r m s
of a t h r e e - d i m e n s i o n a l s t r u c t u r e .
/.
The Real-Space
Correlation
Function
T h e s t r u c t u r e s of simple c o v a l e n t crystalline a n d
a m o r p h o u s solids a r e c o m p a r e d schematically in t w o
d i m e n s i o n s in Fig. 1. F o r t h e crystal, t h e s t r u c t u r e
m a y b e specified in t e r m s of a u n i t cell a n d t r a n s l a tional s y m m e t r y , t h e latter leading t o t h e s h a r p B r a g g
p e a k s which a r e characteristic of t h e diffraction p a t
tern of crystalline solids. T h e s t r u c t u r e of a n a m o r
p h o u s solid, o n t h e o t h e r h a n d , is c h a r a c t e r i z e d b y a
lack of s y m m e t r y , periodicity a n d l o n g - r a n g e o r d e r ,
resulting in a diffraction p a t t e r n which is a c o n t i n u o u s
function of t h e scattering vector Q. T h u s , in o r d e r t o
completely specify t h e s t r u c t u r e of a n a m o r p h o u s
solid it w o u l d b e necessary t o specify t h e c o o r d i n a t e s
of all the a t o m s p r e s e n t , which is clearly impossible
for a n y real m a t e r i a l .
T h e i s o t r o p i c n a t u r e of a n a m o r p h o u s m a t e r i a l
leads t o a s t r u c t u r a l d e s c r i p t i o n in t e r m s of a o n e d i m e n s i o n a l real-space c o r r e l a t i o n function, w h i c h is
essentially a o n e - d i m e n s i o n a l a n a l o g u e of t h e P a t e r son function used for single crystals. F o r a m o n a t o
mic m a t e r i a l , t h e r a d i a l density p(r) describes t h e
n u m b e r density a t a d i s t a n c e r from a n a r b i t r a r i l y
chosen origin a t o m (see Fig. 2), a n d is a gross a v e r a g e
over all the a t o m s in t h e s a m p l e t a k e n as center. p is
the a v e r a g e n u m b e r density for the w h o l e s a m p l e . T h e
n u m b e r of n e i g h b o r s b e t w e e n r a n d r 4- dr is given by
2
dr
in which g(r) is k n o w n as t h e r a d i a l
function. T h e c o r r e l a t i o n function,
t(r) = 4nrp(r)
(1)
(2)
(3)
F o r a s a m p l e c o n t a i n i n g elements t h e s t r u c t u r e m a y
be described in t e r m s of n(n 4- l ) / 2 i n d e p e n d e n t c o m
p o n e n t c o r r e l a t i o n functions of t h e f o r m
tjk(r)
= 4nrpjk{r)
(b)
distribution
(4)
Figure 1
Structures of simple covalent (a) crystalline and
(b) amorphous solids
2. Experimental
Techniques
(5)
w h e r e is t h e incident w a v e l e n g t h a n d 20 is the
scattering angle. A l t h o u g h for a n a m o r p h o u s solid
t h e s t r u c t u r a l i n f o r m a t i o n is essentially c o n t a i n e d
within t h e elastic scattering, it is c o n v e n t i o n a l t o
p e r f o r m a t o t a l diffraction e x p e r i m e n t in which the
559
X-Ray
and Neutron
Diffraction
(a)
t (r)
-- 4
Studies
of Amorphous
(b)
(r)
(d )
Figure 2
Real-space correlation functions: (a) radial density;
(b) radial-distribution function; (c) total correlation
function; (d) differential correlation function
Solids
rise t o a s t r o n g e p i t h e r m a l c o m p o n e n t in (). T h e s e
s h o r t - w a v e l e n g t h n e u t r o n s allow d a t a to be o b t a i n e d
to m u c h higher values of Q, resulting in a c o r r e s p o n d
ing increase in real-space resolution.
A c c u r a t e q u a n t i t a t i v e x-ray diffraction m e a s u r e
m e n t s o n a m o r p h o u s solids usually e m p l o y a m o d i
fied p o w d e r - c o u n t e r diffractometer
(see
X-Ray
Powder Diffraction). T h e situation for x-rays is c o m
plicated by t h e presence of i n c o h e r e n t C o m p t o n scat
tering which a t high values of Q c a n completely
s w a m p the r e q u i r e d c o h e r e n t c o n t r i b u t i o n . Since
neither the w a v e l e n g t h d i s t r i b u t i o n n o r the i n t e g r a t e d
intensity of the C o m p t o n scattering from a given
s a m p l e c a n b e satisfactorily calculated, it is necessary
t o r e m o v e this c o n t r i b u t i o n by m e a n s of a diffractedb e a m m o n o c h r o m a t o r . M a n y researchers h a v e used a
single m o n o c h r o m a t o r in t h e diffracted b e a m b u t t h e
difficulty with this a r r a n g e m e n t is t h a t white b a c k
g r o u n d r a d i a t i o n from the x-ray t u b e c a n be C o m p
t o n scattered i n t o the m o n o c h r o m a t o r envelope. A
m u c h better a r r a n g e m e n t , s h o w n in Fig. 5, e m p l o y s a
m o n o c h r o m a t o r in b o t h t h e incident a n d diffracted
b e a m s ( W a r r e n a n d M a v e l 1965). A c o n v e n t i o n a l
curved-crystal m o n o c h r o m a t o r is used in t h e incident
b e a m (silver ^ = 0.05594 n m ) b u t t h a t in the
diffracted b e a m c o m p r i s e s a foil with a n a b s o r p t i o n
edge at a w a v e l e n g t h slightly longer t h a n the c h a r a c
teristic line of the x-ray t u b e ( r u t h e n i u m edge:
= 0.05605 n m ) such t h a t t h e c o h e r e n t intensity will
excite fluorescence w h e r e a s t h e C o m p t o n scattering
will n o t . T h e fluorescent r a d i a t i o n is t h e n r e c o r d e d by
the detector.
T h e dispersion t e c h n i q u e is also possible with rays
using a s e m i c o n d u c t o r detector. T h e a d v a n t a g e of this
m e t h o d is t h a t for c o m p l e x s a m p l e e n v i r o n m e n t s
(such as c r y o s t a t s , furnaces a n d high-pressure cells)
only t w o o r three small w i n d o w s a r e needed, a fixed
angle a p a r t . Similarly, all values of Q a r e e x a m i n e d
simultaneously, m a k i n g the t e c h n i q u e ideally suited
t o following p h a s e c h a n g e s o r s t u d y i n g kinetic effects.
O u t s i d e such special a p p l i c a t i o n s , however, x-ray
variable-wavelength experiments are unlikely t o p r o v e
i m p o r t a n t for w o r k o n a m o r p h o u s m a t e r i a l s o w i n g t o
the difficulty of accurately d e t e r m i n i n g t h e incident
s p e c t r u m a n d m a k i n g c o r r e c t i o n s for a b s o r p t i o n a n d
C o m p t o n scattering.
A n y m e a s u r e m e n t requires a certain n u m b e r of
c o r r e c t i o n s t o t h e basic d a t a b u t in a g o o d e x p e r i m e n t
these c o r r e c t i o n s a r e minimized o r p u t i n t o a form in
which they a r e easily h a n d l e d . N o r m a l l y , corrections
a r e included for:
(a)
c o u n t e r paralysis t i m e t h i s c o r r e c t i o n is b e c o m
ing increasingly i m p o r t a n t with m o d e r n highintensity x-ray a n d n e u t r o n sources;
(b)
i n s t r u m e n t a l b a c k g r o u n d a n d scattering
a n y s a m p l e c o n t a i n e r used;
(c)
from
X-Ray
and Neutron
Diffraction
Studies
of Amorphous
Solids
Figure 3
Conventional neutron diffractometer
c a n only be t r e a t e d i n d e p e n d e n t l y if o n e o r o t h e r
of t h e m is small;
(d)
(e)
F o l l o w i n g c o r r e c t i o n it is necessary t o n o r m a l i z e t h e
d a t a t o a b s o l u t e units. T h i s m a y be achieved either b y
the use of self-consistent i n t e g r a t i o n t e c h n i q u e s or, for
n e u t r o n s , by m e a s u r i n g t h e ( i n c o h e r e n t ) s c a t t e r i n g
from a s t a n d a r d v a n a d i u m s a m p l e .
3. Outline
Theory
i(0
pattern
ma
T{r) =
j*g/(0M(0sin rQ dQ (7)
(8)
T(r) = 4nrp^bj)2
(6)
T(r) = T\r) +
TLt)k{r)
J k
/OO
tjk(u)[P'jk(r
- u)
Jo
-P'jk(r
+ u)]du
(9)
X-Ray
and Neutron
Diffraction
Studies
of Amorphous
Target
Pulsed
electron
BEAM
'olyethylene moderator
Concrete shielding wall
Solids
Borax in resin
92
U fjssion chamber
Focusing angle
B4C in resin
Variable Second
f|ight-pbth
BAC in rubber
Figure 4
Time-of-flight neutron diffractometer
P%(r)
= ( ^ )
M ( 0 C O S rQ dQ
(10)
define t h e e x p e r i m e n t a l resolution in real space.
fj(Q) a n d fk(Q)
being a t o m i c scattering factors
a n d / e(0 the a v e r a g e form factor p e r electron for the
s a m p l e j n q u e s t i o n . F o r n e u t r o n s , t h e scattering
lengths b a r e i n d e p e n d e n t of Q a n d the factor bjbk is a
simple scaling factor, w h e r e a s for rays it is c o n v e n
tional t o divide Qi(Q) b y t h e " s h a r p e n i n g " function
562
of
Interpretation
Qijk(Q)
-r , ^
njkfj(Q)fk(Q)
in
ikQ
e x p i - i g ^ ) (11)
w h e r e nJk is t h e n u m b e r of /c-type a t o m s a r o u n d a t o m
j at this distance, a n d f{Q) represents either f(Q) o r b
for rays o r n e u t r o n s , respectively. T h e c o r r e s p o n d
ing real-space c o r r e l a t i o n function, including the c o n -
X-Ray
and Neutron
Diffraction
Studies
of Amorphous
Solids
Scaler
Figure 5
Fluorescent-foil x-ray diffraction technique
t r i b u t i o n from P(r), c a n b e o b t a i n e d b y F o u r i e r
t r a n s f o r m a t i o n of E q n . (11) w i t h t h e s a m e value of
g m ax a n d modification function a s used e x p e r i m e n
tally. It is t h u s possible t o o b t a i n t h e p a r a m e t e r s njk,rjk
1 /2
a n d (w#) b y p e r f o r m i n g a least-squares fit t o t h e
e x p e r i m e n t a l d a t a in real space o r t o t h e e x p e r i m e n t a l
interference function a t h i g h Q, w h e r e only t h e s h a r p
est real-space p e a k s c o n t r i b u t e .
7(0)=/ (0)*/(0)
self
()=
{)+
J Q/lQ)M[Q)
distinct
sin rO
dO
Figure 6
Steps in the calculation of the real-space correlation
function T(r) from the corrected intensity / ( g )
4.2 Model
Calculations
T h e limited n a t u r e of t h e m e a s u r e d c o r r e l a t i o n func
tion m e a n s t h a t in o r d e r t o e x t r a c t m o r e t h a n j u s t
average interatomic distances a n d coordination
n u m b e r s it is necessary t o r e s o r t t o s o m e f o r m of
m o d e l a n d t o ascertain h o w well this agrees with
e x p e r i m e n t . Qi(Q) a n d T(r) e m p h a s i z e different a s
pects of t h e s t r u c t u r e a n d it is therefore m o s t i m p o r t
a n t t o m a k e such c o m p a r i s o n s in b o t h real a n d
intensity space, a n d in t h e f o r m e r t o correctly incor
p o r a t e t h e p e a k function P(r). Similarly, n o m a t t e r
h o w g o o d t h e a g r e e m e n t o b t a i n e d is, t h e m o d e l in
q u e s t i o n is only o n e possible fit t o t h e d a t a a n d hence
it is essential t o c o n s i d e r , a n d if possible eliminate, all
a l t e r n a t i v e m o d e l s . A variety of s t r u c t u r a l m o d e l s a n d
m o d e l l i n g t e c h n i q u e s h a s b e e n e m p l o y e d in t h e s t u d y
of a m o r p h o u s solids a n d s o m e of t h e m o r e i m p o r t a n t
of these a r e s u m m a r i z e d b e l o w .
(a)
C r y s t a l - b a s e d m o d e l s . A g r e a t deal of i n f o r m a
tion o n t h e s t r u c t u r e of a m o r p h o u s solids c a n be
o b t a i n e d from a simple c o m p a r i s o n with t h e
c o r r e s p o n d i n g crystalline p o l y m o r p h s . M o r e
f o r m a l crystal-based m o d e l s , such as t h e q u a s i crystalline m o d e l , s t a r t w i t h a n a p p r o p r i a t e crys
tal s t r u c t u r e a n d restrict t h e l o n g e r - r a n g e o r d e r
t o i n t e r a t o m i c spacings less t h a n s o m e c h a r a c t e r
istic c o r r e l a t i o n length.
(b)
563
X-Ray
and Neutron
Diffraction
Studies
of Amorphous
C h a i n a n d ring m o d e l s . T h e s e m o d e l s a r e a p p r o
p r i a t e for m a t e r i a l s c o n t a i n i n g only divalent
a t o m s (e.g., selenium) o r larger t w o - c o n n e c t e d
g r o u p i n g s of a t o m s such as t h o s e f o u n d in or
ganic p o l y m e r s ( e . g . , C H 2 ) .
(d)
Random-sphere-packing
models.
Random
sphere p a c k i n g s p r o v i d e a useful s t a r t i n g p o i n t
for m o d e l s of a m o r p h o u s metallic alloys a n d
m a t e r i a l s w h o s e s t r u c t u r e s a r e g o v e r n e d by p r e
d o m i n a n t l y ionic forces such as vitreous Z n C l 2 .
(e)
(f)
A m o r p h o u s - c l u s t e r m o d e l s . A m o r p h o u s clusters
a r e c o m p o s e d of a t o m s in a regular b u t n o n c r y s t a l l o g r a p h i c configuration frequently b a s e d o n
p e n t a g o n a l d o d e c a h e d r a o r fivefold s y m m e t r y .
Cluster size is limited d u e t o a slight m i s m a t c h
between adjacent s t r u c t u r a l u n i t s , w h i c h leads t o
increasing d i s t o r t i o n as t h e cluster g r o w s .
(g)
M o n t e C a r l o a n d m o l e c u l a r d y n a m i c s simula
tions. T h e s t r u c t u r e s of a r a n g e of simple inor
ganic glasses h a v e been s i m u l a t e d using p u r e l y
ionic p o t e n t i a l s . A g a i n t h e m e t h o d s e m p l o y e d
closely follow t h o s e for related liquids.
5. Neutron
Magnetic
Diffraction
6. Accuracy
and
Limitations
564
Solids
a u t h o r s either p l o t t h e r a d i a l d i s t r i b u t i o n function
r 7 \ r ) , w h i c h h a s t h e effect of r e d u c i n g t h e a m p l i t u d e
of e r r o r ripples a t low r, o r use these false oscillations
as a criterion for tidying their d a t a before p u b l i c a t i o n
a n d d o n o t include the original u n t r e a t e d t r a n s f o r m .
In t h e a b s e n c e of o t h e r i n f o r m a t i o n such d a t a m u s t be
r e g a r d e d with t h e u t m o s t suspicion.
Similar t e c h n i q u e s a r e s o m e t i m e s used t o r e m o v e
t h e effects of t e r m i n a t i n g t h e d a t a a t finite Q m a x.
I n f o r m a t i o n t h e o r y , h o w e v e r , indicates t h a t it is im
possible t o replace t h e u n m e a s u r e d d a t a w i t h o u t
making some assumption a b o u t the material under
investigation so t h a t t h e resulting c o r r e l a t i o n function
merely b e c o m e s o n e possible m o d e l which fits the
results r a t h e r t h a n a n u n b i a s e d F o u r i e r t r a n s f o r m . It
s h o u l d also be n o t e d t h a t in principle b o t h Qi(Q) a n d
T(r) c o n t a i n t h e s a m e i n f o r m a t i o n expressed in a
different f o r m , a l t h o u g h in practice t h e i n f o r m a t i o n
c o n t e n t of T(r) is slightly r e d u c e d by t h e use of a
modification function. T h e finite u p p e r limit in Q
m e a n s t h a t in T(r) e a c h c o m p o n e n t tjk{r) is c o n v o
luted with t h e a p p r o p r i a t e p e a k f u n c t i o n p ( r ) , b u t the
i n f o r m a t i o n for a p a r t i c u l a r d i s t a n c e is still c o n c e n
t r a t e d a r o u n d t h a t d i s t a n c e (whereas it is s p r e a d
t h r o u g h o u t reciprocal space).
T h e u n i q u e n e s s of a n y s t r u c t u r a l i n f o r m a t i o n
e x t r a c t e d from t h e d a t a is m u c h m o r e difficult t o
j u d g e . A s a l r e a d y stressed, t h e o n e - d i m e n s i o n a l
n a t u r e of t h e c o r r e l a t i o n function m e a n s t h a t it is
impossible t o u n a m b i g u o u s l y d e t e r m i n e t h e s t r u c t u r e
of a n a m o r p h o u s solid. T h e reliability of a n y i n t e r p r e
t a t i o n , therefore, d e p e n d s n o t only o n t h e q u a l i t y of
the fit t o the e x p e r i m e n t a l d a t a in b o t h real a n d
reciprocal space, b u t also o n the n u m b e r of o t h e r
possible m o d e l s w h i c h h a v e been tried a n d satisfactor
ily rejected. T h e fact t h a t diffraction d a t a a r e a n
a v e r a g e for t h e w h o l e i r r a d i a t e d v o l u m e , a n d include
a t m o s t only p a r t of a n y small-angle scattering which
m a y be p r e s e n t , m e a n s t h a t t h e d a t a a r e relatively
insensitive t o p h a s e s e p a r a t i o n . In m o s t cases, it is
n o t possible t o d e t e r m i n e t h e individual c o m p o n e n t
a n d in this situation
c o r r e l a t i o n functions tjk(r),
e x t e n d e d x-ray a b s o r p t i o n fine-structure t e c h n i q u e s
can provide important complementary information.
Finally, it m u s t n o t be f o r g o t t e n t h a t a great deal of
o t h e r s t r u c t u r a l i n f o r m a t i o n c a n be o b t a i n e d from the
results of indirect p r o b e s such as optical s p e c t r o s c o p y
a n d m a g n e t i c r e s o n a n c e s p e c t r o s c o p y . All of these
d a t a m u s t also be consistent with a n y c h o s e n struc
tural model.
See also: Single-Crystal X-Ray Diffraction; X-Ray Absorp
tion Spectroscopy: EXAFS and XANES Techniques;
X-Ray Powder Diffraction
Bibliography
Elliott S R 1984 Physics of Amorphous Materials. Longman,
London
X-Ray
and Neutron
I. Diffuse
X-Ray
Scattering
Diffuse
Scattering
of Radiation-Induced
Defects
(1)
S=c\F(k)\
(2)
occ(AF)
(3)
e f o r e
S a [ l eor c ( c / ) ( A F )
(4)
565
X-Ray
and Neutron
022
Diffuse
Scattering
of Radiation-Induced
Defects
222
? _
Scattering angle
()
Figure 1
Comparison of the measured diffuse scattering intensity from electron-irradiated aluminum with intensities calculated
assuming different self-interstitial atom configurations (after Haubold 1975)
2. Neutron
(5)
Diffuse
Elastic
Scattering
+ ( , ) + , ( . )
2
+ ? ( 1 , 2 , 3 ) + 2 ( 2 , 3 )
+ ^ ^ , , ) + A,
h2Sxy(hh2,h3)
+ MjS^Mj,*,) + , 5 ^ (
, 2)
(6)
with
^SRO
lmn
a
os
sc
2 COS
7TNAJ
(7)
c o s 2 cos 3
(8)
l,m,n
Figure 2
Scattering intensities close to (400) reflections in a [100] q
direction calculated for dislocation loops with radius
20 A in nickel (after Ehrhart et al. 1982)
566
Qx
l,m,n
yimn '
lh\
X-Ray
Rx
(9)
l,m,n
*mn
sm
ms
(10)
l,m,n
C, a r e c o n c e n t r a t i o n s of species a n d b\ a r e n e u t r o n
scattering lengths weighted b y a p p r o p r i a t e D e b y e Waller factors. A detailed discussion c a n b e f o u n d in
S c h m a t z (1973) a n d B a u r (1979). T h e t e r m s in Rx
c o n t a i n i n f o r m a t i o n a b o u t static d i s p l a c e m e n t effects
described in Sect. 1; 7 S RO p r o v i d e s details o f s h o r t r a n g e o r d e r a n d clustering a m o n g defects. T h e u s e o f
s y m m e t r y a r g u m e n t s in a detailed discussion o f these
e q u a t i o n s c a n b e f o u n d in S c h w a r t z a n d C o h e n
(1977). T h e p o i n t h e r e is t h a t t h e F o u r i e r coefficients
in E q n s . ( 8 - 1 0 ) , for r a y s , c o n t a i n a t o m i c scattering
factors f(Q) a n d t h u s a r e n o t strictly periodic. F o r
n e u t r o n s , n u c l e a r scattering lengths a r e a p p r o p r i a t e
a n d hence t h e a p p l i c a t i o n o f n e u t r o n s offers signific
a n t a d v a n t a g e over r a y s .
Diffuse elastic n e u t r o n scattering ( D E N S ) tech
niques allow u s t o r e m o v e t h e c o m p l i c a t i o n s o f
t i m e - d e p e n d e n t p h e n o m e n a such a s p h o n o n inelastic
scattering, a n d a r e m u c h less sensitive t o surface
effects since n e u t r o n a b s o r p t i o n cross sections a r e
m u c h smaller t h a n x-ray c o u n t e r p a r t s . T h e largest
sources of b a c k g r o u n d in x-ray m e a s u r e m e n t s a r e
C o m p t o n a n d t h e r m a l diffuse scattering; these a r e
eliminated using D E N S t e c h n i q u e s . H o w e v e r , c a r e
m u s t b e t a k e n in t h e n e u t r o n case t o a v o i d n u c l e a r
spin a n d i s o t r o p i c d i s o r d e r scattering. T h e m a i n dis
a d v a n t a g e s o f D E N S stem from limited n e u t r o n
fluxes available a t steady state sources; h o w e v e r , n e w
i n s t r u m e n t a t i o n a n d t h e a d v e n t of pulsed n e u t r o n
sources m a y allow u s t o m i n i m i z e this limitation (see
C o h e n et al. (1975)).
Acknowledgement
T h e w o r k o f t h e a u t h o r s is s u p p o r t e d b y t h e U S
Government under contract N o . W-31-109-ENG-38.
See also: Electron Microscope Analysis of Defect Clusters,
Voids and Bubbles; X-Ray Powder Diffraction
Bibliography
Baur G S 1979 Diffuse elastic neutron scattering from non
magnetic materials. In: Herman (ed.) 1979 A Treatise
on Materials Science and Technology, Vol. 15. Academic
Press, New York, pp. 291
Borie B, Sparks C J Jr 1971 The interpretation of intensity
distributions from distorted binary alloys. Acta Crystallogr. Sect. A 27: 198-201
Cohen J B, Faber J, Batterman W, Baur G S, King S S,
Larson C, Summerfeld G C 1975 Advanced Uses of
Pulsed Neutron Sources, ANL-76-10, Vol. 2. Argonne
National Laboratory, Argonne, IL, p. 88
Diffraction,
Time-Resolved
X-Ray
Diffraction,
Time-Resolved
/.
Direct
Measurements
568
m o r e t h a n six o r d e r s of m a g n i t u d e b r i g h t e r t h a n
c o n v e n t i o n a l r o t a t i n g a n o d e x-ray sources a n d synch
r o t r o n facilities scheduled t o b e c o m p l e t e d in t h e m i d 1990s will b e yet a n o t h e r t h o u s a n d times brighter.
H a v i n g selected a s o u r c e , three w a y s exist t o increase
the t o t a l flux in t h e incident b e a m : use m o r e w a v e
lengths of t h e s o u r c e , use m o r e angles of t h e s o u r c e o r
use s o m e c o m b i n a t i o n of b o t h . Often, t h e resulting
increase in flux is a t t h e expense of lowering t h e
diffraction r e s o l u t i o n of t h e e x p e r i m e n t .
Before p r o c e e d i n g , it is w o r t h w h i l e m e n t i o n i n g a n
essential difference b e t w e e n t w o types of m e a s u r e
m e n t s , p o w d e r diffraction a n d single-crystal dif
fraction. B r a g g ' s law requires t w o c o n d i t i o n s t o b e
satisfied for diffraction. O n e results b e c a u s e t h e angle
of incidence of t h e r a y s o n t h e diffracting p l a n e s
m u s t b e correct a n d t h e s e c o n d b e c a u s e rays will
diffract only in certain directions. T h e incident angle
r e q u i r e m e n t m e a n s t h a t for time-resolved diffraction
o n single crystals it is also necessary, except in special
cases, t o c h a n g e t h e o r i e n t a t i o n of t h e crystal. F o r
p o w d e r s , crystallites exist a t all o r i e n t a t i o n s a n d so
t h e first r e q u i r e m e n t is always satisfied a n d only t h e
p l a c e m e n t of t h e x-ray d e t e c t o r a t t h e correct scatter
ing angles is needed. A n o t h e r i m p o r t a n t difference
b e t w e e n a single crystal a n d a p o w d e r s a m p l e of t h e
s a m e m a t e r i a l is t h e relative intensity of a typical
B r a g g p e a k . F o r a single crystal t h e intensity of a
B r a g g p e a k is localized i n t o a n intense small solid
angle of scattering. I n c o n t r a s t , t h e m a n y o r i e n t a t i o n s
of crystallites in a polycrystalline s a m p l e result in a
c o n e of scattering of w h i c h diffractometers only
m e a s u r e a small fraction.
T h e m o s t o b v i o u s w a y t o i m p r o v e t h e detection
efficiency in a c o n v e n t i o n a l p o w d e r diffraction experi
m e n t is t o use m a n y d e t e c t o r s a n d therefore collect
m a n y scattering angles s i m u l t a n e o u s l y . T h i s is c o n
veniently d o n e using o n e - d i m e n s i o n a l a n d t w o d i m e n s i o n a l d e t e c t o r a r r a y s , w h i c h a r e often referred
to a s position-sensitive d e t e c t o r s . T h e diffraction reso
lution of these d e t e c t o r s is partially d e t e r m i n e d b y t h e
physical size o f e a c h d e t e c t o r element a n d t h e time
r e s o l u t i o n is d e t e r m i n e d b y t h e electronics, which
limits t h e m a x i m u m m e a s u r a b l e c o u n t r a t e . T h e
oldest position-sensitive d e t e c t o r is a p r o p o r t i o n a l
wire d e t e c t o r . T h e y c o n v e n t i o n a l l y give 100 spa
tial r e s o l u t i o n a n d c a n s p a n a region of 510 c m in
either a straight line o r a l o n g a circular a r c . T h e s e
d e t e c t o r s h a v e a very l o w intrinsic b a c k g r o u n d . T h e i r
p r i m a r y deficiency is t h a t they h a v e a relatively low
m a x i m u m c o u n t r a t e of a r o u n d 50 000 rays p e r
second i n t e g r a t e d over t h e w h o l e detector. Since
50 000 c o u n t s s p r e a d over a diffraction p a t t e r n is
a b o u t t h e m i n i m u m n u m b e r of c o u n t s r e q u i r e d t o
define a diffraction p a t t e r n , this limits t h e m i n i m u m
time p e r diffraction p a t t e r n t o a r o u n d 1 s. M o r e
recently, p h o t o d i o d e a r r a y s ( S t e p h e n s o n 1988) a n d
c h a r g e - c o u p l e d device ( C C D ) a r r a y s ( R o d r i c k s et al.
1989) h a v e b e c o m e available for x-ray detection. T h e y
X-Ray
Diffraction,
Time-Resolved
Measurements
569
X-Ray
Diffraction,
Time-Resolved
5. Future
Possibilities
Measurements,
Subsecond;
Bibliography
Baublitz A Jr, Arnold V, Ruoff A L 1981 Energy
dispersive x-ray diffraction from high pressure polycrystalline specimens using synchrotron radiation. Rev. Sci.
Instrum. 52: 1616-24
Brauer S, Ryan D H, Strom-Olsen J O, Sutton M, Stephen
son G 1990 Pyrometric temperature controller for
million degree per second heating. Rev. Sci. Instrum. 61:
2214-19
570
1. Definition,
Scope,
Advantages,
Limitations
X - r a y fluorescence s p e c t r o m e t r y is a n o n d e s t r u c t i v e
i n s t r u m e n t a l m e t h o d of qualitative a n d q u a n t i t a t i v e
analysis for chemical elements b a s e d o n the w a v e
lengths a n d intensities of their x-ray-excited spectral
X-Ray
Spectra
X rays m a y b e defined a s e l e c t r o m a g n e t i c r a d i a t i o n in
5
the wavelength region ~ 1 0 ~ - 1 0 n m p r o d u c e d b y
deceleration of high-energy electrons a n d / o r b y elec-
Fluorescence
Spectrometry
Wavelength
Figure 1
Section of an atom of an element of high atomic number,
showing the electron transitions that produce the principal
characteristic x-ray spectral lines and the x-ray spectrum
from an x-ray tube having a target of high atomic number
and operated at high potential (from Introduction to
X-Ray Spectrometric Analysis, courtesy of Plenum Press)
t r o n t r a n s i t i o n s t o t h e inner orbits of a t o m s . I n
analytical x-ray fluorescence s p e c t r o m e t r y , t h e appli
cable spectral region is ~ 0 . 0 1 - 2 n m a n d with special
accessories t o ~ 1 0 n m . X rays a r e characterized b y
w a v e l e n g t h ( n m ) p h o t o n energy (eV), a n d inten
sity / ( p h o t o n s , o r " c o u n t s , " p e r second). T h e w a v e
length a n d p h o t o n energy a r e related reciprocally:
E= 124 000/A. T h e c o n s t a n t in this e q u a t i o n is (he/
11
e) x 1 0 n m m~ \ w h e r e h is P l a n c k ' s c o n s t a n t , c is t h e
velocity of light a n d e is t h e electron c h a r g e . T h e r e a r e
t w o types of x-ray emission spectra: c o n t i n u o u s a n d
characteristic-line (see F i g . 1).
The continuous spectrum, continuum or "brehmss t r a h l u n g " o c c u r s in significant intensity only with
electron excitation a n d arises from d e c r e m e n t a l decel
e r a t i o n of electrons. It is c h a r a c t e r i z e d by a c o n t i n u
o u s b a n d of wavelengths, s t a r t i n g a t a m i n i m u m
w a v e l e n g t h d e t e r m i n e d b y t h e electron acceleration
p o t e n t i a l V (A m in = 124 000/) rising t o m a x i m u m
intensity a t 1.5 A m i n, a n d decreasing in intensity a t
increasing wavelength (Fig. 1).
C h a r a c t e r i s t i c x-ray line spectra arise w h e n v a c a n
cies o c c u r in t h e K , L a n d shells of a t o m s a n d
electrons from shells further o u t fall i n t o these v a c a n
cies, t h e r e b y losing energy, which a p p e a r s as x-ray
photons. Fig. 1 shows the transitions that produce the
principal lines a n d t h e s y m b o l s a n d relative intensities
571
X-Ray
Fluorescence
Spectrometry
M i l l
3. Excitation
of Characteristic
X-Ray
Spectra
572
Figure 2
Distinction between wavelength dispersion (right of
specimen), in which the rays are dispersed spacially by
wavelength prior to detection, and energy dispersion (left
of specimen), in which all rays are detected
simultaneously and detector output pulses are separated
by amplitude electronically (from Introduction to X-Ray
Spectrometric Analysis, courtesy of Plenum Press)
4.
Dispersion
5. InstrumentationX-Ray
Generator
X-Ray
Fluorescence
Spectrometry
5 0 kV
Figure 3
X-ray generator: the solid and dashed waveforms at the top correspond to the high (solid arrow) and low (dashed arrow)
settings of the autotransformer. The resistor and capacitor constitute the constant-potential filter. The switch represents
various automatic safety devices
6. InstrumentationSpecimen
Spectrogoniometer
Chamber
and
S o m e s p e c t r o g o n i o m e t e r s a r e s e p a r a t e self-contained
table-top instruments having the x-ray-tube window
directed d o w n w a r d i n t o a c h a m b e r h a v i n g a r e m o v
able d r a w e r for specimens ~ 2 . 5 c m in d i a m e t e r a n d
thickness. T h e s e i n s t r u m e n t s c a n be r e a r r a n g e d with
t h e x-ray w i n d o w u p w a r d ("inverted o p t i c s " ) for very
large specimens, such as i n g o t s , engine p a r t s a n d a r t
objects. I n m o s t s p e c t r o m e t e r s , t h e g o n i o m e t e r h a s
inverted optics b u t is enclosed o n all sides, limiting
m a x i m u m specimen size t o ~ 5 c m d i a m e t e r by
~ 2 . 5 c m thick. T h e specimen c h a m b e r m a y h o l d a
single specimen o r p r o v i d e for a u t o m a t i c sequential
i n d e x i n g of u p t o 30.
T h e s p e c t r o g o n i o m e t e r (Fig. 4) c o m p r i s e s t w o colli
m a t o r s , a n a n a l y z e r crystal a n d a d e t e c t o r a r r a n g e d
o n a m a n u a l o r m o t o r - d r i v e n precision r o t a t i n g
m e c h a n i s m . T h e c o l l i m a t o r s consist of spaced parallel
m e t a l foils rigidly held in rectilinear m e t a l tunnels.
T h e single-crystal b a r serves as a n x-ray diffraction
g r a t i n g . T h e d e t e c t o r is described in Section 7. O n e
c o l l i m a t o r is fixed a t t h e o u t p u t e n d of t h e specimen
c h a m b e r . T h e crystal is bisected b y a n d r o t a t e s a b o u t
t h e g o n i o m e t e r axis a t angle 0 p e r u n i t time as the
o t h e r c o l l i m a t o r a n d d e t e c t o r r o t a t e t o g e t h e r a t angle
20 p e r u n i t time. A t w a v e l e n g t h s s h o r t e r t h a n
~ 0 . 2 5 n m the specimen-crystal-detector radiation
p a t h m a y be air, b u t a t longer w a v e l e n g t h s x-ray
573
X-Ray
Fluorescence
Spectrometry
Figure 4
X-ray spectrogoniometer and electronic detection and readout components. The pulse diagrams show pulse height versus
time. The pulse-height selector passes pulses having amplitude between two discriminator settings, baseline BL and
window width W
a b s o r p t i o n in air is p r o h i b i t i v e a n d t h e g o n i o m e t e r is
enclosed in a flexible helium-flushed h o o d o r a rigid
vacuum hood.
T h e c o n s t i t u e n t elements in t h e specimen emit their
characteristic x-ray spectra in all directions, b u t only a
b u n d l e of rays parallel t o the foils of t h e first collima
t o r reaches t h e crystal. A t each a n g u l a r p o s i t i o n , t h e
crystal diffracts only t h e w a v e l e n g t h t h a t satisfies
the B r a g g law: = 2d sin 0, w h e r e d is the i n t e r p l a n a r
spacing of the crystal planes parallel t o the surface
a n d is a n integer defining the diffraction o r d e r . N o t e
t h a t a t a specified m o r e t h a n o n e w a v e l e n g t h c a n be
diffracted: in first o r d e r (n = 1), /2 in second o r d e r
(n 2 ) , . . . , / in t h o r d e r . T h u s , as t h e crystal
r o t a t e s over its r a n g e , it diffracts in sequence all
incident x-ray w a v e l e n g t h s u p t o a m a x i m u m of
2d n m . Several crystals h a v i n g different d spacings a r e
required t o cover t h e entire w a v e l e n g t h region, for
e x a m p l e , lithium fluoride (2d 0.403 n m ) , p e n t a e r y t h r i tol ( P E T , 2 ^ 0 . 8 7 4 n m ) a n d p o t a s s i u m h y d r o g e n
p h t h a l a t e ( K H P , 2</2.66 n m ) .
7. InstrumentationElectronic
Readout
Components
Detection
and
574
(Fig. 4) c o m p r i s e s a cylindrical m e t a l - t u b e c a t h o d e
h a v i n g a n axial wire a n o d e a n d insulating e n d s , a n d
filled with a gas, usually a r g o n o r x e n o n . T w o d i a m e t
rically o p p o s i t e x-ray w i n d o w s a r e p r o v i d e d . F o r
wavelengths shorter than ~ 0 . 2 5 n m the windows m a y
be p e r m a n e n t l y sealed beryllium o r mica. F o r longer
w a v e l e n g t h s , the w i n d o w s m u s t be of thin plastic,
usually 6- o r 3- M y l a r , t o reduce x-ray a b s o r p t i o n .
Such w i n d o w s a r e n o t gas-tight, so t h e gas, usually a
9 0 - 1 0 v o l . % m i x t u r e of a r g o n a n d m e t h a n e , is passed
c o n t i n u o u s l y t h r o u g h these "flow c o u n t e r s . " T h e
scintillation c o u n t e r c o m p r i s e s a disk of t h a l l i u m activated s o d i u m iodide, N a l ( T l ) , affixed o u t s i d e t h e
p h o t o c a t h o d e e n d of a multiplier p h o t o t u b e . T h e
lithium-drifted silicon, Si(Li), d e t e c t o r is a disk of
specially t r e a t e d single-crystal silicon.
E a c h x-ray p h o t o n a b s o r b e d in a gas-filled, scintil
lation o r silicon d e t e c t o r ejects a n electron from, say,
the o u t e r m o s t orbital of a gas, iodine o r silicon a t o m ,
respectively, a n d i m p a r t s substantially all of its p h o
t o n energy t o kinetic energy of this p h o t o e l e c t r o n . I n
t h e gas-filled detector, this p h o t o e l e c t r o n e x p e n d s its
energy in p r o d u c i n g m o r e gas-ion/electron p a i r s .
E a c h of these s e c o n d a r y electrons initiates a n " a v a
l a n c h e " of still m o r e i o n - e l e c t r o n p a i r s so t h a t for
4
e a c h electron p r o d u c e d b y the p h o t o e l e c t r o n ~ 1 0 6
10 electrons r e a c h t h e a n o d e wire t o c o n s t i t u t e a n
o u t p u t pulse. I n t h e scintillation detector, t h e p h o t o
electron e x p e n d s its energy in f o r m i n g a b u r s t of
blue-light p h o t o n s , ~ 1 0 % of w h i c h strike t h e p h o t o c a t h o d e of t h e multiplier p h o t o t u b e a n d result in a
p h o t o e l e c t r o n arriving a t t h e electron multiplier. E a c h
X-Ray
8. InstrumentationAutomated
Special-Purpose
Spectrometers
and
Fluorescence
Spectrometry
specimen i n t o p o s i t i o n a n d r e p e a t t h e process c o n
tinually, all a u t o m a t i c a l l y a n d u n a t t e n d e d .
The simultaneous multichannel spectrometer has
a r r a y e d a b o u t t h e specimen, like s p o k e s a b o u t a wheel
h u b , u p t o 15 m e t a l p l a t e s , e a c h h o u s i n g o n e o r t w o
s p e c t r o m e t e r s c o m p r i s i n g c o l l i m a t o r s , crystal a n d d e
tector, a n d e a c h h a v i n g a r e a d o u t c h a i n . T h u s , the
i n s t r u m e n t c o m p r i s e s u p t o 30 c h a n n e l s . M o s t of
these a r e preset t o a specific x-ray line. T h e o t h e r s a r e
m o t o r - d r i v e n " s c a n n i n g " s p e c t r o m e t e r s of t h e type
described in Section 6. T h e s e a r e used for qualitative
analysis a n d for elements d e t e r m i n e d t o o infrequently
t o w a r r a n t preset c h a n n e l s . T h e s e i n s t r u m e n t s c a n
a c c u m u l a t e intensity d a t a for u p t o 30 elements in 1-2
m i n , w h e r e u p o n t h e next specimen is indexed i n t o
p o s i t i o n a n d m e a s u r e d , a n d so o n , all a u t o m a t i c a l l y
and unattended.
I n b o t h sequential a n d s i m u l t a n e o u s i n s t r u m e n t s ,
t h e intensity d a t a for s a m p l e s a n d s t a n d a r d s is i n p u t
t o a (usually) d e d i c a t e d c o m p u t e r for direct calcu
l a t i o n a n d p r i n t o u t of c o m p o s i t i o n . Such fully
a u t o m a t e d i n s t r u m e n t s a r e of inestimable value for
i n d u s t r i a l l a b o r a t o r i e s r e q u i r e d t o a n a l y z e daily very
large n u m b e r s of specific alloys, c e m e n t s , ceramics,
glasses, a n d so o n , a t m i n i m a l cost.
S p e c t r o m e t e r s for t h e u l t r a l o n g - w a v e l e n g t h region
( ^ 2 n m ) use x-ray g e n e r a t o r s c o m p r i s i n g special wind o wless x-ray t u b e s o p e r a t e d a t u p t o ~ 10 k V a n d t o
~ 500 m A , special p s e u d o c r y s t a l s h a v i n g 2d spacings
of 1 0 - 1 5 n m a n d w i n d o w l e s s d e t e c t o r s , all o p e r a t i n g
in high, clean v a c u u m .
T h e r e a r e relatively lightweight p o r t a b l e w a v e
length-dispersive s p e c t r o m e t e r s t h a t o p e r a t e from
b a t t e r i e s o r g e n e r a t o r s for field a n d e n v i r o n m e n t a l
use, b u t m o s t such a p p l i c a t i o n s use energy-dispersive
spectrometers.
Dynamic process-control spectrometers monitor
a n d c o n t r o l industrial processes, such as plating, ore
p r o c e s s i n g a n d reclaiming of p r e c i o u s m e t a l s . A n xray spectrometer at some point along the production
line m o n i t o r s , say, t i n - p l a t e thickness o n c o n t i n u o u s l y
m o v i n g sheet steel. W h e n t h e m o n i t o r e d x-ray inten
sity falls o u t s i d e previously established limits, the
i n s t r u m e n t either signals a n o p e r a t o r o r adjusts the
p l a t i n g c o n d i t i o n s t o c o r r e c t t h e fault.
9.
Operation
575
X-Ray
Fluorescence
Spectrometry
Q u a n t i t a t i v e analysis is p e r f o r m e d by setting t h e
g o n i o m e t e r at t h e 20 angle of a specified x-ray line,
say c o p p e r . T h e s e a l e r - t i m e r c o u n t s c o p p e r
pulses for a " p r e s e t t i m e " o r times the a c c u m u l a t i o n
of a " p r e s e t c o u n t . " M e a s u r e m e n t s a r e m a d e o n e a c h
s a m p l e a n d o n s t a n d a r d s similar t o t h e s a m p l e s b u t
h a v i n g k n o w n c o m p o s i t i o n . T h e s t a n d a r d d a t a is used
to establish a m a t h e m a t i c a l r e l a t i o n s h i p o r c a l i b r a t i o n
curve of c o p p e r intensity against c o p p e r c o n c e n
t r a t i o n , t o which the s a m p l e intensity d a t a is applied.
Alternatively, t h e intensity d a t a m a y be e n t e r e d in t h e
c o m p u t e r for calculation of c o m p o s i t i o n . T h e s a m e
p r o c e d u r e is followed for the o t h e r s a m p l e elements.
10. Matrix
Effects
11. Specimen
Forms and
Preparation
576
X-Ray
12. Analytical
Methods
Standardization
T h e c a l i b r a t i o n - s t a n d a r d m e t h o d is i m p r o v e d b y
q u a n t i t a t i v e a d d i t i o n t o all s a m p l e s a n d s t a n d a r d s of
a n element h a v i n g excitation, a b s o r p t i o n a n d en
h a n c e m e n t p r o p e r t i e s similar t o t h o s e of t h e a n a l y t e
in t h e p a r t i c u l a r m a t r i x . T h e c a l i b r a t i o n function is
the a n a l y t e / i n t e r n a l - s t a n d a r d intensity r a t i o versus
analyte concentration.
12.3 Standardization
with Scattered X Rays
T h e intensity of a selected w a v e l e n g t h from t h e p r i m
ary rays scattered by t h e specimen is used t o c o r r e c t
a b s o r p t i o n - e n h a n c e m e n t ( a n d o t h e r ) effects. T h e
wavelength m a y be from t h e c o n t i n u u m o r a t a r g e t
line. T h e c a l i b r a t i o n function is a n a l y t e / s c a t t e r e d
intensity r a t i o versus c o n c e n t r a t i o n .
12.4 Matrix-Dilution
Methods
All samples a n d s t a n d a r d s a r e t r e a t e d with a
" d i l u e n t , " which c o n s t i t u t e s a n e w c o n s t a n t m a t r i x .
T h e diluent m a y be a high c o n c e n t r a t i o n of lowa t o m i c - n u m b e r m a t e r i a l , such as a p o w d e r , solvent o r
Microanalysis,
Quantitative
Bibliography
Bertin 1975 Principles and Practice of X-Ray Spectro
metric Analysis, 2nd edn. Plenum, New York
Bertin 1978 Introduction to X-Ray Spectrometric Analy
sis. Plenum, New York
Herglotz , Birks L S (eds.) 1978 X-Ray Spectrometry.
Dekker, New York
Jenkins R 1974 An Introduction to X-Ray Spectrometry.
Heyden, London
Jenkins R, De Vries J L 1969 Practical X-Ray Spectrometry,
2nd edn. Springer, New York
E. P. Bertin
[RCA Laboratories, Princeton,
N e w Jersey, U S A ]
X-Ray
Microanalysis,
Quantitative
/.
ZAF
Corrections
O f t h e v a r i o u s m e t h o d s used t o calculate c o n c e n t r a
tions from net elemental intensities, t h e c o n v e n t i o n a l
Z A F m e t h o d is b y far t h e m o s t widely used for b u l k
specimens. Z A F refers t o t h e s e p a r a t e a t o m i c n u m b e r
Z , a b s o r p t i o n A a n d fluorescence F c o r r e c t i o n s w h i c h
a r e calculated as a function of a n ( a s s u m e d ) c o m p o s i
tion a n d multiplied b y t h e m e a s u r e d intensity r a t i o
( m e a s u r e d intensity divided b y p u r e element intensity
m e a s u r e d u n d e r identical circumstances):
Concentration = (
Intensity \
V P u r e intensity /
578
/
1_
\ ZAF )
X-Ray
2. Other Specimen
Microanalysis,
Quantitative
Figure 1
Example of a Monte Carlo simulation of a few trajectories
for 20 keV electrons in nickel
Geometries
F o r thin specimens, as e n c o u n t e r e d in t h e A E M ,
a b s o r p t i o n is negligible a n d fluorescence d i s a p p e a r s ,
so t h e c o r r e c t i o n p r o c e d u r e is further simplified. O n l y
the relative efficiency with w h i c h different e l e m e n t s
c a n be excited a n d emit characteristic rays a n d t h e
sensitivity of t h e s p e c t r o m e t e r a t different energies
r e m a i n . T h i s c a n be calculated either from f u n d a m e n
tal p a r a m e t e r s o r m e a s u r e d from a s t a n d a r d specimen
( b o t h m e t h o d s h a v e their a d h e r e n t s ) , t o p r o d u c e a
factor relating t h e m e a s u r e d intensity r a t i o s from
different elements t o their c o n c e n t r a t i o n s :
Concentration!
Concentration
Intensity!
2 1
Intensity2
c o p y . Alternatively, s p e c t r a c a n b e o b t a i n e d a t t w o
different accelerating voltages a n d c a l c u l a t i o n used t o
d e t e r m i n e t h e o r i e n t a t i o n angle t h a t gives t h e s a m e
c o m p o s i t i o n a n s w e r for b o t h analyses.
T h e accelerating v o l t a g e is a l w a y s a p a r a m e t e r of
p r i m e i m p o r t a n c e for q u a n t i t a t i v e analysis. W i t h a n
E D s p e c t r o m e t e r , it is best d e t e r m i n e d b y t h e cutoff
p o i n t of t h e c o n t i n u u m b a c k g r o u n d . T h i s is generally
more accurate than any meter on the microscope, and
also t a k e s i n t o a c c o u n t a n y deceleration of t h e elec
tron beam that m a y occur due to sample charging.
3. Monte
Carlo
Modelling
T h e m e t h o d w h i c h is in principle c a p a b l e of dealing
with a n y k i n d of specimen g e o m e t r y is M o n t e C a r l o
m o d e l l i n g . R a t h e r g o o d m o d e l s a r e n o w available for
e a c h of t h e individual processes b y w h i c h m o v i n g
electrons lose energy a n d slow d o w n , a n d excite
characteristic o r c o n t i n u u m rays from a t o m s . By
using c o m p u t e r r a n d o m - n u m b e r g e n e r a t o r s t o s a m p l e
these p r o b a b i l i t y d i s t r i b u t i o n s it is possible t o follow
t h e p a t h s of a statistically useful n u m b e r (typically a t
least several t h o u s a n d , a n d m a n y m o r e in s o m e cases)
of electrons as they scatter from a t o m s in t h e speci
men, encounter various geometric boundaries and
generate rays which can be summed. (Figure 1
s h o w s a n e x a m p l e of a M o n t e C a r l o p l o t of electron
trajectories.) T h i s m e a n s t h a t a n y b o u n d a r y c o n
d i t i o n s , surface o r subsurface irregularities, c o m p o s i
t i o n h e t e r o g e n e i t y o r o t h e r s a m p l e peculiarities c a n be
set u p a n d t h e x-ray yield calculated.
I n practice, this is n o t a g o o d q u a n t i t a t i v e c o r r e c
tion t o o l , for several r e a s o n s . First, t h e calculation
p r o c e e d s from t h e full d e s c r i p t i o n of t h e s a m p l e ,
w h i c h is u n k n o w n , t o t h e x-ray intensities, which c a n
be m e a s u r e d . E x c e p t in simple cases, for instance, the
thickness of a c o a t i n g layer, it is difficult t o iterate the
u n k n o w n p a r a m e t e r s t o achieve a g r e e m e n t . Second,
t h e c o m p u t e r t i m e n e e d e d t o t r a c k e n o u g h electrons
t o o b t a i n g o o d results is n o t trivial. S o m e very useful
simplifications of t h e full M o n t e C a r l o a p p r o a c h h a v e
579
X-Ray
Microanalysis,
Quantitative
4. Dimensions
of
Analysis
F o r h e t e r o g e n e o u s samples o r n o n i d e a l surfaces it is
i m p o r t a n t t o k n o w the d i m e n s i o n s of t h e region in
which the electrons scatter a n d rays a r e g e n e r a t e d .
In thin sections ( A E M ) this is basically a t r u n c a t e d
c o n e , s p r e a d i n g from t h e incident electron b e a m ,
w h o s e angle d e p e n d s u p o n electron voltage a n d t h e
s a m p l e ' s a t o m i c n u m b e r a n d density. W h i l e t h e m e a n
d i a m e t e r of the a n a l y z e d v o l u m e c a n be very small
(less t h a n 50 n m ) for thin specimens, this is often still
i n a d e q u a t e t o analyze selectively individual precipi
tates a n d inclusions. T h e m a t r i x is included in t h e
excited region a n d m a k e s q u a n t i t a t i v e analysis diffi
cult if n o t impossible. Physical s e p a r a t i o n of t h e
features of interest from t h e m a t r i x , for e x a m p l e , with
a n e x t r a c t i o n replica, is s o m e t i m e s a practical solu
tion. In analyzing small features in thin specimens, the
use of extremely small electron b e a m s (to achieve t h e
best possible spatial resolution) p r o d u c e s very low
c o u n t rates, w h i c h m a k e s a n y e x t r a n e o u s b a c k g r o u n d
d u e t o electron scattering in t h e m i c r o s c o p e , for
instance, m o r e i m p o r t a n t , a n d also restricts a c c u r a c y
because of limited c o u n t i n g statistics.
In b u l k samples, subsurface s t r u c t u r e s m a y be
invisible in t h e S E M i m a g e b u t still c o n t r i b u t e t o t h e
analysis. T h e excited region is generally described as a
t e a r d r o p o r sphere. T h e p r o b a b i l i t y of electron scat
tering d e p e n d s o n a t o m i c n u m b e r (the c h a r g e o n t h e
nucleus) so t h a t the s h a p e of t h e excited v o l u m e
b e c o m e s m o r e flattened ( b r o a d c o m p a r e d t o its d e p t h )
for h i g h - Z specimens, a n d conversely b e c o m e s d e e p e r
c o m p a r e d t o its b r e a d t h for l o w - Z specimens. T h e
electron r a n g e d e p e n d s p r i m a r i l y o n t h e electron
580
Figure 2
Schematic diagram of the variation in size and shape of
the electron excited region with specimen atomic number
and electron accelerating voltage
X-Ray
Bibliography
Heinrich F J 1981 Electron Beam X-Ray Microanalysis.
Van Nostrand Reinhold, New York
Heinrich F J, Newbury D E, Yokowitz (eds.) 1976 Use
of Monte-Carlo Calculations in Electron Probe Microana
lysis and Scanning Electron Microscopy, National Bureau
of Standards Special Publication 460. US Department of
Commerce, Washington, DC
Russ J C 1984 Fundamentals of Dispersive X-Ray Analysis.
Butterworth, London
Scott V D, Love G 1983 Quantitative Electron Probe Mic
roanalysis. Ellis Horwood, Chichester, UK
Vollath D 1986 Some fundamental considerations to pre
cede image analysis. Bull. Mater. Sci. (India) 8: 169-82
J. C. R u s s
[ N o r t h C a r o l i n a State University,
Raleigh, N o r t h C a r o l i n a , U S A ]
Diffraction
m e t h o d . H o w e v e r , as in all analytical m e t h o d s it is
advisable w h e n e v e r possible t o s u p p l e m e n t x-ray in
f o r m a t i o n with d a t a from related m e t h o d s such a s
electron m i c r o s c o p y , x-ray fluorescence s p e c t r o s c o p y
a n d electron m i c r o p r o b e analysis.
T h e principal uses of t h e x-ray p o w d e r m e t h o d a r e :
(a)
(b)
distinguishing b e t w e e n m i x t u r e s , v a r i o u s types
of solid s o l u t i o n s a n d p o l y m o r p h s ;
(c)
distinguishing b e t w e e n t h e a m o r p h o u s a n d crys
talline states;
(d)
precision m e a s u r e m e n t o f lattice p a r a m e t e r s a n d
thermal expansion;
(e)
(f)
(g)
d e t e r m i n a t i o n of p h a s e s a n d p r o p e r t i e s as a
function of specimen e n v i r o n m e n t either in situ
o r after t r e a t m e n t a t t e m p e r a t u r e s from liquid
helium t o a b o u t 2000 C, a n d pressures u p t o
several h u n d r e d k b a r , in air, v a c u u m o r selected
gas.
Powder
1. Basis of
Method
(1)
2 0 = 2 s i n - [ A / 2 ^ / )]
(2)
581
X-Ray
Powder
Diffraction
CuKa,
rays a t 28.44 (20), from
which
d{lu) = 0.31357 n m . T h e second o r d e r d o e s n o t o c c u r
because of t h e lattice s y m m e t r y of the silicon a n d the
= 0.10453 n m . In
third o r d e r = 3 is a t 94.95
333)
is used instead of
crystallographic w o r k (hkl) =
= 3.
T h e relative intensities of the reflections a r e given
by
I,(hkl)
,|2
=
'
( 1+
cos-
K s i n 2 0 s i n
2 0 '\
2
)
(in:
Si ( 2 2 0 )
Si (311) --
D(220)
Si (422)
Si ( 4 0 0 ) | ? i (331)
0 (311J
(
(b)
|"">
(220)
(311)
(200)
(40
l ?2 2) )2
0)(33)
(422)
I
|(420) '
(I00).j
(C )
002)
(101)
(110)
(103) J
(112)
(102)
(300)
30
40
50
60
70
80
90
29
Figure 1
X-ray powder diffraction patterns of substances with
similar atomic arrangements: (a) silicon and diamond,
(b) sphalerite (face-centered-cubic ZnS), and (c) wurtzite
(hexagonal ZnS). The dashed lines connect the common
fundamental reflections
(4)
582
(III)
...
Si
(a)
2. Instrument
and Experimental
Methods
X-Ray
3. Phase
12.398
2nne.E,hkl)
Diffraction
s o r t e d i n t o n a r r o w energy c h a n n e l s b y t h e pulse
height analyzer. T h e Si(Li) crystal d e t e c t o r m u s t be
k e p t a t l i q u i d - n i t r o g e n t e m p e r a t u r e a t all times.
T h e r e is n o need for s c a n n i n g b e c a u s e all the
reflections a r e r e c o r d e d s i m u l t a n e o u s l y . T h e m e t h o d
h a s t h e a d v a n t a g e t h a t a recognizable p a t t e r n (with
low statistical a c c u r a c y ) c a n be o b t a i n e d in less t h a n a
m i n u t e with a c o n v e n t i o n a l x-ray t u b e , o r in a few
s e c o n d s with a s y n c h r o t o n x-ray b e a m ; f u r t h e r m o r e ,
since there a r e n o m o v i n g p a r t s , specimen devices for
h e a t i n g a n d c o o l i n g a r e relatively easy t o m a k e .
H o w e v e r , t h e r e s o l u t i o n , w h i c h is d e t e r m i n e d by t h e
d e t e c t o r , is m o r e t h a n o n e o r d e r of m a g n i t u d e lower
t h a n t h a t of a s c a n n i n g diffractometer, a n d t h e p e a k t o - b a c k g r o u n d r a t i o m u c h lower, m a k i n g it useful
only for t h e simple p a t t e r n s .
C o n s i d e r a b l e c a r e is r e q u i r e d t o p r e p a r e speci
m e n s for x-ray diffraction. O n l y t h e surface layer of
thickness d e t e r m i n e d b y t h e a b s o r p t i o n c o n t r i b u t e s t o
t h e diffraction, a n d therefore h o m o g e n e i t y , flatness,
p a c k i n g a n d similar factors a r e i m p o r t a n t in s a m p l e
p r e p a r a t i o n . T h e specimen s h o u l d b e a b o u t 1-2 c m in
d i a m e t e r , a l t h o u g h smaller specimens c a n b e used.
T h e crystallites s h o u l d b e small, preferably less t h a n
a b o u t 20 , a n d t h e specimen r o t a t e d a b o u t 70 r p m
a r o u n d a n axis n o r m a l t o t h e surface t o o b t a i n g o o d
values of t h e relative intensities. T h e p o w d e r m a y be
c e m e n t e d with a 5 % s o l u t i o n of a m y l a c e t a t e in
c o l l o d i o n , o r with vaseline t o a glass slide, a shallow
cylindrical h o l d e r o r single-crystal p l a t e c u t in a
direction t h a t d o e s n o t p r o d u c e a reflection in t h e
a n g u l a r r a n g e r e c o r d e d [e.g., silicon (510)]. F i l m s a s
thin as 3 0 - 4 0 n m c a n be a n a l y z e d if they a r e well
crystallized.
Figure 2
Geometry of the x-ray powder diffractometer in the
focusing plane: F, line focus of x-ray tube; PS, parallel foil
assembly to limit divergence in plane of drawing; DS,
divergence slit; Sp, specimen; O, diffractometer axis of
rotation; , Bragg angle; RS, receiving slit; AS, antiscatter
slits; M, curved crystal monochromator; D, scintillation or
proportional counter; SpFC, specimen focusing circle
(radius varies with 0); DC, diffractometer circle with 20
scale; MFC, monochromator focusing circle
Powder
( 5
Identification
583
X-Ray
Powder
Diffraction
p r o g r a m s use selectable t e r r o r w i n d o w s , a u t o m a t i c
d a t a c o r r e c t i o n with internal s t a n d a r d s , chemicald a t a prescreening a n d o t h e r o p t i o n s t o facilitate the
identification, a n d c o m p u t e a figure of merit w h i c h
gives the " g o o d n e s s of fit" of the u n k n o w n c o m p a r e d
with each of the selected p o t e n t i a l s t a n d a r d s . T h e
c o m p u t e r also displays the p a t t e r n s of the u n k n o w n
with each of the selected s t a n d a r d s for direct visual
c o m p a r i s o n . (All the p o w d e r p a t t e r n s in this article
are c o m p u t e r - g e n e r a t e d . ) It is n o w possible t o collect
the d a t a , reduce it t o a set of d a n d / values a n d
identify the c o n s t i t u e n t s of a n a v e r a g e m a t e r i a l in 1 0 20 m i n . If a user file is m a d e with a g r o u p of m a t e r i a l s
likely t o be f o u n d in a p a r t i c u l a r type of a p p l i c a t i o n ,
identification time is greatly reduced because the size
of the s t a n d a r d file is m u c h smaller a n d its q u a l i t y c a n
be controlled.
T h e r e are a large n u m b e r of a p p l i c a t i o n s of the
p o w d e r m e t h o d based o n p h a s e identification. A
typical l a b o r a t o r y use is t o follow the c o u r s e of a
solid-state chemical r e a c t i o n which c a n n o t be per
formed by chemical analysis b e c a u s e the b a t c h
c o m p o s i t i o n r e m a i n s the s a m e . F o r e x a m p l e , large
single-crystal b o u l e s of G d 3 G a 5 0 1 2, g a r n e t are used as
substrates for m a g n e t i c b u b b l e devices. T h e i r g r o w t h
requires a starting g a r n e t p o w d e r p r e p a r e d by sinter
ing a blend of G d 2 0 3 a n d G a 2 0 3 in p r o p e r p r o p o r t i o n s
to the correct t e m p e r a t u r e .
T h e p a t t e r n s required for this analysis were m a d e
with a m i n i c o m p u t e r - a u t o m a t e d diffractometer (see
Fig. 3). T h e u p p e r p a t t e r n is the s t a r t i n g oxide mix
ture blend a n d the tick m a r k s a r e the p e a k p o s i t i o n s .
T h e following t w o p a t t e r n s are the s t a n d a r d s identi
fied by c o m p u t e r s e a r c h - m a t c h : the cubic form of aG d 2 0 3 a n d the m o n o c l i n i c / ? - G a 2 0 3 . T h e intensities in
b o t h s t a n d a r d s h a v e been scaled by the c o m p u t e r t o
a p p r o x i m a t e t h o s e in the blend. T h o s e p e a k s m a t c h
ing the blend a r e identified by the lower set of tick
m a r k s . T h e e x p a n d e d p a t t e r n (Fig. 3b) s h o w s the
partially c o m p l e t e d c o n v e r s i o n t o g a r n e t a n d the
small a m o u n t of residual / ? - G a 2 0 3 indicates the cor
rect sintering c o n d i t i o n s h a v e a l m o s t been r e a c h e d .
T h e m a x i m u m n u m b e r of p h a s e s t h a t c a n be identi
fied in a specimen d e p e n d s o n the complexity of the
p a t t e r n s a n d the degree of o v e r l a p p i n g . Profile fitting
c a n be used t o s e p a r a t e the o v e r l a p p i n g reflections
a n d t o d e t e r m i n e the individual intensities (Parrish
a n d H u a n g 1979). M i x t u r e s of six p h a s e s c a n b e
p e r f o r m e d routinely with c o m p u t e r m e t h o d s .
T h e m i n i m u m a m o u n t of a p h a s e t h a t is detectable
in a m i x t u r e is d e p e n d e n t o n the a b s o r p t i o n , crystalli
nity a n d p e a k - t o - b a c k g r o u n d r a t i o s . T h e lower limits
r a n g e from a b o u t 0 . 1 - 5 w t % . Very small a m o u n t s of
a sample (in the m i c r o g r a m r a n g e ) c a n be detected,
b u t even smaller samples require special t e c h n i q u e s
using high-brilliance r o t a t i n g - a n o d e x-ray t u b e s .
Q u a n t i t a t i v e d e t e r m i n a t i o n of t h e c o n c e n t r a t i o n of
each p h a s e in a m i x t u r e requires careful specimen
p r e p a r a t i o n a n d m e a s u r e m e n t s of a few of the higher-
584
Oxide
mixture
ci-
Ll
J-
.A,
G d 20 3
, A,
> . A ,..-
/ 3 - G a 20 3
...
30
, 6 A A
. A
40
50
<
I
26
32
G A
38
20
Figure 3
Patterns of (a) mixed blend of two oxides and the phases
identified by computer search-match, and (b) after
sintering showing conversion to garnet Gd 3Ga 50 12 (G) and
residual -Ga 20 3(A) and a-Gd 2Q 3(D)
X-Ray
4. Lattice-Parameter
Powder
Diffraction
Determination
T h e lattice p a r a m e t e r a0 is frequently r e q u i r e d in
m a t e r i a l s c h a r a c t e r i z a t i o n . A n u m b e r of reflections
s h o u l d be m e a s u r e d a n d their relation t o a0 is given by
E q n . (4). Careful e x p e r i m e n t a l t e c h n i q u e s m u s t be
used t o o b t a i n a c c u r a t e values. S y s t e m a t i c e r r o r s are
t h e p r i n c i p a l c a u s e of low a c c u r a c y a n d they c a n be
m i n i m i z e d by using h i g h e r - a n g l e reflections. T h e r e a r e
t w o basic r e a s o n s for this: (a) i n s t r u m e n t a l a b e r r a
t i o n s a n d specimen d i s p l a c e m e n t e r r o r s increase
r a p i d l y with decreasing reflection angle, a n d (b) the
h i g h e r t h e reflection angle t h e g r e a t e r t h e a c c u r a c y , as
s h o w n b y t h e differential f o r m of t h e B r a g g e q u a t i o n :
Figure 4
X-ray diffractometer pattern of a small quantity of
crystalline quartz (two peaks) on a glass substrate
c h a n g e s in t h e lattice p a r a m e t e r a0 if t h e s u b s t i t u t i n g
a t o m s h a v e different sizes. T h e r e is a very r o u g h linear
relation b e t w e e n c o m p o s i t i o n a n d a0 a n d t h e c o m p o
sition m a y b e d e t e r m i n e d from t h e shifts in p e a k
positions. The substituting atoms are randomly
a r r a n g e d o n t h e lattice sites, b u t in s o m e cases p r o p e r
annealing may produce a long-range order which can
be detected b y t h e a p p e a r a n c e of a d d i t i o n a l p e a k s
called s u p e r s t r u c t u r e reflections. T h e y a r e generally
m u c h w e a k e r t h a n t h e f u n d a m e n t a l reflections a n d
d e p a r t u r e s from perfect l o n g - r a n g e o r d e r further
w e a k e n s t h e m . Interstitial a n d defect types of solid
solutions m a y b e detected b y c o m p a r i n g t h e m e a s u r e d
density with t h e density c a l c u l a t e d from t h e unit-cell
volume.
T h e crystalline a n d a m o r p h o u s states c a n be readily
distinguished. A n a m o r p h o u s solid h a s only local
short-range order without the repeating long-range
lattice o r d e r characteristic of t h e crystalline state. T h e
diffraction from a n a m o r p h o u s s u b s t a n c e is a b r o a d
h u m p e x t e n d i n g o v e r a w i d e a n g u l a r r a n g e as s h o w n
b y t h e p a t t e r n of a m i c r o s c o p e slide ( F i g . 4). If t h e
m a t e r i a l c o n t a i n s a crystalline p o r t i o n o r begins t o
devitrify, t h e crystalline p a t t e r n is s u p e r i m p o s e d as
illustrated b y t h e a d d i t i o n of a few m i c r o g r a m s of
q u a r t z p o w d e r o n t o t h e slide. T h e crystalline p e a k
intensities a r e m u c h higher a n d t h e (101) reflection of
the s a m e m a s s of q u a r t z w o u l d b e a b o u t 260 times
higher t h a n t h e t o p of t h e a m o r p h o u s b a n d . M o s t
a m o r p h o u s p a t t e r n s a r e similar a n d c a n n o t b e used t o
identify m a t e r i a l s . R a d i a l d i s t r i b u t i o n functions c a n
be derived t o d e t e r m i n e local a t o m i c a r r a n g e m e n t s
( W a r r e n 1969). C r y s t a l l i n e - t o - a m o r p h o u s weight
ratios m a y be a p p r o x i m a t e l y d e t e r m i n e d f r o m t h e
relative intensities of all t h e crystalline reflections a n d
the a m o r p h o u s p a r t . T h i s usually requires s t a n d a r d s
of k n o w n r a t i o s . H o w e v e r , if p o o r l y crystallized
m a t e r i a l is p r e s e n t t h e d e t e r m i n a t i o n b e c o m e s m u c h
m o r e difficult o r impossible.
Ad/d=
-A0cos 0
(6)
585
X-Ray
Powder
Diffraction
5. Preferred
Orientation
N o n r a n d o m d i s t r i b u t i o n of crystallites in a m a t e r i a l is
called preferred o r i e n t a t i o n o r t e x t u r e . It m a y result
from t h e m e t h o d of p r e p a r a t i o n a n d c a n m a r k e d l y
affect t h e p r o p e r t i e s . F o r e x a m p l e , t h e crystallites in a
c o l d - d r a w n wire orient w i t h t h e s a m e c r y s t a l l o g r a p h i c
direction parallel t o t h e wire axis, a n d in rolled m e t a l
sheets certain p l a n e s orient parallel t o t h e surface a n d
t h e rolling direction w h e n t h e grains r o t a t e a n d align
d u r i n g t h e plastic d e f o r m a t i o n . Preferred o r i e n t a t i o n
also o c c u r s in castings, electrochemical d e p o s i t i o n
a n d t h i n films. T h e degree of preferred o r i e n t a t i o n c a n
be d e t e r m i n e d with a pole-figure device a t t a c h e d t o
t h e diffractometer t o m e a s u r e intensities for different
specimen o r i e n t a t i o n s . T h e intensities c a n b e p l o t t e d
o n a s t e r e o g r a p h i c projection a n d c o n t o u r e d t o s h o w
t h e a n g u l a r d i s t r i b u t i o n of t h e n o r m a l s t o selected
lattice p l a n e s in v a r i o u s c r y s t a l l o g r a p h i c directions.
Such p l o t s a r e used t o follow s t r u c t u r a l c h a n g e s in
metallurgical m a t e r i a l s subjected t o m e c h a n i c a l a n d
t h e r m a l processes.
(b)
Figure 5
(a) Method for precision lattice-parameter measurement of
single-crystal plate and mismatch of epitaxial film on
substrate by parallel double-crystal method, and
(b) profiles of pair of films F and C on substrate S
uses a n o n d i v e r g e n t m o n o c h r o m a t i c b e a m from a
high-quality g a r n e t wafer C 2 m o u n t e d a p p r o x i m a t e l y
parallel t o C I , d e t e c t o r D l is m o v e d t o , a n d t h e
specimen C I r o t a t e d t o pick u p t h e reflections s h o w n
in the lower p a r t of Fig. 5. (In p r a c t i c e C I a n d C 2 c a n
be i n t e r c h a n g e d . ) T h e e x a m p l e s h o w n is a p a i r of
films F a n d C of different c o m p o s i t i o n s g r o w n o n t h e
s u b s t r a t e S with lattice p a r a m e t e r s of F > S > C . T h e
p e a k s e p a r a t i o n of C a n d S is 112" ( c o r r e s p o n d i n g t o
4
Aa/a = 2.1 x 10~ ) a n d b e t w e e n F a n d S is
4
76" = 2.2 x 1 0 " from which t h e m e a n strain in e a c h
film c a n be calculated. T h e large difference in a0
between film F d e p o s i t e d o n film C c a u s e d a s y m m e t
ric b r o a d e n i n g of t h e F profile i n d i c a t i n g n o n u n i f o r m
strain. T h i s is a n e x a m p l e of t h e u n i q u e analytical
capabilities of x-ray diffraction in which t h e indi
vidual p r o p e r t i e s of physically s u p e r i m p o s e d m a t e r
ials c a n be d e t e r m i n e d .
586
Imperfections
X-Ray
84
85
86
87
88
1
89
20
Figure 6
X-ray diffractometer reflection profiles of Pd(222) thin
film broadened by strain and standard well-crystallized
powder W(220); peak intensities normalized
Powder
Diffraction
X - r a y m e t h o d s a r e used a s a n o n d e s t r u c t i v e
m e t h o d t o d e t e r m i n e residual elastic strains. A l
t h o u g h t h e elastic c o n s t a n t s v a r y c o n s i d e r a b l y with
c r y s t a l l o g r a p h i c d i r e c t i o n they a r e r o u g h l y i s o t r o p i c
in r a n d o m polycrystalline m a t e r i a l s . U s i n g small xr a y b e a m s , s t r a i n s c a n b e m e a s u r e d in small a r e a s a n d
steep s t r a i n g r a d i e n t s c a n b e d e t e r m i n e d . T h e m e t h o d
is b a s e d o n t h e fact t h a t t h e lattice s p a c i n g d{hkl,
c h a n g e s w i t h a p p l i e d stress a n d acts a s a n i n t e r n a l
s t r a i n g a u g e . U n i f o r m l o n g - r a n g e tensile strain in
creases t h e d values a n d shifts t h e p e a k s t o smaller
angles w i t h o u t b r o a d e n i n g . N o n u n i f o r m s t r a i n s c a u s e
b r o a d e n i n g w i t h o u t shifts. B o t h elastic a n d plastic
d e f o r m a t i o n strains c a u s e shifts a n d b r o a d e n i n g .
W h e n t h e d i m e n s i o n s of crystallites a r e less t h a n
a b o u t 1 t h e profiles begin t o b r o a d e n a n d t h e
b r o a d e n i n g increases w i t h d e c r e a s i n g size. B o t h size
a n d strain b r o a d e n i n g c a n b e m e a s u r e d w h e n they
coexist b y u s i n g t h e F o u r i e r m e t h o d a n d several
o r d e r s o f a reflection; t h e size factor is i n d e p e n d e n t of,
a n d t h e d i s t o r t i o n d e p e n d e n t o n , t h e o r d e r of t h e
reflection.
A simplified m e t h o d frequently used t o d e t e r m i n e
small crystallite sizes a s s u m e s t h e r e a r e n o strains o r
o t h e r sources of line b r o a d e n i n g . It uses t h e Scherrer
equation:
=
cos 0 ^ B( 2 0 )
w h e r e t{hkl) is t h e a v e r a g e d i m e n s i o n o f t h e crystallites
n o r m a l t o t h e (hkl) diffracting p l a n e , k is a c o n s t a n t
usually t a k e n a s 0.9, is t h e w a v e l e n g t h ( n m ) 0
t h e B r a g g angle a n d PB (2) t h e particle size line
b r o a d e n i n g in r a d i a n s m e a s u r e d a s t h e full-width
h a l f - m a x i m u m ( F W H M ) . (2) is o b t a i n e d from
>
>
/ B(2^) = [ / O ^ ) - ^ S T ( 2 ^ ) ]
1 /2
(8)
w h e r e P0 (20) is t h e w i d t h o f t h e m e a s u r e d profile a n d
PST(29) t h e w i d t h of t h e i n s t r u m e n t function profile.
F o r a given t t h e b r o a d e n i n g increases a s l / c o s 0 ,
b u t t h e intensities decrease w i t h increasing 2 a n d
d e c r e a s i n g r, m a k i n g it m o r e difficult t o m a k e accur
a t e m e a s u r e m e n t s . I n p r a c t i c e t h e useful r a n g e of t h e
m e t h o d is a b o u t 5 - 3 0 0 n m . A l t h o u g h t c a n b e deter
m i n e d for several d i r e c t i o n s b y u s i n g different (hkl)
p l a n e s , it is desirable t o u s e s c a n n i n g electron m i c r o s
c o p y t o d e t e r m i n e t h e m o r p h o l o g y b e c a u s e if t h e
particles a r e needles o r p l a t e s t h e results c o u l d b e in
e r r o r . T h e t w o m e t h o d s a r e c o m p l e m e n t a r y since t h e
x-ray m e t h o d gives t h e a v e r a g e crystallite size a n d t h e
m i c r o s c o p e t h e particle size, w h i c h m a y b e clusters of
crystallites.
Diffuse s c a t t e r i n g within a few degrees o f t h e direct
b e a m (small-angle diffraction) is a m e t h o d used for
particle size d e t e r m i n a t i o n typically from a few n a n o
m e t e r s t o tens o f n a n o m e t e r s . It is a p p l i c a b l e t o
a m o r p h o u s a s well a s crystalline m a t e r i a l s , a n d is used
for a n a l y z i n g s u s p e n s i o n s , single-chain d i m e n s i o n s of
587
X-Ray
Powder
Diffraction
Bibliography
Azaroff L V, Buerger J 1958 The Powder Method in XRay Crystallography. McGraw-Hill, New York
Barrett C S, Massalski 1966 Structure of Metals:
Crystallographic Methods, Principles and Data, 3rd edn.
McGraw-Hill, New York
Guinier A 1956 Theorie et Technique de la Radiocristallographie. Dunod, Paris
International Tables for X-Ray Crystallography
1969.
Kynoch, Birmingham, UK
Klug , Alexander L 1974 X-Ray Diffraction Proced
ures for Poly crystalline and Amorphous Materials, 2nd
588
X-Ray Absorption Spectroscopy:
EXAFS and XANES Techniques
X - r a y spectroscopies, in v a r i o u s forms, h a v e l o n g
been exploited for s t u d y i n g t h e electronic a n d crystallographic s t r u c t u r e of solids. M o s t extensively uti
lized, of c o u r s e , a r e diffraction t e c h n i q u e s e m p l o y e d
for the p u r p o s e of e x t r a c t i n g c r y s t a l l o g r a p h i c infor
m a t i o n . H o w e v e r , x-ray a b s o r p t i o n studies a r e cur
rently experiencing a s t r o n g surge of scientific interest
resulting from recent i m p o r t a n t a d v a n c e s , b o t h in
theoretical u n d e r s t a n d i n g a n d in e x p e r i m e n t a l c a p a
bility. E x p e r i m e n t a l l y , t h e E X A F S (extended x-ray
a b s o r p t i o n fine structure) a n d X A N E S (x-ray a b s o r p
tion near-edge fine s t r u c t u r e ) techniques a r e dis
tinguished simply b y their spectral r a n g e s ( m e a s u r e d
relative t o a n x-ray a b s o r p t i o n edge). T h e distinction
is m a d e since x-ray-induced electronic excitations in
the vicinity of t h e edge involve c o n s i d e r a t i o n s t h a t a r e
s o m e w h a t different from t h e m o r e energetic p r o
cesses. Oscillatory s t r u c t u r e in t h e x-ray a b s o r p t i o n
coefficient t h a t m a y b e o b s e r v e d in t h e higher spectral
r a n g e (40 eV ^ hv ^ 1000 eV a b o v e t h e edge) is called
E X A F S , while X A N E S refers t o t h e s t r u c t u r e in t h e
i m m e d i a t e vicinity of t h e edge (i.e., for hv ^ 50 eV
a b o v e t h e edge). T h e s e x-ray a b s o r p t i o n t e c h n i q u e s
h a v e u n i q u e capabilities a n d a r e being used t o s t u d y a
wide variety of c o m p l e x m a t e r i a l s . Studies of a m o r
p h o u s m a t e r i a l s , catalysts, biological m a t e r i a l s a n d
solutions h a v e been r e p o r t e d .
I n this article, t h e u n d e r l y i n g theoretical c o n c e p t s
of E X A F S a n d X A N E S a r e outlined a n d recent
experimental a d v a n c e s a r e discussed. A d v a n t a g e s a n d
limitations of t h e x-ray a b s o r p t i o n spectroscopies,
a n d types of p r o b l e m s m o s t suited for these tech
niques, will b e discussed. M o r e detailed discussions
are available in literature reviews, a n d t h e extensive
review b y Lee et al. (1981) is particularly r e c o m
m e n d e d t o t h e interested reader.
1. Theory
and Comparison
with
()\(/\}\ ()
*(*) = Z^jH)f(k)sm[2krj
)]
j
2
(2)
1.6,-
Experiment
W i t h i n t h e electric dipole a p p r o x i m a t i o n , t h a t p a r t of
the a b s o r p t i o n coefficient resulting from p h o t o e m i s sion from a core state is given b y
2
0.7h
0)
8500
9000
Energy
(eV)
Figure 1
The absorption coefficient (multiplied by the thickness
JC) of nickel as a function of energy at 38
555
X-Ray
Absorption
Spectroscopy:
EXAFS
and XANES
Ac
(b)
Figure 2
(a) The EXAFS spectrum, kx{k) vs k, and (b) the radial
distribution function, ^(r) vs r, for nickel at 38 K. The
numbers in parentheses are the number of atoms per shell,
indicated at the known shell distances
w h e r e r} is t h e d i s t a n c e from t h e c e n t r a l ( a b s o r b e r )
a t o m t o t h e yth shell of a t o m s , Nj is t h e n u m b e r of
a t o m s in the shell, is a D e b y e - W a l l e r - l i k e factor
which m e a s u r e s t h e a i s o r d e r of t h e a t o m s in t h e yth
shell relative t o t h e central a t o m a n d is a m e a n free
p a t h , e s t i m a t e d t o be 3.5-5 A. T h e a m p l i t u d e function
ffi) a n d t h e p h a s e function ) c a n be calculated
theoretically o r d e t e r m i n e d empirically from c o m
p o u n d s of k n o w n s t r u c t u r e . I n principle, therefore,
the p a r a m e t e r s Np rp cr, a n d c a n b e d e t e r m i n e d
for the first few n e a r - n e i g h b o r shells. I n practice,
however, there a r e limits o n t h e n u m b e r of p a r a m e t e r s
t h a t c a n be i n d e p e n d e n t l y d e t e r m i n e d a n d also o n t h e
a c c u r a c y of t h e d e t e r m i n a t i o n s . In m a n y cases, dis
tances between the central a t o m a n d t h e first shell of
s u r r o u n d i n g n e i g h b o r s in a n u n k n o w n m a t e r i a l c a n
be d e t e r m i n e d t o 0 . 0 1 A, a n d t h e n u m b e r of first
n e a r n e i g h b o r s c a n be m e a s u r e d t o b e t t e r t h a n 2 0 %
accuracy.
Analysis of E X A F S spectra is c o n s i d e r a b l y a i d e d
by calculating t h e F o u r i e r t r a n s f o r m of kx(k).
Because of the special form of E q n . (2), t h e F o u r i e r
t r a n s f o r m of kx(k) is a p a r t i c u l a r l y useful inter
p r e t a t i o n . T h e t r a n s f o r m #?(r) is a r a d i a l - d e p e n d e n t
function t h a t a p p r o x i m a t e l y m e a s u r e s the spatial dis
t r i b u t i o n of b a c k s c a t t e r i n g a t o m s relative t o t h e cen
556
Techniques
(A)
Figure 3
The uranium L-edge radial-distribution function, <p(R) vs
R, for a 0.02 molar uranium aqueous solution
X-Ray
Absorption
2. Experimental
Considerations
Spectroscopy:
EXAFS
and XANES
CaO
: V / \ ^ L o T i 0 3_
V.
;
/ / ^ \
Techniques
MnO
f.
Fe0 M
5 q Q 05
LaMn03
w / /
L
/ : ^ \
'
J*
(b)
A^CeVO^
N d/ 0 > M
5 o
At
^ l
T5 i 0
r\
_ 0
C O A I 2O 4
\ ^
Pi
NiO
.*
(a)
CoO
1 1 1 1 1 1 1 1 1
'
1
Ve
1 1 1 1 1 1
IA\
Energy
Figure 4
K-edge XANES spectra for (a) perovskites,
(b) monoxides, (c) zircon-type oxides and (d) spinels
557
X-Ray
Absorption
Spectroscopy:
EXAFS
and XANES
3. Strengths
and Weaknesses
of EXAFS
and
XANES
E X A F S is a t e c h n i q u e t h a t is p r i m a r i l y useful for
measuring crystallographic structure parameters. The
m e a s u r e m e n t is a t o m specific, p r o v i d i n g a local r a d i a l
d i s t r i b u t i o n function for t h o s e a t o m s d i s t r i b u t e d
a b o u t the central ( a b s o r b e r ) a t o m .
F o r simple systems with l o n g - r a n g e o r d e r , a c c u r a
cies in t h e s t r u c t u r a l p a r a m e t e r s achievable w i t h
E X A F S a r e inferior t o t h o s e achievable using diffrac
tion t e c h n i q u e s p r o v i d i n g t h a t t h e m a t e r i a l s a r e n o n dilute. E X A F S plays t h e m o r e i m p o r t a n t role in
o b t a i n i n g s t r u c t u r a l i n f o r m a t i o n for a m o r p h o u s
m a t e r i a l s , solutions a n d dilute systems of v a r i o u s
k i n d s (such as h e t e r o g e n e o u s catalysts, biological
m a t e r i a l s a n d i m p u r i t y a t o m s in crystalline solids).
X A N E S is a spectroscopic t o o l useful for p r o b i n g
the u n o c c u p i e d electron states within 50 eV of t h e
F e r m i level. By m o n i t o r i n g a b s o r p t i o n edges associ
a t e d with different c o r e levels, electric dipole selection
rules c a n be used t o a d v a n t a g e in identifying e m p t y
states of specific a n g u l a r m o m e n t u m c h a r a c t e r . A s a
tool for p r o b i n g these e m p t y electron states, X A N E S
c o m p l e m e n t s a n u m b e r of o t h e r spectroscopies (such
as b r e m s s t r a h l u n g i s o c h r o m a t s p e c t r o s c o p y , u l t r a
558
Techniques
violet
photoemission
and
optical
reflectivity).
X A N E S c a n b e used a s a m a t e r i a l s c h a r a c t e r i z a t i o n
t o o l . N o v a c u u m is r e q u i r e d for these m e a s u r e m e n t s
(a significant e x p e r i m e n t a l convenience) a n d , often,
m a t e r i a l s with very low c o n c e n t r a t i o n of a b s o r b e r c a n
be studied w i t h ease.
E X A F S a n d X A N E S a r e , in a certain sense, redis
covered spectroscopies. T h e p h e n o m e n a h a v e b e e n
k n o w n for d e c a d e s , b u t only recently h a v e a d v a n c e s
in theoretical u n d e r s t a n d i n g a n d i n s t r u m e n t d e v e l o p
m e n t b e e n a d e q u a t e t o d e m o n s t r a t e t h e p r o m i s e of
t h e spectroscopies for m a t e r i a l s studies.
See also: X-Ray and Neutron Diffraction Studies of Amor
phous Solids; X-Ray Powder Diffraction
Bibliography
Lee A, Citrin , Eisenberger , Kincaid 1981
Extended x-ray absorption fine structure: its strengths
and limitations as a structural tool. Rev. Mod. Phys. 53:
769-806
Maylotte D H, Wong J, St Peters R L, Lytle L W, Greegor
R 1981 X-ray absorption spectroscopic investigation of
trace vanadium sites in coal. Science 214: 554-6
Sayers D E, Stern A, Lytle F W 1971 New technique for
investigating noncrystalline structures: Fourier analysis
of the extended x-ray absorption fine structure. Phys. Rev.
Lett. 27: 1204-7
Stern A (ed.) 1980 Workshop on Laboratory EXAFS
Facilities and Their Relation to Synchroton Radiation
Sources, AIP Conference Proceedings No. 64. American
Institute of Physics, New York
G . S. K n a p p a n d B. W . Veal
[Argonne National Laboratory,
A r g o n n e , Illinois, U S A ]
X-Ray
and Neutron
Diffraction
Studies
of Amorphous
Solids
r e g e n e r a t i o n of t h e u n d e r l y i n g t h r e e - d i m e n s i o n a l
s t r u c t u r e c a n never be u n i q u e . T h u s , diffraction s t u d
ies of a m o r p h o u s solid s t r u c t u r e s fall n a t u r a l l y i n t o
t w o stages: t h e a c t u a l e x p e r i m e n t c u l m i n a t i n g in t h e
d e r i v a t i o n of a real-space c o r r e l a t i o n function, a n d
the i n t e r p r e t a t i o n of this c o r r e l a t i o n function in t e r m s
of a t h r e e - d i m e n s i o n a l s t r u c t u r e .
/.
The Real-Space
Correlation
Function
T h e s t r u c t u r e s of simple c o v a l e n t crystalline a n d
a m o r p h o u s solids a r e c o m p a r e d schematically in t w o
d i m e n s i o n s in Fig. 1. F o r t h e crystal, t h e s t r u c t u r e
m a y b e specified in t e r m s of a u n i t cell a n d t r a n s l a tional s y m m e t r y , t h e latter leading t o t h e s h a r p B r a g g
p e a k s which a r e characteristic of t h e diffraction p a t
tern of crystalline solids. T h e s t r u c t u r e of a n a m o r
p h o u s solid, o n t h e o t h e r h a n d , is c h a r a c t e r i z e d b y a
lack of s y m m e t r y , periodicity a n d l o n g - r a n g e o r d e r ,
resulting in a diffraction p a t t e r n which is a c o n t i n u o u s
function of t h e scattering vector Q. T h u s , in o r d e r t o
completely specify t h e s t r u c t u r e of a n a m o r p h o u s
solid it w o u l d b e necessary t o specify t h e c o o r d i n a t e s
of all the a t o m s p r e s e n t , which is clearly impossible
for a n y real m a t e r i a l .
T h e i s o t r o p i c n a t u r e of a n a m o r p h o u s m a t e r i a l
leads t o a s t r u c t u r a l d e s c r i p t i o n in t e r m s of a o n e d i m e n s i o n a l real-space c o r r e l a t i o n function, w h i c h is
essentially a o n e - d i m e n s i o n a l a n a l o g u e of t h e P a t e r son function used for single crystals. F o r a m o n a t o
mic m a t e r i a l , t h e r a d i a l density p(r) describes t h e
n u m b e r density a t a d i s t a n c e r from a n a r b i t r a r i l y
chosen origin a t o m (see Fig. 2), a n d is a gross a v e r a g e
over all the a t o m s in t h e s a m p l e t a k e n as center. p is
the a v e r a g e n u m b e r density for the w h o l e s a m p l e . T h e
n u m b e r of n e i g h b o r s b e t w e e n r a n d r 4- dr is given by
2
dr
in which g(r) is k n o w n as t h e r a d i a l
function. T h e c o r r e l a t i o n function,
t(r) = 4nrp(r)
(1)
(2)
(3)
F o r a s a m p l e c o n t a i n i n g elements t h e s t r u c t u r e m a y
be described in t e r m s of n(n 4- l ) / 2 i n d e p e n d e n t c o m
p o n e n t c o r r e l a t i o n functions of t h e f o r m
tjk(r)
= 4nrpjk{r)
(b)
distribution
(4)
Figure 1
Structures of simple covalent (a) crystalline and
(b) amorphous solids
2. Experimental
Techniques
(5)
w h e r e is t h e incident w a v e l e n g t h a n d 20 is the
scattering angle. A l t h o u g h for a n a m o r p h o u s solid
t h e s t r u c t u r a l i n f o r m a t i o n is essentially c o n t a i n e d
within t h e elastic scattering, it is c o n v e n t i o n a l t o
p e r f o r m a t o t a l diffraction e x p e r i m e n t in which the
559
X-Ray
and Neutron
Diffraction
(a)
t (r)
-- 4
Studies
of Amorphous
(b)
(r)
(d )
Figure 2
Real-space correlation functions: (a) radial density;
(b) radial-distribution function; (c) total correlation
function; (d) differential correlation function
Solids
rise t o a s t r o n g e p i t h e r m a l c o m p o n e n t in (). T h e s e
s h o r t - w a v e l e n g t h n e u t r o n s allow d a t a to be o b t a i n e d
to m u c h higher values of Q, resulting in a c o r r e s p o n d
ing increase in real-space resolution.
A c c u r a t e q u a n t i t a t i v e x-ray diffraction m e a s u r e
m e n t s o n a m o r p h o u s solids usually e m p l o y a m o d i
fied p o w d e r - c o u n t e r diffractometer
(see
X-Ray
Powder Diffraction). T h e situation for x-rays is c o m
plicated by t h e presence of i n c o h e r e n t C o m p t o n scat
tering which a t high values of Q c a n completely
s w a m p the r e q u i r e d c o h e r e n t c o n t r i b u t i o n . Since
neither the w a v e l e n g t h d i s t r i b u t i o n n o r the i n t e g r a t e d
intensity of the C o m p t o n scattering from a given
s a m p l e c a n b e satisfactorily calculated, it is necessary
t o r e m o v e this c o n t r i b u t i o n by m e a n s of a diffractedb e a m m o n o c h r o m a t o r . M a n y researchers h a v e used a
single m o n o c h r o m a t o r in t h e diffracted b e a m b u t t h e
difficulty with this a r r a n g e m e n t is t h a t white b a c k
g r o u n d r a d i a t i o n from the x-ray t u b e c a n be C o m p
t o n scattered i n t o the m o n o c h r o m a t o r envelope. A
m u c h better a r r a n g e m e n t , s h o w n in Fig. 5, e m p l o y s a
m o n o c h r o m a t o r in b o t h t h e incident a n d diffracted
b e a m s ( W a r r e n a n d M a v e l 1965). A c o n v e n t i o n a l
curved-crystal m o n o c h r o m a t o r is used in t h e incident
b e a m (silver ^ = 0.05594 n m ) b u t t h a t in the
diffracted b e a m c o m p r i s e s a foil with a n a b s o r p t i o n
edge at a w a v e l e n g t h slightly longer t h a n the c h a r a c
teristic line of the x-ray t u b e ( r u t h e n i u m edge:
= 0.05605 n m ) such t h a t t h e c o h e r e n t intensity will
excite fluorescence w h e r e a s t h e C o m p t o n scattering
will n o t . T h e fluorescent r a d i a t i o n is t h e n r e c o r d e d by
the detector.
T h e dispersion t e c h n i q u e is also possible with rays
using a s e m i c o n d u c t o r detector. T h e a d v a n t a g e of this
m e t h o d is t h a t for c o m p l e x s a m p l e e n v i r o n m e n t s
(such as c r y o s t a t s , furnaces a n d high-pressure cells)
only t w o o r three small w i n d o w s a r e needed, a fixed
angle a p a r t . Similarly, all values of Q a r e e x a m i n e d
simultaneously, m a k i n g the t e c h n i q u e ideally suited
t o following p h a s e c h a n g e s o r s t u d y i n g kinetic effects.
O u t s i d e such special a p p l i c a t i o n s , however, x-ray
variable-wavelength experiments are unlikely t o p r o v e
i m p o r t a n t for w o r k o n a m o r p h o u s m a t e r i a l s o w i n g t o
the difficulty of accurately d e t e r m i n i n g t h e incident
s p e c t r u m a n d m a k i n g c o r r e c t i o n s for a b s o r p t i o n a n d
C o m p t o n scattering.
A n y m e a s u r e m e n t requires a certain n u m b e r of
c o r r e c t i o n s t o t h e basic d a t a b u t in a g o o d e x p e r i m e n t
these c o r r e c t i o n s a r e minimized o r p u t i n t o a form in
which they a r e easily h a n d l e d . N o r m a l l y , corrections
a r e included for:
(a)
c o u n t e r paralysis t i m e t h i s c o r r e c t i o n is b e c o m
ing increasingly i m p o r t a n t with m o d e r n highintensity x-ray a n d n e u t r o n sources;
(b)
i n s t r u m e n t a l b a c k g r o u n d a n d scattering
a n y s a m p l e c o n t a i n e r used;
(c)
from
X-Ray
and Neutron
Diffraction
Studies
of Amorphous
Solids
Figure 3
Conventional neutron diffractometer
c a n only be t r e a t e d i n d e p e n d e n t l y if o n e o r o t h e r
of t h e m is small;
(d)
(e)
F o l l o w i n g c o r r e c t i o n it is necessary t o n o r m a l i z e t h e
d a t a t o a b s o l u t e units. T h i s m a y be achieved either b y
the use of self-consistent i n t e g r a t i o n t e c h n i q u e s or, for
n e u t r o n s , by m e a s u r i n g t h e ( i n c o h e r e n t ) s c a t t e r i n g
from a s t a n d a r d v a n a d i u m s a m p l e .
3. Outline
Theory
i(0
pattern
ma
T{r) =
j*g/(0M(0sin rQ dQ (7)
(8)
T(r) = 4nrp^bj)2
(6)
T(r) = T\r) +
TLt)k{r)
J k
/OO
tjk(u)[P'jk(r
- u)
Jo
-P'jk(r
+ u)]du
(9)
X-Ray
and Neutron
Diffraction
Studies
of Amorphous
Target
Pulsed
electron
BEAM
'olyethylene moderator
Concrete shielding wall
Solids
Borax in resin
92
U fjssion chamber
Focusing angle
B4C in resin
Variable Second
f|ight-pbth
BAC in rubber
Figure 4
Time-of-flight neutron diffractometer
P%(r)
= ( ^ )
M ( 0 C O S rQ dQ
(10)
define t h e e x p e r i m e n t a l resolution in real space.
fj(Q) a n d fk(Q)
being a t o m i c scattering factors
a n d / e(0 the a v e r a g e form factor p e r electron for the
s a m p l e j n q u e s t i o n . F o r n e u t r o n s , t h e scattering
lengths b a r e i n d e p e n d e n t of Q a n d the factor bjbk is a
simple scaling factor, w h e r e a s for rays it is c o n v e n
tional t o divide Qi(Q) b y t h e " s h a r p e n i n g " function
562
of
Interpretation
Qijk(Q)
-r , ^
njkfj(Q)fk(Q)
in
ikQ
e x p i - i g ^ ) (11)
w h e r e nJk is t h e n u m b e r of /c-type a t o m s a r o u n d a t o m
j at this distance, a n d f{Q) represents either f(Q) o r b
for rays o r n e u t r o n s , respectively. T h e c o r r e s p o n d
ing real-space c o r r e l a t i o n function, including the c o n -
X-Ray
and Neutron
Diffraction
Studies
of Amorphous
Solids
Scaler
Figure 5
Fluorescent-foil x-ray diffraction technique
t r i b u t i o n from P(r), c a n b e o b t a i n e d b y F o u r i e r
t r a n s f o r m a t i o n of E q n . (11) w i t h t h e s a m e value of
g m ax a n d modification function a s used e x p e r i m e n
tally. It is t h u s possible t o o b t a i n t h e p a r a m e t e r s njk,rjk
1 /2
a n d (w#) b y p e r f o r m i n g a least-squares fit t o t h e
e x p e r i m e n t a l d a t a in real space o r t o t h e e x p e r i m e n t a l
interference function a t h i g h Q, w h e r e only t h e s h a r p
est real-space p e a k s c o n t r i b u t e .
7(0)=/ (0)*/(0)
self
()=
{)+
J Q/lQ)M[Q)
distinct
sin rO
dO
Figure 6
Steps in the calculation of the real-space correlation
function T(r) from the corrected intensity / ( g )
4.2 Model
Calculations
T h e limited n a t u r e of t h e m e a s u r e d c o r r e l a t i o n func
tion m e a n s t h a t in o r d e r t o e x t r a c t m o r e t h a n j u s t
average interatomic distances a n d coordination
n u m b e r s it is necessary t o r e s o r t t o s o m e f o r m of
m o d e l a n d t o ascertain h o w well this agrees with
e x p e r i m e n t . Qi(Q) a n d T(r) e m p h a s i z e different a s
pects of t h e s t r u c t u r e a n d it is therefore m o s t i m p o r t
a n t t o m a k e such c o m p a r i s o n s in b o t h real a n d
intensity space, a n d in t h e f o r m e r t o correctly incor
p o r a t e t h e p e a k function P(r). Similarly, n o m a t t e r
h o w g o o d t h e a g r e e m e n t o b t a i n e d is, t h e m o d e l in
q u e s t i o n is only o n e possible fit t o t h e d a t a a n d hence
it is essential t o c o n s i d e r , a n d if possible eliminate, all
a l t e r n a t i v e m o d e l s . A variety of s t r u c t u r a l m o d e l s a n d
m o d e l l i n g t e c h n i q u e s h a s b e e n e m p l o y e d in t h e s t u d y
of a m o r p h o u s solids a n d s o m e of t h e m o r e i m p o r t a n t
of these a r e s u m m a r i z e d b e l o w .
(a)
C r y s t a l - b a s e d m o d e l s . A g r e a t deal of i n f o r m a
tion o n t h e s t r u c t u r e of a m o r p h o u s solids c a n be
o b t a i n e d from a simple c o m p a r i s o n with t h e
c o r r e s p o n d i n g crystalline p o l y m o r p h s . M o r e
f o r m a l crystal-based m o d e l s , such as t h e q u a s i crystalline m o d e l , s t a r t w i t h a n a p p r o p r i a t e crys
tal s t r u c t u r e a n d restrict t h e l o n g e r - r a n g e o r d e r
t o i n t e r a t o m i c spacings less t h a n s o m e c h a r a c t e r
istic c o r r e l a t i o n length.
(b)
563
X-Ray
and Neutron
Diffraction
Studies
of Amorphous
C h a i n a n d ring m o d e l s . T h e s e m o d e l s a r e a p p r o
p r i a t e for m a t e r i a l s c o n t a i n i n g only divalent
a t o m s (e.g., selenium) o r larger t w o - c o n n e c t e d
g r o u p i n g s of a t o m s such as t h o s e f o u n d in or
ganic p o l y m e r s ( e . g . , C H 2 ) .
(d)
Random-sphere-packing
models.
Random
sphere p a c k i n g s p r o v i d e a useful s t a r t i n g p o i n t
for m o d e l s of a m o r p h o u s metallic alloys a n d
m a t e r i a l s w h o s e s t r u c t u r e s a r e g o v e r n e d by p r e
d o m i n a n t l y ionic forces such as vitreous Z n C l 2 .
(e)
(f)
A m o r p h o u s - c l u s t e r m o d e l s . A m o r p h o u s clusters
a r e c o m p o s e d of a t o m s in a regular b u t n o n c r y s t a l l o g r a p h i c configuration frequently b a s e d o n
p e n t a g o n a l d o d e c a h e d r a o r fivefold s y m m e t r y .
Cluster size is limited d u e t o a slight m i s m a t c h
between adjacent s t r u c t u r a l u n i t s , w h i c h leads t o
increasing d i s t o r t i o n as t h e cluster g r o w s .
(g)
M o n t e C a r l o a n d m o l e c u l a r d y n a m i c s simula
tions. T h e s t r u c t u r e s of a r a n g e of simple inor
ganic glasses h a v e been s i m u l a t e d using p u r e l y
ionic p o t e n t i a l s . A g a i n t h e m e t h o d s e m p l o y e d
closely follow t h o s e for related liquids.
5. Neutron
Magnetic
Diffraction
6. Accuracy
and
Limitations
564
Solids
a u t h o r s either p l o t t h e r a d i a l d i s t r i b u t i o n function
r 7 \ r ) , w h i c h h a s t h e effect of r e d u c i n g t h e a m p l i t u d e
of e r r o r ripples a t low r, o r use these false oscillations
as a criterion for tidying their d a t a before p u b l i c a t i o n
a n d d o n o t include the original u n t r e a t e d t r a n s f o r m .
In t h e a b s e n c e of o t h e r i n f o r m a t i o n such d a t a m u s t be
r e g a r d e d with t h e u t m o s t suspicion.
Similar t e c h n i q u e s a r e s o m e t i m e s used t o r e m o v e
t h e effects of t e r m i n a t i n g t h e d a t a a t finite Q m a x.
I n f o r m a t i o n t h e o r y , h o w e v e r , indicates t h a t it is im
possible t o replace t h e u n m e a s u r e d d a t a w i t h o u t
making some assumption a b o u t the material under
investigation so t h a t t h e resulting c o r r e l a t i o n function
merely b e c o m e s o n e possible m o d e l which fits the
results r a t h e r t h a n a n u n b i a s e d F o u r i e r t r a n s f o r m . It
s h o u l d also be n o t e d t h a t in principle b o t h Qi(Q) a n d
T(r) c o n t a i n t h e s a m e i n f o r m a t i o n expressed in a
different f o r m , a l t h o u g h in practice t h e i n f o r m a t i o n
c o n t e n t of T(r) is slightly r e d u c e d by t h e use of a
modification function. T h e finite u p p e r limit in Q
m e a n s t h a t in T(r) e a c h c o m p o n e n t tjk{r) is c o n v o
luted with t h e a p p r o p r i a t e p e a k f u n c t i o n p ( r ) , b u t the
i n f o r m a t i o n for a p a r t i c u l a r d i s t a n c e is still c o n c e n
t r a t e d a r o u n d t h a t d i s t a n c e (whereas it is s p r e a d
t h r o u g h o u t reciprocal space).
T h e u n i q u e n e s s of a n y s t r u c t u r a l i n f o r m a t i o n
e x t r a c t e d from t h e d a t a is m u c h m o r e difficult t o
j u d g e . A s a l r e a d y stressed, t h e o n e - d i m e n s i o n a l
n a t u r e of t h e c o r r e l a t i o n function m e a n s t h a t it is
impossible t o u n a m b i g u o u s l y d e t e r m i n e t h e s t r u c t u r e
of a n a m o r p h o u s solid. T h e reliability of a n y i n t e r p r e
t a t i o n , therefore, d e p e n d s n o t only o n t h e q u a l i t y of
the fit t o the e x p e r i m e n t a l d a t a in b o t h real a n d
reciprocal space, b u t also o n the n u m b e r of o t h e r
possible m o d e l s w h i c h h a v e been tried a n d satisfactor
ily rejected. T h e fact t h a t diffraction d a t a a r e a n
a v e r a g e for t h e w h o l e i r r a d i a t e d v o l u m e , a n d include
a t m o s t only p a r t of a n y small-angle scattering which
m a y be p r e s e n t , m e a n s t h a t t h e d a t a a r e relatively
insensitive t o p h a s e s e p a r a t i o n . In m o s t cases, it is
n o t possible t o d e t e r m i n e t h e individual c o m p o n e n t
a n d in this situation
c o r r e l a t i o n functions tjk(r),
e x t e n d e d x-ray a b s o r p t i o n fine-structure t e c h n i q u e s
can provide important complementary information.
Finally, it m u s t n o t be f o r g o t t e n t h a t a great deal of
o t h e r s t r u c t u r a l i n f o r m a t i o n c a n be o b t a i n e d from the
results of indirect p r o b e s such as optical s p e c t r o s c o p y
a n d m a g n e t i c r e s o n a n c e s p e c t r o s c o p y . All of these
d a t a m u s t also be consistent with a n y c h o s e n struc
tural model.
See also: Single-Crystal X-Ray Diffraction; X-Ray Absorp
tion Spectroscopy: EXAFS and XANES Techniques;
X-Ray Powder Diffraction
Bibliography
Elliott S R 1984 Physics of Amorphous Materials. Longman,
London
X-Ray
and Neutron
I. Diffuse
X-Ray
Scattering
Diffuse
Scattering
of Radiation-Induced
Defects
(1)
S=c\F(k)\
(2)
occ(AF)
(3)
e f o r e
S a [ l eor c ( c / ) ( A F )
(4)
565
X-Ray
and Neutron
022
Diffuse
Scattering
of Radiation-Induced
Defects
222
? _
Scattering angle
()
Figure 1
Comparison of the measured diffuse scattering intensity from electron-irradiated aluminum with intensities calculated
assuming different self-interstitial atom configurations (after Haubold 1975)
2. Neutron
(5)
Diffuse
Elastic
Scattering
+ ( , ) + , ( . )
2
+ ? ( 1 , 2 , 3 ) + 2 ( 2 , 3 )
+ ^ ^ , , ) + A,
h2Sxy(hh2,h3)
+ MjS^Mj,*,) + , 5 ^ (
, 2)
(6)
with
^SRO
lmn
a
os
sc
2 COS
7TNAJ
(7)
c o s 2 cos 3
(8)
l,m,n
Figure 2
Scattering intensities close to (400) reflections in a [100] q
direction calculated for dislocation loops with radius
20 A in nickel (after Ehrhart et al. 1982)
566
Qx
l,m,n
yimn '
lh\
X-Ray
Rx
(9)
l,m,n
*mn
sm
ms
(10)
l,m,n
C, a r e c o n c e n t r a t i o n s of species a n d b\ a r e n e u t r o n
scattering lengths weighted b y a p p r o p r i a t e D e b y e Waller factors. A detailed discussion c a n b e f o u n d in
S c h m a t z (1973) a n d B a u r (1979). T h e t e r m s in Rx
c o n t a i n i n f o r m a t i o n a b o u t static d i s p l a c e m e n t effects
described in Sect. 1; 7 S RO p r o v i d e s details o f s h o r t r a n g e o r d e r a n d clustering a m o n g defects. T h e u s e o f
s y m m e t r y a r g u m e n t s in a detailed discussion o f these
e q u a t i o n s c a n b e f o u n d in S c h w a r t z a n d C o h e n
(1977). T h e p o i n t h e r e is t h a t t h e F o u r i e r coefficients
in E q n s . ( 8 - 1 0 ) , for r a y s , c o n t a i n a t o m i c scattering
factors f(Q) a n d t h u s a r e n o t strictly periodic. F o r
n e u t r o n s , n u c l e a r scattering lengths a r e a p p r o p r i a t e
a n d hence t h e a p p l i c a t i o n o f n e u t r o n s offers signific
a n t a d v a n t a g e over r a y s .
Diffuse elastic n e u t r o n scattering ( D E N S ) tech
niques allow u s t o r e m o v e t h e c o m p l i c a t i o n s o f
t i m e - d e p e n d e n t p h e n o m e n a such a s p h o n o n inelastic
scattering, a n d a r e m u c h less sensitive t o surface
effects since n e u t r o n a b s o r p t i o n cross sections a r e
m u c h smaller t h a n x-ray c o u n t e r p a r t s . T h e largest
sources of b a c k g r o u n d in x-ray m e a s u r e m e n t s a r e
C o m p t o n a n d t h e r m a l diffuse scattering; these a r e
eliminated using D E N S t e c h n i q u e s . H o w e v e r , c a r e
m u s t b e t a k e n in t h e n e u t r o n case t o a v o i d n u c l e a r
spin a n d i s o t r o p i c d i s o r d e r scattering. T h e m a i n dis
a d v a n t a g e s o f D E N S stem from limited n e u t r o n
fluxes available a t steady state sources; h o w e v e r , n e w
i n s t r u m e n t a t i o n a n d t h e a d v e n t of pulsed n e u t r o n
sources m a y allow u s t o m i n i m i z e this limitation (see
C o h e n et al. (1975)).
Acknowledgement
T h e w o r k o f t h e a u t h o r s is s u p p o r t e d b y t h e U S
Government under contract N o . W-31-109-ENG-38.
See also: Electron Microscope Analysis of Defect Clusters,
Voids and Bubbles; X-Ray Powder Diffraction
Bibliography
Baur G S 1979 Diffuse elastic neutron scattering from non
magnetic materials. In: Herman (ed.) 1979 A Treatise
on Materials Science and Technology, Vol. 15. Academic
Press, New York, pp. 291
Borie B, Sparks C J Jr 1971 The interpretation of intensity
distributions from distorted binary alloys. Acta Crystallogr. Sect. A 27: 198-201
Cohen J B, Faber J, Batterman W, Baur G S, King S S,
Larson C, Summerfeld G C 1975 Advanced Uses of
Pulsed Neutron Sources, ANL-76-10, Vol. 2. Argonne
National Laboratory, Argonne, IL, p. 88
Diffraction,
Time-Resolved
X-Ray
Diffraction,
Time-Resolved
/.
Direct
Measurements
568
m o r e t h a n six o r d e r s of m a g n i t u d e b r i g h t e r t h a n
c o n v e n t i o n a l r o t a t i n g a n o d e x-ray sources a n d synch
r o t r o n facilities scheduled t o b e c o m p l e t e d in t h e m i d 1990s will b e yet a n o t h e r t h o u s a n d times brighter.
H a v i n g selected a s o u r c e , three w a y s exist t o increase
the t o t a l flux in t h e incident b e a m : use m o r e w a v e
lengths of t h e s o u r c e , use m o r e angles of t h e s o u r c e o r
use s o m e c o m b i n a t i o n of b o t h . Often, t h e resulting
increase in flux is a t t h e expense of lowering t h e
diffraction r e s o l u t i o n of t h e e x p e r i m e n t .
Before p r o c e e d i n g , it is w o r t h w h i l e m e n t i o n i n g a n
essential difference b e t w e e n t w o types of m e a s u r e
m e n t s , p o w d e r diffraction a n d single-crystal dif
fraction. B r a g g ' s law requires t w o c o n d i t i o n s t o b e
satisfied for diffraction. O n e results b e c a u s e t h e angle
of incidence of t h e r a y s o n t h e diffracting p l a n e s
m u s t b e correct a n d t h e s e c o n d b e c a u s e rays will
diffract only in certain directions. T h e incident angle
r e q u i r e m e n t m e a n s t h a t for time-resolved diffraction
o n single crystals it is also necessary, except in special
cases, t o c h a n g e t h e o r i e n t a t i o n of t h e crystal. F o r
p o w d e r s , crystallites exist a t all o r i e n t a t i o n s a n d so
t h e first r e q u i r e m e n t is always satisfied a n d only t h e
p l a c e m e n t of t h e x-ray d e t e c t o r a t t h e correct scatter
ing angles is needed. A n o t h e r i m p o r t a n t difference
b e t w e e n a single crystal a n d a p o w d e r s a m p l e of t h e
s a m e m a t e r i a l is t h e relative intensity of a typical
B r a g g p e a k . F o r a single crystal t h e intensity of a
B r a g g p e a k is localized i n t o a n intense small solid
angle of scattering. I n c o n t r a s t , t h e m a n y o r i e n t a t i o n s
of crystallites in a polycrystalline s a m p l e result in a
c o n e of scattering of w h i c h diffractometers only
m e a s u r e a small fraction.
T h e m o s t o b v i o u s w a y t o i m p r o v e t h e detection
efficiency in a c o n v e n t i o n a l p o w d e r diffraction experi
m e n t is t o use m a n y d e t e c t o r s a n d therefore collect
m a n y scattering angles s i m u l t a n e o u s l y . T h i s is c o n
veniently d o n e using o n e - d i m e n s i o n a l a n d t w o d i m e n s i o n a l d e t e c t o r a r r a y s , w h i c h a r e often referred
to a s position-sensitive d e t e c t o r s . T h e diffraction reso
lution of these d e t e c t o r s is partially d e t e r m i n e d b y t h e
physical size o f e a c h d e t e c t o r element a n d t h e time
r e s o l u t i o n is d e t e r m i n e d b y t h e electronics, which
limits t h e m a x i m u m m e a s u r a b l e c o u n t r a t e . T h e
oldest position-sensitive d e t e c t o r is a p r o p o r t i o n a l
wire d e t e c t o r . T h e y c o n v e n t i o n a l l y give 100 spa
tial r e s o l u t i o n a n d c a n s p a n a region of 510 c m in
either a straight line o r a l o n g a circular a r c . T h e s e
d e t e c t o r s h a v e a very l o w intrinsic b a c k g r o u n d . T h e i r
p r i m a r y deficiency is t h a t they h a v e a relatively low
m a x i m u m c o u n t r a t e of a r o u n d 50 000 rays p e r
second i n t e g r a t e d over t h e w h o l e detector. Since
50 000 c o u n t s s p r e a d over a diffraction p a t t e r n is
a b o u t t h e m i n i m u m n u m b e r of c o u n t s r e q u i r e d t o
define a diffraction p a t t e r n , this limits t h e m i n i m u m
time p e r diffraction p a t t e r n t o a r o u n d 1 s. M o r e
recently, p h o t o d i o d e a r r a y s ( S t e p h e n s o n 1988) a n d
c h a r g e - c o u p l e d device ( C C D ) a r r a y s ( R o d r i c k s et al.
1989) h a v e b e c o m e available for x-ray detection. T h e y
X-Ray
Diffraction,
Time-Resolved
Measurements
569
X-Ray
Diffraction,
Time-Resolved
5. Future
Possibilities
Measurements,
Subsecond;
Bibliography
Baublitz A Jr, Arnold V, Ruoff A L 1981 Energy
dispersive x-ray diffraction from high pressure polycrystalline specimens using synchrotron radiation. Rev. Sci.
Instrum. 52: 1616-24
Brauer S, Ryan D H, Strom-Olsen J O, Sutton M, Stephen
son G 1990 Pyrometric temperature controller for
million degree per second heating. Rev. Sci. Instrum. 61:
2214-19
570
1. Definition,
Scope,
Advantages,
Limitations
X - r a y fluorescence s p e c t r o m e t r y is a n o n d e s t r u c t i v e
i n s t r u m e n t a l m e t h o d of qualitative a n d q u a n t i t a t i v e
analysis for chemical elements b a s e d o n the w a v e
lengths a n d intensities of their x-ray-excited spectral
X-Ray
Spectra
X rays m a y b e defined a s e l e c t r o m a g n e t i c r a d i a t i o n in
5
the wavelength region ~ 1 0 ~ - 1 0 n m p r o d u c e d b y
deceleration of high-energy electrons a n d / o r b y elec-
Fluorescence
Spectrometry
Wavelength
Figure 1
Section of an atom of an element of high atomic number,
showing the electron transitions that produce the principal
characteristic x-ray spectral lines and the x-ray spectrum
from an x-ray tube having a target of high atomic number
and operated at high potential (from Introduction to
X-Ray Spectrometric Analysis, courtesy of Plenum Press)
t r o n t r a n s i t i o n s t o t h e inner orbits of a t o m s . I n
analytical x-ray fluorescence s p e c t r o m e t r y , t h e appli
cable spectral region is ~ 0 . 0 1 - 2 n m a n d with special
accessories t o ~ 1 0 n m . X rays a r e characterized b y
w a v e l e n g t h ( n m ) p h o t o n energy (eV), a n d inten
sity / ( p h o t o n s , o r " c o u n t s , " p e r second). T h e w a v e
length a n d p h o t o n energy a r e related reciprocally:
E= 124 000/A. T h e c o n s t a n t in this e q u a t i o n is (he/
11
e) x 1 0 n m m~ \ w h e r e h is P l a n c k ' s c o n s t a n t , c is t h e
velocity of light a n d e is t h e electron c h a r g e . T h e r e a r e
t w o types of x-ray emission spectra: c o n t i n u o u s a n d
characteristic-line (see F i g . 1).
The continuous spectrum, continuum or "brehmss t r a h l u n g " o c c u r s in significant intensity only with
electron excitation a n d arises from d e c r e m e n t a l decel
e r a t i o n of electrons. It is c h a r a c t e r i z e d by a c o n t i n u
o u s b a n d of wavelengths, s t a r t i n g a t a m i n i m u m
w a v e l e n g t h d e t e r m i n e d b y t h e electron acceleration
p o t e n t i a l V (A m in = 124 000/) rising t o m a x i m u m
intensity a t 1.5 A m i n, a n d decreasing in intensity a t
increasing wavelength (Fig. 1).
C h a r a c t e r i s t i c x-ray line spectra arise w h e n v a c a n
cies o c c u r in t h e K , L a n d shells of a t o m s a n d
electrons from shells further o u t fall i n t o these v a c a n
cies, t h e r e b y losing energy, which a p p e a r s as x-ray
photons. Fig. 1 shows the transitions that produce the
principal lines a n d t h e s y m b o l s a n d relative intensities
571
X-Ray
Fluorescence
Spectrometry
M i l l
3. Excitation
of Characteristic
X-Ray
Spectra
572
Figure 2
Distinction between wavelength dispersion (right of
specimen), in which the rays are dispersed spacially by
wavelength prior to detection, and energy dispersion (left
of specimen), in which all rays are detected
simultaneously and detector output pulses are separated
by amplitude electronically (from Introduction to X-Ray
Spectrometric Analysis, courtesy of Plenum Press)
4.
Dispersion
5. InstrumentationX-Ray
Generator
X-Ray
Fluorescence
Spectrometry
5 0 kV
Figure 3
X-ray generator: the solid and dashed waveforms at the top correspond to the high (solid arrow) and low (dashed arrow)
settings of the autotransformer. The resistor and capacitor constitute the constant-potential filter. The switch represents
various automatic safety devices
6. InstrumentationSpecimen
Spectrogoniometer
Chamber
and
S o m e s p e c t r o g o n i o m e t e r s a r e s e p a r a t e self-contained
table-top instruments having the x-ray-tube window
directed d o w n w a r d i n t o a c h a m b e r h a v i n g a r e m o v
able d r a w e r for specimens ~ 2 . 5 c m in d i a m e t e r a n d
thickness. T h e s e i n s t r u m e n t s c a n be r e a r r a n g e d with
t h e x-ray w i n d o w u p w a r d ("inverted o p t i c s " ) for very
large specimens, such as i n g o t s , engine p a r t s a n d a r t
objects. I n m o s t s p e c t r o m e t e r s , t h e g o n i o m e t e r h a s
inverted optics b u t is enclosed o n all sides, limiting
m a x i m u m specimen size t o ~ 5 c m d i a m e t e r by
~ 2 . 5 c m thick. T h e specimen c h a m b e r m a y h o l d a
single specimen o r p r o v i d e for a u t o m a t i c sequential
i n d e x i n g of u p t o 30.
T h e s p e c t r o g o n i o m e t e r (Fig. 4) c o m p r i s e s t w o colli
m a t o r s , a n a n a l y z e r crystal a n d a d e t e c t o r a r r a n g e d
o n a m a n u a l o r m o t o r - d r i v e n precision r o t a t i n g
m e c h a n i s m . T h e c o l l i m a t o r s consist of spaced parallel
m e t a l foils rigidly held in rectilinear m e t a l tunnels.
T h e single-crystal b a r serves as a n x-ray diffraction
g r a t i n g . T h e d e t e c t o r is described in Section 7. O n e
c o l l i m a t o r is fixed a t t h e o u t p u t e n d of t h e specimen
c h a m b e r . T h e crystal is bisected b y a n d r o t a t e s a b o u t
t h e g o n i o m e t e r axis a t angle 0 p e r u n i t time as the
o t h e r c o l l i m a t o r a n d d e t e c t o r r o t a t e t o g e t h e r a t angle
20 p e r u n i t time. A t w a v e l e n g t h s s h o r t e r t h a n
~ 0 . 2 5 n m the specimen-crystal-detector radiation
p a t h m a y be air, b u t a t longer w a v e l e n g t h s x-ray
573
X-Ray
Fluorescence
Spectrometry
Figure 4
X-ray spectrogoniometer and electronic detection and readout components. The pulse diagrams show pulse height versus
time. The pulse-height selector passes pulses having amplitude between two discriminator settings, baseline BL and
window width W
a b s o r p t i o n in air is p r o h i b i t i v e a n d t h e g o n i o m e t e r is
enclosed in a flexible helium-flushed h o o d o r a rigid
vacuum hood.
T h e c o n s t i t u e n t elements in t h e specimen emit their
characteristic x-ray spectra in all directions, b u t only a
b u n d l e of rays parallel t o the foils of t h e first collima
t o r reaches t h e crystal. A t each a n g u l a r p o s i t i o n , t h e
crystal diffracts only t h e w a v e l e n g t h t h a t satisfies
the B r a g g law: = 2d sin 0, w h e r e d is the i n t e r p l a n a r
spacing of the crystal planes parallel t o the surface
a n d is a n integer defining the diffraction o r d e r . N o t e
t h a t a t a specified m o r e t h a n o n e w a v e l e n g t h c a n be
diffracted: in first o r d e r (n = 1), /2 in second o r d e r
(n 2 ) , . . . , / in t h o r d e r . T h u s , as t h e crystal
r o t a t e s over its r a n g e , it diffracts in sequence all
incident x-ray w a v e l e n g t h s u p t o a m a x i m u m of
2d n m . Several crystals h a v i n g different d spacings a r e
required t o cover t h e entire w a v e l e n g t h region, for
e x a m p l e , lithium fluoride (2d 0.403 n m ) , p e n t a e r y t h r i tol ( P E T , 2 ^ 0 . 8 7 4 n m ) a n d p o t a s s i u m h y d r o g e n
p h t h a l a t e ( K H P , 2</2.66 n m ) .
7. InstrumentationElectronic
Readout
Components
Detection
and
574
(Fig. 4) c o m p r i s e s a cylindrical m e t a l - t u b e c a t h o d e
h a v i n g a n axial wire a n o d e a n d insulating e n d s , a n d
filled with a gas, usually a r g o n o r x e n o n . T w o d i a m e t
rically o p p o s i t e x-ray w i n d o w s a r e p r o v i d e d . F o r
wavelengths shorter than ~ 0 . 2 5 n m the windows m a y
be p e r m a n e n t l y sealed beryllium o r mica. F o r longer
w a v e l e n g t h s , the w i n d o w s m u s t be of thin plastic,
usually 6- o r 3- M y l a r , t o reduce x-ray a b s o r p t i o n .
Such w i n d o w s a r e n o t gas-tight, so t h e gas, usually a
9 0 - 1 0 v o l . % m i x t u r e of a r g o n a n d m e t h a n e , is passed
c o n t i n u o u s l y t h r o u g h these "flow c o u n t e r s . " T h e
scintillation c o u n t e r c o m p r i s e s a disk of t h a l l i u m activated s o d i u m iodide, N a l ( T l ) , affixed o u t s i d e t h e
p h o t o c a t h o d e e n d of a multiplier p h o t o t u b e . T h e
lithium-drifted silicon, Si(Li), d e t e c t o r is a disk of
specially t r e a t e d single-crystal silicon.
E a c h x-ray p h o t o n a b s o r b e d in a gas-filled, scintil
lation o r silicon d e t e c t o r ejects a n electron from, say,
the o u t e r m o s t orbital of a gas, iodine o r silicon a t o m ,
respectively, a n d i m p a r t s substantially all of its p h o
t o n energy t o kinetic energy of this p h o t o e l e c t r o n . I n
t h e gas-filled detector, this p h o t o e l e c t r o n e x p e n d s its
energy in p r o d u c i n g m o r e gas-ion/electron p a i r s .
E a c h of these s e c o n d a r y electrons initiates a n " a v a
l a n c h e " of still m o r e i o n - e l e c t r o n p a i r s so t h a t for
4
e a c h electron p r o d u c e d b y the p h o t o e l e c t r o n ~ 1 0 6
10 electrons r e a c h t h e a n o d e wire t o c o n s t i t u t e a n
o u t p u t pulse. I n t h e scintillation detector, t h e p h o t o
electron e x p e n d s its energy in f o r m i n g a b u r s t of
blue-light p h o t o n s , ~ 1 0 % of w h i c h strike t h e p h o t o c a t h o d e of t h e multiplier p h o t o t u b e a n d result in a
p h o t o e l e c t r o n arriving a t t h e electron multiplier. E a c h
X-Ray
8. InstrumentationAutomated
Special-Purpose
Spectrometers
and
Fluorescence
Spectrometry
specimen i n t o p o s i t i o n a n d r e p e a t t h e process c o n
tinually, all a u t o m a t i c a l l y a n d u n a t t e n d e d .
The simultaneous multichannel spectrometer has
a r r a y e d a b o u t t h e specimen, like s p o k e s a b o u t a wheel
h u b , u p t o 15 m e t a l p l a t e s , e a c h h o u s i n g o n e o r t w o
s p e c t r o m e t e r s c o m p r i s i n g c o l l i m a t o r s , crystal a n d d e
tector, a n d e a c h h a v i n g a r e a d o u t c h a i n . T h u s , the
i n s t r u m e n t c o m p r i s e s u p t o 30 c h a n n e l s . M o s t of
these a r e preset t o a specific x-ray line. T h e o t h e r s a r e
m o t o r - d r i v e n " s c a n n i n g " s p e c t r o m e t e r s of t h e type
described in Section 6. T h e s e a r e used for qualitative
analysis a n d for elements d e t e r m i n e d t o o infrequently
t o w a r r a n t preset c h a n n e l s . T h e s e i n s t r u m e n t s c a n
a c c u m u l a t e intensity d a t a for u p t o 30 elements in 1-2
m i n , w h e r e u p o n t h e next specimen is indexed i n t o
p o s i t i o n a n d m e a s u r e d , a n d so o n , all a u t o m a t i c a l l y
and unattended.
I n b o t h sequential a n d s i m u l t a n e o u s i n s t r u m e n t s ,
t h e intensity d a t a for s a m p l e s a n d s t a n d a r d s is i n p u t
t o a (usually) d e d i c a t e d c o m p u t e r for direct calcu
l a t i o n a n d p r i n t o u t of c o m p o s i t i o n . Such fully
a u t o m a t e d i n s t r u m e n t s a r e of inestimable value for
i n d u s t r i a l l a b o r a t o r i e s r e q u i r e d t o a n a l y z e daily very
large n u m b e r s of specific alloys, c e m e n t s , ceramics,
glasses, a n d so o n , a t m i n i m a l cost.
S p e c t r o m e t e r s for t h e u l t r a l o n g - w a v e l e n g t h region
( ^ 2 n m ) use x-ray g e n e r a t o r s c o m p r i s i n g special wind o wless x-ray t u b e s o p e r a t e d a t u p t o ~ 10 k V a n d t o
~ 500 m A , special p s e u d o c r y s t a l s h a v i n g 2d spacings
of 1 0 - 1 5 n m a n d w i n d o w l e s s d e t e c t o r s , all o p e r a t i n g
in high, clean v a c u u m .
T h e r e a r e relatively lightweight p o r t a b l e w a v e
length-dispersive s p e c t r o m e t e r s t h a t o p e r a t e from
b a t t e r i e s o r g e n e r a t o r s for field a n d e n v i r o n m e n t a l
use, b u t m o s t such a p p l i c a t i o n s use energy-dispersive
spectrometers.
Dynamic process-control spectrometers monitor
a n d c o n t r o l industrial processes, such as plating, ore
p r o c e s s i n g a n d reclaiming of p r e c i o u s m e t a l s . A n xray spectrometer at some point along the production
line m o n i t o r s , say, t i n - p l a t e thickness o n c o n t i n u o u s l y
m o v i n g sheet steel. W h e n t h e m o n i t o r e d x-ray inten
sity falls o u t s i d e previously established limits, the
i n s t r u m e n t either signals a n o p e r a t o r o r adjusts the
p l a t i n g c o n d i t i o n s t o c o r r e c t t h e fault.
9.
Operation
575
X-Ray
Fluorescence
Spectrometry
Q u a n t i t a t i v e analysis is p e r f o r m e d by setting t h e
g o n i o m e t e r at t h e 20 angle of a specified x-ray line,
say c o p p e r . T h e s e a l e r - t i m e r c o u n t s c o p p e r
pulses for a " p r e s e t t i m e " o r times the a c c u m u l a t i o n
of a " p r e s e t c o u n t . " M e a s u r e m e n t s a r e m a d e o n e a c h
s a m p l e a n d o n s t a n d a r d s similar t o t h e s a m p l e s b u t
h a v i n g k n o w n c o m p o s i t i o n . T h e s t a n d a r d d a t a is used
to establish a m a t h e m a t i c a l r e l a t i o n s h i p o r c a l i b r a t i o n
curve of c o p p e r intensity against c o p p e r c o n c e n
t r a t i o n , t o which the s a m p l e intensity d a t a is applied.
Alternatively, t h e intensity d a t a m a y be e n t e r e d in t h e
c o m p u t e r for calculation of c o m p o s i t i o n . T h e s a m e
p r o c e d u r e is followed for the o t h e r s a m p l e elements.
10. Matrix
Effects
11. Specimen
Forms and
Preparation
576
X-Ray
12. Analytical
Methods
Standardization
T h e c a l i b r a t i o n - s t a n d a r d m e t h o d is i m p r o v e d b y
q u a n t i t a t i v e a d d i t i o n t o all s a m p l e s a n d s t a n d a r d s of
a n element h a v i n g excitation, a b s o r p t i o n a n d en
h a n c e m e n t p r o p e r t i e s similar t o t h o s e of t h e a n a l y t e
in t h e p a r t i c u l a r m a t r i x . T h e c a l i b r a t i o n function is
the a n a l y t e / i n t e r n a l - s t a n d a r d intensity r a t i o versus
analyte concentration.
12.3 Standardization
with Scattered X Rays
T h e intensity of a selected w a v e l e n g t h from t h e p r i m
ary rays scattered by t h e specimen is used t o c o r r e c t
a b s o r p t i o n - e n h a n c e m e n t ( a n d o t h e r ) effects. T h e
wavelength m a y be from t h e c o n t i n u u m o r a t a r g e t
line. T h e c a l i b r a t i o n function is a n a l y t e / s c a t t e r e d
intensity r a t i o versus c o n c e n t r a t i o n .
12.4 Matrix-Dilution
Methods
All samples a n d s t a n d a r d s a r e t r e a t e d with a
" d i l u e n t , " which c o n s t i t u t e s a n e w c o n s t a n t m a t r i x .
T h e diluent m a y be a high c o n c e n t r a t i o n of lowa t o m i c - n u m b e r m a t e r i a l , such as a p o w d e r , solvent o r
Microanalysis,
Quantitative
Bibliography
Bertin 1975 Principles and Practice of X-Ray Spectro
metric Analysis, 2nd edn. Plenum, New York
Bertin 1978 Introduction to X-Ray Spectrometric Analy
sis. Plenum, New York
Herglotz , Birks L S (eds.) 1978 X-Ray Spectrometry.
Dekker, New York
Jenkins R 1974 An Introduction to X-Ray Spectrometry.
Heyden, London
Jenkins R, De Vries J L 1969 Practical X-Ray Spectrometry,
2nd edn. Springer, New York
E. P. Bertin
[RCA Laboratories, Princeton,
N e w Jersey, U S A ]
X-Ray
Microanalysis,
Quantitative
/.
ZAF
Corrections
O f t h e v a r i o u s m e t h o d s used t o calculate c o n c e n t r a
tions from net elemental intensities, t h e c o n v e n t i o n a l
Z A F m e t h o d is b y far t h e m o s t widely used for b u l k
specimens. Z A F refers t o t h e s e p a r a t e a t o m i c n u m b e r
Z , a b s o r p t i o n A a n d fluorescence F c o r r e c t i o n s w h i c h
a r e calculated as a function of a n ( a s s u m e d ) c o m p o s i
tion a n d multiplied b y t h e m e a s u r e d intensity r a t i o
( m e a s u r e d intensity divided b y p u r e element intensity
m e a s u r e d u n d e r identical circumstances):
Concentration = (
Intensity \
V P u r e intensity /
578
/
1_
\ ZAF )
X-Ray
2. Other Specimen
Microanalysis,
Quantitative
Figure 1
Example of a Monte Carlo simulation of a few trajectories
for 20 keV electrons in nickel
Geometries
F o r thin specimens, as e n c o u n t e r e d in t h e A E M ,
a b s o r p t i o n is negligible a n d fluorescence d i s a p p e a r s ,
so t h e c o r r e c t i o n p r o c e d u r e is further simplified. O n l y
the relative efficiency with w h i c h different e l e m e n t s
c a n be excited a n d emit characteristic rays a n d t h e
sensitivity of t h e s p e c t r o m e t e r a t different energies
r e m a i n . T h i s c a n be calculated either from f u n d a m e n
tal p a r a m e t e r s o r m e a s u r e d from a s t a n d a r d specimen
( b o t h m e t h o d s h a v e their a d h e r e n t s ) , t o p r o d u c e a
factor relating t h e m e a s u r e d intensity r a t i o s from
different elements t o their c o n c e n t r a t i o n s :
Concentration!
Concentration
Intensity!
2 1
Intensity2
c o p y . Alternatively, s p e c t r a c a n b e o b t a i n e d a t t w o
different accelerating voltages a n d c a l c u l a t i o n used t o
d e t e r m i n e t h e o r i e n t a t i o n angle t h a t gives t h e s a m e
c o m p o s i t i o n a n s w e r for b o t h analyses.
T h e accelerating v o l t a g e is a l w a y s a p a r a m e t e r of
p r i m e i m p o r t a n c e for q u a n t i t a t i v e analysis. W i t h a n
E D s p e c t r o m e t e r , it is best d e t e r m i n e d b y t h e cutoff
p o i n t of t h e c o n t i n u u m b a c k g r o u n d . T h i s is generally
more accurate than any meter on the microscope, and
also t a k e s i n t o a c c o u n t a n y deceleration of t h e elec
tron beam that m a y occur due to sample charging.
3. Monte
Carlo
Modelling
T h e m e t h o d w h i c h is in principle c a p a b l e of dealing
with a n y k i n d of specimen g e o m e t r y is M o n t e C a r l o
m o d e l l i n g . R a t h e r g o o d m o d e l s a r e n o w available for
e a c h of t h e individual processes b y w h i c h m o v i n g
electrons lose energy a n d slow d o w n , a n d excite
characteristic o r c o n t i n u u m rays from a t o m s . By
using c o m p u t e r r a n d o m - n u m b e r g e n e r a t o r s t o s a m p l e
these p r o b a b i l i t y d i s t r i b u t i o n s it is possible t o follow
t h e p a t h s of a statistically useful n u m b e r (typically a t
least several t h o u s a n d , a n d m a n y m o r e in s o m e cases)
of electrons as they scatter from a t o m s in t h e speci
men, encounter various geometric boundaries and
generate rays which can be summed. (Figure 1
s h o w s a n e x a m p l e of a M o n t e C a r l o p l o t of electron
trajectories.) T h i s m e a n s t h a t a n y b o u n d a r y c o n
d i t i o n s , surface o r subsurface irregularities, c o m p o s i
t i o n h e t e r o g e n e i t y o r o t h e r s a m p l e peculiarities c a n be
set u p a n d t h e x-ray yield calculated.
I n practice, this is n o t a g o o d q u a n t i t a t i v e c o r r e c
tion t o o l , for several r e a s o n s . First, t h e calculation
p r o c e e d s from t h e full d e s c r i p t i o n of t h e s a m p l e ,
w h i c h is u n k n o w n , t o t h e x-ray intensities, which c a n
be m e a s u r e d . E x c e p t in simple cases, for instance, the
thickness of a c o a t i n g layer, it is difficult t o iterate the
u n k n o w n p a r a m e t e r s t o achieve a g r e e m e n t . Second,
t h e c o m p u t e r t i m e n e e d e d t o t r a c k e n o u g h electrons
t o o b t a i n g o o d results is n o t trivial. S o m e very useful
simplifications of t h e full M o n t e C a r l o a p p r o a c h h a v e
579
X-Ray
Microanalysis,
Quantitative
4. Dimensions
of
Analysis
F o r h e t e r o g e n e o u s samples o r n o n i d e a l surfaces it is
i m p o r t a n t t o k n o w the d i m e n s i o n s of t h e region in
which the electrons scatter a n d rays a r e g e n e r a t e d .
In thin sections ( A E M ) this is basically a t r u n c a t e d
c o n e , s p r e a d i n g from t h e incident electron b e a m ,
w h o s e angle d e p e n d s u p o n electron voltage a n d t h e
s a m p l e ' s a t o m i c n u m b e r a n d density. W h i l e t h e m e a n
d i a m e t e r of the a n a l y z e d v o l u m e c a n be very small
(less t h a n 50 n m ) for thin specimens, this is often still
i n a d e q u a t e t o analyze selectively individual precipi
tates a n d inclusions. T h e m a t r i x is included in t h e
excited region a n d m a k e s q u a n t i t a t i v e analysis diffi
cult if n o t impossible. Physical s e p a r a t i o n of t h e
features of interest from t h e m a t r i x , for e x a m p l e , with
a n e x t r a c t i o n replica, is s o m e t i m e s a practical solu
tion. In analyzing small features in thin specimens, the
use of extremely small electron b e a m s (to achieve t h e
best possible spatial resolution) p r o d u c e s very low
c o u n t rates, w h i c h m a k e s a n y e x t r a n e o u s b a c k g r o u n d
d u e t o electron scattering in t h e m i c r o s c o p e , for
instance, m o r e i m p o r t a n t , a n d also restricts a c c u r a c y
because of limited c o u n t i n g statistics.
In b u l k samples, subsurface s t r u c t u r e s m a y be
invisible in t h e S E M i m a g e b u t still c o n t r i b u t e t o t h e
analysis. T h e excited region is generally described as a
t e a r d r o p o r sphere. T h e p r o b a b i l i t y of electron scat
tering d e p e n d s o n a t o m i c n u m b e r (the c h a r g e o n t h e
nucleus) so t h a t the s h a p e of t h e excited v o l u m e
b e c o m e s m o r e flattened ( b r o a d c o m p a r e d t o its d e p t h )
for h i g h - Z specimens, a n d conversely b e c o m e s d e e p e r
c o m p a r e d t o its b r e a d t h for l o w - Z specimens. T h e
electron r a n g e d e p e n d s p r i m a r i l y o n t h e electron
580
Figure 2
Schematic diagram of the variation in size and shape of
the electron excited region with specimen atomic number
and electron accelerating voltage
X-Ray
Bibliography
Heinrich F J 1981 Electron Beam X-Ray Microanalysis.
Van Nostrand Reinhold, New York
Heinrich F J, Newbury D E, Yokowitz (eds.) 1976 Use
of Monte-Carlo Calculations in Electron Probe Microana
lysis and Scanning Electron Microscopy, National Bureau
of Standards Special Publication 460. US Department of
Commerce, Washington, DC
Russ J C 1984 Fundamentals of Dispersive X-Ray Analysis.
Butterworth, London
Scott V D, Love G 1983 Quantitative Electron Probe Mic
roanalysis. Ellis Horwood, Chichester, UK
Vollath D 1986 Some fundamental considerations to pre
cede image analysis. Bull. Mater. Sci. (India) 8: 169-82
J. C. R u s s
[ N o r t h C a r o l i n a State University,
Raleigh, N o r t h C a r o l i n a , U S A ]
Diffraction
m e t h o d . H o w e v e r , as in all analytical m e t h o d s it is
advisable w h e n e v e r possible t o s u p p l e m e n t x-ray in
f o r m a t i o n with d a t a from related m e t h o d s such a s
electron m i c r o s c o p y , x-ray fluorescence s p e c t r o s c o p y
a n d electron m i c r o p r o b e analysis.
T h e principal uses of t h e x-ray p o w d e r m e t h o d a r e :
(a)
(b)
distinguishing b e t w e e n m i x t u r e s , v a r i o u s types
of solid s o l u t i o n s a n d p o l y m o r p h s ;
(c)
distinguishing b e t w e e n t h e a m o r p h o u s a n d crys
talline states;
(d)
precision m e a s u r e m e n t o f lattice p a r a m e t e r s a n d
thermal expansion;
(e)
(f)
(g)
d e t e r m i n a t i o n of p h a s e s a n d p r o p e r t i e s as a
function of specimen e n v i r o n m e n t either in situ
o r after t r e a t m e n t a t t e m p e r a t u r e s from liquid
helium t o a b o u t 2000 C, a n d pressures u p t o
several h u n d r e d k b a r , in air, v a c u u m o r selected
gas.
Powder
1. Basis of
Method
(1)
2 0 = 2 s i n - [ A / 2 ^ / )]
(2)
581
X-Ray
Powder
Diffraction
CuKa,
rays a t 28.44 (20), from
which
d{lu) = 0.31357 n m . T h e second o r d e r d o e s n o t o c c u r
because of t h e lattice s y m m e t r y of the silicon a n d the
= 0.10453 n m . In
third o r d e r = 3 is a t 94.95
333)
is used instead of
crystallographic w o r k (hkl) =
= 3.
T h e relative intensities of the reflections a r e given
by
I,(hkl)
,|2
=
'
( 1+
cos-
K s i n 2 0 s i n
2 0 '\
2
)
(in:
Si ( 2 2 0 )
Si (311) --
D(220)
Si (422)
Si ( 4 0 0 ) | ? i (331)
0 (311J
(
(b)
|"">
(220)
(311)
(200)
(40
l ?2 2) )2
0)(33)
(422)
I
|(420) '
(I00).j
(C )
002)
(101)
(110)
(103) J
(112)
(102)
(300)
30
40
50
60
70
80
90
29
Figure 1
X-ray powder diffraction patterns of substances with
similar atomic arrangements: (a) silicon and diamond,
(b) sphalerite (face-centered-cubic ZnS), and (c) wurtzite
(hexagonal ZnS). The dashed lines connect the common
fundamental reflections
(4)
582
(III)
...
Si
(a)
2. Instrument
and Experimental
Methods
X-Ray
3. Phase
12.398
2nne.E,hkl)
Diffraction
s o r t e d i n t o n a r r o w energy c h a n n e l s b y t h e pulse
height analyzer. T h e Si(Li) crystal d e t e c t o r m u s t be
k e p t a t l i q u i d - n i t r o g e n t e m p e r a t u r e a t all times.
T h e r e is n o need for s c a n n i n g b e c a u s e all the
reflections a r e r e c o r d e d s i m u l t a n e o u s l y . T h e m e t h o d
h a s t h e a d v a n t a g e t h a t a recognizable p a t t e r n (with
low statistical a c c u r a c y ) c a n be o b t a i n e d in less t h a n a
m i n u t e with a c o n v e n t i o n a l x-ray t u b e , o r in a few
s e c o n d s with a s y n c h r o t o n x-ray b e a m ; f u r t h e r m o r e ,
since there a r e n o m o v i n g p a r t s , specimen devices for
h e a t i n g a n d c o o l i n g a r e relatively easy t o m a k e .
H o w e v e r , t h e r e s o l u t i o n , w h i c h is d e t e r m i n e d by t h e
d e t e c t o r , is m o r e t h a n o n e o r d e r of m a g n i t u d e lower
t h a n t h a t of a s c a n n i n g diffractometer, a n d t h e p e a k t o - b a c k g r o u n d r a t i o m u c h lower, m a k i n g it useful
only for t h e simple p a t t e r n s .
C o n s i d e r a b l e c a r e is r e q u i r e d t o p r e p a r e speci
m e n s for x-ray diffraction. O n l y t h e surface layer of
thickness d e t e r m i n e d b y t h e a b s o r p t i o n c o n t r i b u t e s t o
t h e diffraction, a n d therefore h o m o g e n e i t y , flatness,
p a c k i n g a n d similar factors a r e i m p o r t a n t in s a m p l e
p r e p a r a t i o n . T h e specimen s h o u l d b e a b o u t 1-2 c m in
d i a m e t e r , a l t h o u g h smaller specimens c a n b e used.
T h e crystallites s h o u l d b e small, preferably less t h a n
a b o u t 20 , a n d t h e specimen r o t a t e d a b o u t 70 r p m
a r o u n d a n axis n o r m a l t o t h e surface t o o b t a i n g o o d
values of t h e relative intensities. T h e p o w d e r m a y be
c e m e n t e d with a 5 % s o l u t i o n of a m y l a c e t a t e in
c o l l o d i o n , o r with vaseline t o a glass slide, a shallow
cylindrical h o l d e r o r single-crystal p l a t e c u t in a
direction t h a t d o e s n o t p r o d u c e a reflection in t h e
a n g u l a r r a n g e r e c o r d e d [e.g., silicon (510)]. F i l m s a s
thin as 3 0 - 4 0 n m c a n be a n a l y z e d if they a r e well
crystallized.
Figure 2
Geometry of the x-ray powder diffractometer in the
focusing plane: F, line focus of x-ray tube; PS, parallel foil
assembly to limit divergence in plane of drawing; DS,
divergence slit; Sp, specimen; O, diffractometer axis of
rotation; , Bragg angle; RS, receiving slit; AS, antiscatter
slits; M, curved crystal monochromator; D, scintillation or
proportional counter; SpFC, specimen focusing circle
(radius varies with 0); DC, diffractometer circle with 20
scale; MFC, monochromator focusing circle
Powder
( 5
Identification
583
X-Ray
Powder
Diffraction
p r o g r a m s use selectable t e r r o r w i n d o w s , a u t o m a t i c
d a t a c o r r e c t i o n with internal s t a n d a r d s , chemicald a t a prescreening a n d o t h e r o p t i o n s t o facilitate the
identification, a n d c o m p u t e a figure of merit w h i c h
gives the " g o o d n e s s of fit" of the u n k n o w n c o m p a r e d
with each of the selected p o t e n t i a l s t a n d a r d s . T h e
c o m p u t e r also displays the p a t t e r n s of the u n k n o w n
with each of the selected s t a n d a r d s for direct visual
c o m p a r i s o n . (All the p o w d e r p a t t e r n s in this article
are c o m p u t e r - g e n e r a t e d . ) It is n o w possible t o collect
the d a t a , reduce it t o a set of d a n d / values a n d
identify the c o n s t i t u e n t s of a n a v e r a g e m a t e r i a l in 1 0 20 m i n . If a user file is m a d e with a g r o u p of m a t e r i a l s
likely t o be f o u n d in a p a r t i c u l a r type of a p p l i c a t i o n ,
identification time is greatly reduced because the size
of the s t a n d a r d file is m u c h smaller a n d its q u a l i t y c a n
be controlled.
T h e r e are a large n u m b e r of a p p l i c a t i o n s of the
p o w d e r m e t h o d based o n p h a s e identification. A
typical l a b o r a t o r y use is t o follow the c o u r s e of a
solid-state chemical r e a c t i o n which c a n n o t be per
formed by chemical analysis b e c a u s e the b a t c h
c o m p o s i t i o n r e m a i n s the s a m e . F o r e x a m p l e , large
single-crystal b o u l e s of G d 3 G a 5 0 1 2, g a r n e t are used as
substrates for m a g n e t i c b u b b l e devices. T h e i r g r o w t h
requires a starting g a r n e t p o w d e r p r e p a r e d by sinter
ing a blend of G d 2 0 3 a n d G a 2 0 3 in p r o p e r p r o p o r t i o n s
to the correct t e m p e r a t u r e .
T h e p a t t e r n s required for this analysis were m a d e
with a m i n i c o m p u t e r - a u t o m a t e d diffractometer (see
Fig. 3). T h e u p p e r p a t t e r n is the s t a r t i n g oxide mix
ture blend a n d the tick m a r k s a r e the p e a k p o s i t i o n s .
T h e following t w o p a t t e r n s are the s t a n d a r d s identi
fied by c o m p u t e r s e a r c h - m a t c h : the cubic form of aG d 2 0 3 a n d the m o n o c l i n i c / ? - G a 2 0 3 . T h e intensities in
b o t h s t a n d a r d s h a v e been scaled by the c o m p u t e r t o
a p p r o x i m a t e t h o s e in the blend. T h o s e p e a k s m a t c h
ing the blend a r e identified by the lower set of tick
m a r k s . T h e e x p a n d e d p a t t e r n (Fig. 3b) s h o w s the
partially c o m p l e t e d c o n v e r s i o n t o g a r n e t a n d the
small a m o u n t of residual / ? - G a 2 0 3 indicates the cor
rect sintering c o n d i t i o n s h a v e a l m o s t been r e a c h e d .
T h e m a x i m u m n u m b e r of p h a s e s t h a t c a n be identi
fied in a specimen d e p e n d s o n the complexity of the
p a t t e r n s a n d the degree of o v e r l a p p i n g . Profile fitting
c a n be used t o s e p a r a t e the o v e r l a p p i n g reflections
a n d t o d e t e r m i n e the individual intensities (Parrish
a n d H u a n g 1979). M i x t u r e s of six p h a s e s c a n b e
p e r f o r m e d routinely with c o m p u t e r m e t h o d s .
T h e m i n i m u m a m o u n t of a p h a s e t h a t is detectable
in a m i x t u r e is d e p e n d e n t o n the a b s o r p t i o n , crystalli
nity a n d p e a k - t o - b a c k g r o u n d r a t i o s . T h e lower limits
r a n g e from a b o u t 0 . 1 - 5 w t % . Very small a m o u n t s of
a sample (in the m i c r o g r a m r a n g e ) c a n be detected,
b u t even smaller samples require special t e c h n i q u e s
using high-brilliance r o t a t i n g - a n o d e x-ray t u b e s .
Q u a n t i t a t i v e d e t e r m i n a t i o n of t h e c o n c e n t r a t i o n of
each p h a s e in a m i x t u r e requires careful specimen
p r e p a r a t i o n a n d m e a s u r e m e n t s of a few of the higher-
584
Oxide
mixture
ci-
Ll
J-
.A,
G d 20 3
, A,
> . A ,..-
/ 3 - G a 20 3
...
30
, 6 A A
. A
40
50
<
I
26
32
G A
38
20
Figure 3
Patterns of (a) mixed blend of two oxides and the phases
identified by computer search-match, and (b) after
sintering showing conversion to garnet Gd 3Ga 50 12 (G) and
residual -Ga 20 3(A) and a-Gd 2Q 3(D)
X-Ray
4. Lattice-Parameter
Powder
Diffraction
Determination
T h e lattice p a r a m e t e r a0 is frequently r e q u i r e d in
m a t e r i a l s c h a r a c t e r i z a t i o n . A n u m b e r of reflections
s h o u l d be m e a s u r e d a n d their relation t o a0 is given by
E q n . (4). Careful e x p e r i m e n t a l t e c h n i q u e s m u s t be
used t o o b t a i n a c c u r a t e values. S y s t e m a t i c e r r o r s are
t h e p r i n c i p a l c a u s e of low a c c u r a c y a n d they c a n be
m i n i m i z e d by using h i g h e r - a n g l e reflections. T h e r e a r e
t w o basic r e a s o n s for this: (a) i n s t r u m e n t a l a b e r r a
t i o n s a n d specimen d i s p l a c e m e n t e r r o r s increase
r a p i d l y with decreasing reflection angle, a n d (b) the
h i g h e r t h e reflection angle t h e g r e a t e r t h e a c c u r a c y , as
s h o w n b y t h e differential f o r m of t h e B r a g g e q u a t i o n :
Figure 4
X-ray diffractometer pattern of a small quantity of
crystalline quartz (two peaks) on a glass substrate
c h a n g e s in t h e lattice p a r a m e t e r a0 if t h e s u b s t i t u t i n g
a t o m s h a v e different sizes. T h e r e is a very r o u g h linear
relation b e t w e e n c o m p o s i t i o n a n d a0 a n d t h e c o m p o
sition m a y b e d e t e r m i n e d from t h e shifts in p e a k
positions. The substituting atoms are randomly
a r r a n g e d o n t h e lattice sites, b u t in s o m e cases p r o p e r
annealing may produce a long-range order which can
be detected b y t h e a p p e a r a n c e of a d d i t i o n a l p e a k s
called s u p e r s t r u c t u r e reflections. T h e y a r e generally
m u c h w e a k e r t h a n t h e f u n d a m e n t a l reflections a n d
d e p a r t u r e s from perfect l o n g - r a n g e o r d e r further
w e a k e n s t h e m . Interstitial a n d defect types of solid
solutions m a y b e detected b y c o m p a r i n g t h e m e a s u r e d
density with t h e density c a l c u l a t e d from t h e unit-cell
volume.
T h e crystalline a n d a m o r p h o u s states c a n be readily
distinguished. A n a m o r p h o u s solid h a s only local
short-range order without the repeating long-range
lattice o r d e r characteristic of t h e crystalline state. T h e
diffraction from a n a m o r p h o u s s u b s t a n c e is a b r o a d
h u m p e x t e n d i n g o v e r a w i d e a n g u l a r r a n g e as s h o w n
b y t h e p a t t e r n of a m i c r o s c o p e slide ( F i g . 4). If t h e
m a t e r i a l c o n t a i n s a crystalline p o r t i o n o r begins t o
devitrify, t h e crystalline p a t t e r n is s u p e r i m p o s e d as
illustrated b y t h e a d d i t i o n of a few m i c r o g r a m s of
q u a r t z p o w d e r o n t o t h e slide. T h e crystalline p e a k
intensities a r e m u c h higher a n d t h e (101) reflection of
the s a m e m a s s of q u a r t z w o u l d b e a b o u t 260 times
higher t h a n t h e t o p of t h e a m o r p h o u s b a n d . M o s t
a m o r p h o u s p a t t e r n s a r e similar a n d c a n n o t b e used t o
identify m a t e r i a l s . R a d i a l d i s t r i b u t i o n functions c a n
be derived t o d e t e r m i n e local a t o m i c a r r a n g e m e n t s
( W a r r e n 1969). C r y s t a l l i n e - t o - a m o r p h o u s weight
ratios m a y be a p p r o x i m a t e l y d e t e r m i n e d f r o m t h e
relative intensities of all t h e crystalline reflections a n d
the a m o r p h o u s p a r t . T h i s usually requires s t a n d a r d s
of k n o w n r a t i o s . H o w e v e r , if p o o r l y crystallized
m a t e r i a l is p r e s e n t t h e d e t e r m i n a t i o n b e c o m e s m u c h
m o r e difficult o r impossible.
Ad/d=
-A0cos 0
(6)
585
X-Ray
Powder
Diffraction
5. Preferred
Orientation
N o n r a n d o m d i s t r i b u t i o n of crystallites in a m a t e r i a l is
called preferred o r i e n t a t i o n o r t e x t u r e . It m a y result
from t h e m e t h o d of p r e p a r a t i o n a n d c a n m a r k e d l y
affect t h e p r o p e r t i e s . F o r e x a m p l e , t h e crystallites in a
c o l d - d r a w n wire orient w i t h t h e s a m e c r y s t a l l o g r a p h i c
direction parallel t o t h e wire axis, a n d in rolled m e t a l
sheets certain p l a n e s orient parallel t o t h e surface a n d
t h e rolling direction w h e n t h e grains r o t a t e a n d align
d u r i n g t h e plastic d e f o r m a t i o n . Preferred o r i e n t a t i o n
also o c c u r s in castings, electrochemical d e p o s i t i o n
a n d t h i n films. T h e degree of preferred o r i e n t a t i o n c a n
be d e t e r m i n e d with a pole-figure device a t t a c h e d t o
t h e diffractometer t o m e a s u r e intensities for different
specimen o r i e n t a t i o n s . T h e intensities c a n b e p l o t t e d
o n a s t e r e o g r a p h i c projection a n d c o n t o u r e d t o s h o w
t h e a n g u l a r d i s t r i b u t i o n of t h e n o r m a l s t o selected
lattice p l a n e s in v a r i o u s c r y s t a l l o g r a p h i c directions.
Such p l o t s a r e used t o follow s t r u c t u r a l c h a n g e s in
metallurgical m a t e r i a l s subjected t o m e c h a n i c a l a n d
t h e r m a l processes.
(b)
Figure 5
(a) Method for precision lattice-parameter measurement of
single-crystal plate and mismatch of epitaxial film on
substrate by parallel double-crystal method, and
(b) profiles of pair of films F and C on substrate S
uses a n o n d i v e r g e n t m o n o c h r o m a t i c b e a m from a
high-quality g a r n e t wafer C 2 m o u n t e d a p p r o x i m a t e l y
parallel t o C I , d e t e c t o r D l is m o v e d t o , a n d t h e
specimen C I r o t a t e d t o pick u p t h e reflections s h o w n
in the lower p a r t of Fig. 5. (In p r a c t i c e C I a n d C 2 c a n
be i n t e r c h a n g e d . ) T h e e x a m p l e s h o w n is a p a i r of
films F a n d C of different c o m p o s i t i o n s g r o w n o n t h e
s u b s t r a t e S with lattice p a r a m e t e r s of F > S > C . T h e
p e a k s e p a r a t i o n of C a n d S is 112" ( c o r r e s p o n d i n g t o
4
Aa/a = 2.1 x 10~ ) a n d b e t w e e n F a n d S is
4
76" = 2.2 x 1 0 " from which t h e m e a n strain in e a c h
film c a n be calculated. T h e large difference in a0
between film F d e p o s i t e d o n film C c a u s e d a s y m m e t
ric b r o a d e n i n g of t h e F profile i n d i c a t i n g n o n u n i f o r m
strain. T h i s is a n e x a m p l e of t h e u n i q u e analytical
capabilities of x-ray diffraction in which t h e indi
vidual p r o p e r t i e s of physically s u p e r i m p o s e d m a t e r
ials c a n be d e t e r m i n e d .
586
Imperfections
X-Ray
84
85
86
87
88
1
89
20
Figure 6
X-ray diffractometer reflection profiles of Pd(222) thin
film broadened by strain and standard well-crystallized
powder W(220); peak intensities normalized
Powder
Diffraction
X - r a y m e t h o d s a r e used a s a n o n d e s t r u c t i v e
m e t h o d t o d e t e r m i n e residual elastic strains. A l
t h o u g h t h e elastic c o n s t a n t s v a r y c o n s i d e r a b l y with
c r y s t a l l o g r a p h i c d i r e c t i o n they a r e r o u g h l y i s o t r o p i c
in r a n d o m polycrystalline m a t e r i a l s . U s i n g small xr a y b e a m s , s t r a i n s c a n b e m e a s u r e d in small a r e a s a n d
steep s t r a i n g r a d i e n t s c a n b e d e t e r m i n e d . T h e m e t h o d
is b a s e d o n t h e fact t h a t t h e lattice s p a c i n g d{hkl,
c h a n g e s w i t h a p p l i e d stress a n d acts a s a n i n t e r n a l
s t r a i n g a u g e . U n i f o r m l o n g - r a n g e tensile strain in
creases t h e d values a n d shifts t h e p e a k s t o smaller
angles w i t h o u t b r o a d e n i n g . N o n u n i f o r m s t r a i n s c a u s e
b r o a d e n i n g w i t h o u t shifts. B o t h elastic a n d plastic
d e f o r m a t i o n strains c a u s e shifts a n d b r o a d e n i n g .
W h e n t h e d i m e n s i o n s of crystallites a r e less t h a n
a b o u t 1 t h e profiles begin t o b r o a d e n a n d t h e
b r o a d e n i n g increases w i t h d e c r e a s i n g size. B o t h size
a n d strain b r o a d e n i n g c a n b e m e a s u r e d w h e n they
coexist b y u s i n g t h e F o u r i e r m e t h o d a n d several
o r d e r s o f a reflection; t h e size factor is i n d e p e n d e n t of,
a n d t h e d i s t o r t i o n d e p e n d e n t o n , t h e o r d e r of t h e
reflection.
A simplified m e t h o d frequently used t o d e t e r m i n e
small crystallite sizes a s s u m e s t h e r e a r e n o strains o r
o t h e r sources of line b r o a d e n i n g . It uses t h e Scherrer
equation:
=
cos 0 ^ B( 2 0 )
w h e r e t{hkl) is t h e a v e r a g e d i m e n s i o n o f t h e crystallites
n o r m a l t o t h e (hkl) diffracting p l a n e , k is a c o n s t a n t
usually t a k e n a s 0.9, is t h e w a v e l e n g t h ( n m ) 0
t h e B r a g g angle a n d PB (2) t h e particle size line
b r o a d e n i n g in r a d i a n s m e a s u r e d a s t h e full-width
h a l f - m a x i m u m ( F W H M ) . (2) is o b t a i n e d from
>
>
/ B(2^) = [ / O ^ ) - ^ S T ( 2 ^ ) ]
1 /2
(8)
w h e r e P0 (20) is t h e w i d t h o f t h e m e a s u r e d profile a n d
PST(29) t h e w i d t h of t h e i n s t r u m e n t function profile.
F o r a given t t h e b r o a d e n i n g increases a s l / c o s 0 ,
b u t t h e intensities decrease w i t h increasing 2 a n d
d e c r e a s i n g r, m a k i n g it m o r e difficult t o m a k e accur
a t e m e a s u r e m e n t s . I n p r a c t i c e t h e useful r a n g e of t h e
m e t h o d is a b o u t 5 - 3 0 0 n m . A l t h o u g h t c a n b e deter
m i n e d for several d i r e c t i o n s b y u s i n g different (hkl)
p l a n e s , it is desirable t o u s e s c a n n i n g electron m i c r o s
c o p y t o d e t e r m i n e t h e m o r p h o l o g y b e c a u s e if t h e
particles a r e needles o r p l a t e s t h e results c o u l d b e in
e r r o r . T h e t w o m e t h o d s a r e c o m p l e m e n t a r y since t h e
x-ray m e t h o d gives t h e a v e r a g e crystallite size a n d t h e
m i c r o s c o p e t h e particle size, w h i c h m a y b e clusters of
crystallites.
Diffuse s c a t t e r i n g within a few degrees o f t h e direct
b e a m (small-angle diffraction) is a m e t h o d used for
particle size d e t e r m i n a t i o n typically from a few n a n o
m e t e r s t o tens o f n a n o m e t e r s . It is a p p l i c a b l e t o
a m o r p h o u s a s well a s crystalline m a t e r i a l s , a n d is used
for a n a l y z i n g s u s p e n s i o n s , single-chain d i m e n s i o n s of
587
X-Ray
Powder
Diffraction
Bibliography
Azaroff L V, Buerger J 1958 The Powder Method in XRay Crystallography. McGraw-Hill, New York
Barrett C S, Massalski 1966 Structure of Metals:
Crystallographic Methods, Principles and Data, 3rd edn.
McGraw-Hill, New York
Guinier A 1956 Theorie et Technique de la Radiocristallographie. Dunod, Paris
International Tables for X-Ray Crystallography
1969.
Kynoch, Birmingham, UK
Klug , Alexander L 1974 X-Ray Diffraction Proced
ures for Poly crystalline and Amorphous Materials, 2nd
588
LIST OF CONTRIBUTORS
Contributors are listed in alphabetical order together with their addresses. Titles of articles that they have authored follow
in alphabetical order. W h e r e articles are coauthored, this has been indicated by an asterisk preceding the title.
Aubertin, F .
Universitat des Saarlandes
Fachbereich 12.1
Werkstoffwissenschaften
D-6600 Saarbriicken
Germany
*Mossbauer
France
^Ceramic Materials: Cathodoluminescence
Spectroscopy
Averback, R. S.
Materials Science and Technology Division
Building 212
Argonne National Laboratory
9700 South Cass Street
Argonne, IL 60439
USA
*X-Ray and Neutron Diffuse Scattering of RadiationInduced Defects
Bair, . E.
AT&T Bell Laboratories
600 Mountain Avenue
Murray Hill, NJ 07974
USA
Polymers: Tests for Thermal
Polymers: Thermal Analysis
Properties
Bakhru, H.
Physics Department
State University of New York
1400 Washington Avenue
Albany, NY 12222
USA
Ion Backscattering
Analysis
Banerjee, D.
Defence Metallurgical Research Laboratory
Ministry of Defence
Government of India
Kanchanbagh P. O.
Hyderabad 500 258
India
Channelling-Enhanced
Microanalysis
Barrett, R.
CNRS
Laboratoire de Crystallographie
BP 166
F-38042 Grenoble C6dex 09
Analysis
Beall, F . C.
Forest Products Laboratory
University of California
1301 South 46th Street
Berkeley, CA 94720
USA
Wood: Acoustic Emission and
Acousto-Ultrasonic
Characteristics
Benton, J. L.
Room 1E-336
AT&T Bell Laboratories
600 Mountain Avenue
Murray Hill, NJ 07974-2070
USA
Junction Transient
Spectroscopy
Berry, G. C.
Department of Chemistry
Carnegie Mellon University
Pittsburgh, PA 15213
USA
Polymers: Molecular Weight and its
Distribution
Berlin, E. P.
RCA Laboratories
Princeton, NJ 08540
USA
X-Ray Fluorescence
Spectrometry
Blamire, M . G.
Department of Materials Science and Metallurgy
University of Cambridge
Pembroke Street
Cambridge
CB2 3QZ
UK
Anodization
Spectroscopy
Bleichert, H.
Institut fur Festkorperforschung, Kernforschungsanlage
Julich GmbH
KFA Julich
Postfach 1915
D-5170 Julich
Germany
*Gamma-Ray
Diffractometry
589
List of
Bonnell
Contributors
Bonnell, D. A.
Department of Materials Science and Engineering
University of Pennsylvania
3231 Walnut Street
Philadelphia, PA 19104-6272
USA
Castle, J. E.
Department of Metallurgy and Materials Technology
University of Surrey
Guildford
GU2 5XH
UK
and
Spectroscopy
Bremer, F. J.
Choi, C. S.
*Gamma-Ray
Dijfractometry
Brimhall, J. L.
Battelle-Pacific Northwest Laboratories
PO Box 999
Richland, WA 99352
USA
Electron Microscope Analysis of Defect Clusters,
and Bubbles
Voids
Cahn, R. W.
Department of Materials Science and Metallurgy
University of Cambridge
Pembroke Street
Cambridge
CB2 3QZ
UK
Microtextural Analysis
Campana, C. F.
Nicolet Corporation
1006 Bubb Road
Cupertino, CA 95014
USA
Single-Crystal X-Ray Diffraction
Campbell, A. M.
Department of Engineering
University of Cambridge
Trumpington Street
Cambridge
CB2 1PZ
UK
Superconducting
Materials:
Conant, F. S.
143 Gunarh Drive
Akron, OH 44139
USA
Elastomers: Tests for Mechanical
Properties
Cooper, M. J.
Department of Physics
University of Warwick
Coventry
CV4 7AL
UK
Compton
Scattering
Cox, S. F. J.
Measurements
Carnahan, C. Jr
Chemical and Structural Analysis Branch
General Electric Corporate Research and Development
PO Box 8
Schenectady, NY 12301
USA
Gas and Liquid Chromatography
590
Clarke, . T.
Technical Operations Inc.
One Beacon Street
Boston, MA 21108
USA
Gamma Radiography
List of
USA
Polymers: X-Ray
Cullis, A. G.
Defence Research Agency
Electronics Division
Royal Signals and Radar Establishment
St Andrews Road
Malvern
Worcestershire
WR14 3PS
UK
* Semiconducting Materials: Electron Microscopy
Davies, G. J.
Department of Metallurgy
University of Sheffield
Mappen Street
Sheffield
SI 3JD
UK
Functions
D e a n , S . W . Jr
Air Products and Chemicals Inc.
PO Box 538
Allentown, PA 18105
USA
Corrosion: Test Methods
Denoyer, E. R.
The Perkin-Elmer Corporation
761 Main Avenue
Norwalk, CT 06859-0215
USA
Laser Sampling Inductively Coupled Plasma
Spectrometry
Elliott, . E.
MST Division
Los Alamos National Laboratory
Mail Stop 549
Los Alamos, NM 87545
USA
*Microengineering of Materials:
Characterization
F a b e r , J. Jr
Materials Science and Technology Division
Building 212
Argonne National Laboratory
9700 South Cass Street
Argonne, IL 60439
USA
*X-Ray and Neutron Diffuse Scattering of RadiationInduced Defects
Fleischer, R. L.
Earth and Environmental Sciences Department
Rensselaer Polytechnic Institute
Troy, NY 12180-3590
USA
Solid-State Nuclear Track Detectors:
Mass
Donahue, P. E.
General Electric Corporate Research and Development
PO Box 8
Schenectady, NY 12301
USA
*Nuclear Magnetic Resonance
Spectroscopy
Eades, J. A.
Center for Microanalysis of Materials
University of Illinois at Urbana-Champaign
104 Goodwin Avenue
Urbana, IL 61801
USA
Transmission Electron Microscopy:
Convergent-Beam
and Microdiffraction
Techniques
Early, T. A.
Materials Characterization Laboratory
Frank
Scattering
Contributors
Applications
Fleming, S. J.
MASCA, University Museum
University of Pennsylvania
33rd and Spruce Streets
Philadelphia, PA 19104
USA
Art Forgeries: Scientific
Detection
Flower, . M.
Department of Metallurgy and Materials Science
Imperial College of Science, Technology and Medicine
London
SW7 2AZ
UK
Electron Microscopy,
High-Voltage
Foreman, L. R.
MST Division
Los Alamos National Laboratory
Mail Stop 549
Los Alamos, NM 87545
USA
*Microengineering of Materials:
Characterization
Frank, D. G.
The Surface Center
Department of Chemistry
591
Frank
List of
University of Cincinnati
Cincinnati, OH 45221-0172
USA
*Auger Microscopy,
Angular
Distribution
Fray, D. J.
Department of Materials Science and Metallurgy
University of Cambridge
Pembroke Street
Cambridge
CB2 3QZ
UK
Gas Sensors, Solid-State
Gallagher, P. K.
Department of Chemistry
The Ohio State University
120 West 18th Avenue
Columbus, OH 43210-1173
USA
Thermal Analysis: Recent Developments
Radiography
Gaskell, D. R.
School of Materials Engineering
Chemical/Metallurgical Engineering Building
Purdue University
West Lafayette, IN 47907
USA
Thermodynamic Activity: Measurement
Gibson, P. N.
Physics Division
Joint Research CentreCEC
Ispra Establishment
1-21020 Ispra (Varese)
Italy
Thin Films: Characterization
by X Rays
Gilmore, R.
General Electric Corporate Research and Development
PO Box 8
Schenectady, NY 12301
USA
Acoustic
Microscopy
Gonser, U.
Universitat des Saarlandes
Fachbereich 12.1
Werkstoffwissenschaften
D-6600 Saarbriicken
Germany
*Mossbauer
Spectroscopy
592
Graham, C. D. Jr
Department of Materials Science and Engineering
University of Pennsylvania
3231 Walnut Street
Philadelphia, PA 19104-6272
USA
Magnetic Materials:
Measurements
Harrington, J. A.
Hughes Research Laboratories
3011 S Malibu Canyon Road
Malibu, CA 90265
USA
Optical Calorimetry
Hawkins, W. L.
26 High Street
Montclair, NJ 07042
USA
Polymers: Tests for Degradation
and
Stabilization
Haynes, J. M.
School of Chemistry
University of Bristol
Cantocks Close
Bristol
BS8ITS
UK
Garrett, D. A.
National Bureau of Standards
Washington, DC 20234
USA
Neutron
Contributors
Porosity: Characterization
and
Investigation
Hemsley, D. A.
Institute of Polymer Technology
Loughborough University of Technology
Loughborough
Leicestershire
LE11 3TU
UK
Polymers: Light
Microscopy
Henneke, E. G. II
Department of Engineering Science and Mechanics
Virginia Polytechnic Institute and State University
Blacksburg, VA 24061
USA
Vibrothermography
Hofmann, S.
Max-Planck-Institut fur Metallforschung
Institut fur Werkstoffwissenschaft
Seestrasse 92
D-7000 Stuttgart 1
Germany
Depth Profiling
Holik, A. S.
Chemical and Structural Analysis Branch
General Electric Corporate Research and Development
List of
Contributors
Knapp
PO Box 8
Schenectady, NY 12301
USA
Optical Microscopy
Houston, J. E.
Sandia National Laboratories
Albuquerque, NM 37115
USA
Kallmes, O. J.
M/K Systems Inc.
12 Garden Street
Danvers, MA 01923
USA
Suifaces
Hsu, S. L.
Department of Polymer Science and Engineering
University of Massachusetts
Amherst, MA 01003
USA
Polymers: Raman Spectroscopy
Hubbard, A. T.
The Surface Center
Department of Chemistry
University of Cincinnati
Cincinnati, OH 45221-0172
USA
*Auger Microscopy,
Angular
Distribution
Hutchings, . T.
The National Nondestructive Testing Centre
AEA Industrial Technology
Harwell Laboratory
Didcot
Oxfordshire
OX11 OR A
UK
Residual Stresses: Measurement Using Neutron
Diffraction
Jannink, G.
Service de Physique du Solide et de Resonance
Magnetique
Centre d'Etudes Nucleaires Saclay
F-91191 Gif Sur Yvette Cedex
France
Polymers: Neutron Scattering
Johansson, S. A. E .
Department of Nuclear Physics
Lund Institute of Technology
Solvegatan 14
S-223 62 Lund
Sweden
Particle-Induced X-Ray Emission
Johnson, G. E .
Room 7D214
AT&T Bell Laboratories
600 Mountain Avenue
Test Methods
Destructive
Mechanical
Testing
Katz, W .
General Electric Corporate Research and Development
PO Box 8
Schenectady, NY 12301
USA
Secondary-Ion Mass Spectrometry
Kaufman, S.
AT&T Bell Laboratories
2000 Northeast Expressway
Norcross, GA 30071
USA
Polymers: Tests for
Flammability
Kelly, M . A.
Surface Science Laboratories Inc.
1206 Charleston Road
Mountain View, CA 94043
USA
Electron Spectroscopy for Chemical
Kendall, K.
ICI
PO Box 8
Runcorn
Cheshire
WA7 4QE
UK
Powder
Analysis
Mechanics
Kirchheim, R.
Max-Planck-Institut fur Metallforschung
Seestrasse 92
D-7000 Stuttgart 1
Germany
Hydrogen as a Metallurgical
Probe
Klinman, R.
Bethlehem Steel Corporation
Bethlehem, PA 18016
USA
Grain
Size:
Nondestructive
Evaluation
Knapp,
G. S.
Argonne National Laboratory
9700 South Cass Street
Argonne, IL 60439
593
List of
Knapp
USA
*X-Ray Absorption Spectroscopy:
Techniques
Knowles, . M.
Department of Materials Science and Metallurgy
University of Cambridge
Pembroke Street
Cambridge
CB2 3QZ
UK
Electron Microscopy,
Contributors
PO Box 8
Schenectady, NY 12301
USA
Liquid Chromatography Mass
Spectroscopy
Lilley, E.
Norton Company
Goddard Road
Northboro, MA 01532-1545
USA
Thermoluminescence
High-Resolution
Lind, . V.
Koenig, J. L.
Macromolecular Science Department
Case Western Reserve University
University Circle
Cleveland, OH 44106
USA
*Elastomers: Spectroscopic
Characterization
Kostorz, G.
Institut fur Angewandte Physik
Zurich
CH-8093 Zurich
Switzerland
Small-Angle Neutron Scattering in Metallurgy
Leake, J. A.
Department of Materials Science and Metallurgy
University of Cambridge
Pembroke Street
Cambridge
CB2 3QZ
UK
*Laser Microprobe Mass Spectrometry
Leipziger, F. D.
Northern Analytical Laboratory
3 Northern Boulevard
Amherst, NH 03031
USA
Spark-Source Mass
Spectrography
Lifshin, E.
Chemical and Structural Analysis Branch
General Electric Corporate Research and Development
PO Box 8
Schenectady, NY 12301
USA
An Introduction to Investigation and Characterization of
Materials
Electron Microprobe Analysis
Ligon, W. V.
Room 2A40
Building K-l
General Electric Corporate Research and Development
594
Materials: Electron
Microscopy
Marcus, H. L.
Mechanical Engineering Department
University of Texas
Mail Drop TAY167
Austin, TX 78712
USA
Auger Electron
Spectroscopy
Milne, R. H.
Department of Physics and Applied Physics
University of Strathclyde
Colville Building
North Portland Street
Glasgow
G l 1XN
UK
Reflection Electron
Microscopy
Miodownik, A. P.
Department of Materials Science and Engineering
University of Surrey
Guildford
GU2 5XH
UK
Phase Diagrams and Phase Stability:
Calculations
Mordfin, L.
Office of NDE
National Bureau of Standards
Washington, DC 20234
List of
USA
Residual Stresses: Nondestructive
Evaluation
Morris, W . G.
Building K-l
General Electric Corporate Research and Development
PO Box 8
Schenectady, NY 12301
USA
Atomic Force
Microscopy
Murch, G. E .
Department of Chemical and Materials Engineering
University of Newcastle
Newcastle
NSW 2308
Australia
Diffusion: Novel Measurement Methods
Murphy, J. C.
Applied Physics Laboratory
The Johns Hopkins University
Johns Hopkins Road
Laurel, M D 20723-6099
USA
Thermal Wave Imaging
Pendry, J. B.
Department of Physics
The Blackett Laboratory
Imperial College of Science, Technology and Medicine
Prince Consort Road
London
SW7 2B2
UK
Electron Diffraction,
Low-Energy
Pethica, J. B.
Department of Materials
University of Oxford
Parks Road
Oxford
3PH
UK
Electron Tunnelling Spectroscopy
Nondestructive
Evaluation
Pottlacher, G.
Page, T. F .
Materials Division
Department of Mechanical, Materials and Manufacturing
Engineering
Herschel Building
University of Newcastle upon Tyne
Newcastle upon Tyne
NE1 7RU
UK
Parrish, W .
[deceased; late of IBM, USA]
X-Ray Powder Diffraction
Patterson, D. J.
Macromolecular Science Department
Case Western Reserve University
University Circle
Cleveland, OH 44106
USA
* Elastomers: Spectroscopic
Characterization
Characterization
Renton
Pfeifer, R. J.
AccuRay Corporation
650 Ackerman Road
Columbus, OH 43202
USA
Oliver, W . C.
Metals and Ceramics Division
Oak Ridge National Laboratory
PO Box 2008
Oak Ridge, TN 37831
USA
Mechanical Properties
Microprobe
Onoda, G. Y.
157A Metallurgy Building
University of Florida
Gainesville, FL 32611
USA
Ceramic Powders: Packing
Contributors
Analysis
Renton, W . J.
Advanced Composites Division
595
List of
Renton
USA
Vought Corporation
PO Box 225907
Dallas, TX 75265
USA
Powder
Properties
Russ, J. C.
Analytical Instrumentation Facility
Department of Materials Science and Engineering
North Carolina State University
Box 7916
Raleigh, NC 27695
USA
Fractals
Quantitative
Rye, R. R.
Sandia National Laboratories
Albuquerque, NM 37115
USA
*Chemical Analysis of Solid Surfaces
Seidman, D. N.
Graduate School of Applied Science and Technology
Materials Science Division
Bergamann Building
Givat Ram Campus
Hebrew University of Jerusalem
91904 Jerusalem
Israel
Field-Ion Microscopy: Atom-Probe
Microanalysis
Field-Ion Microscopy: Observation of Radiation Effects
Shrader, S. R.
Shrader Analytical and Consulting Laboratories
3450 Lovett Avenue
Detroit, MI 48210
USA
Organic Mass
Characterization
Sobel, H. R.
X-Ray Microanalysis,
Contributors
Spectrometry
Spectroscopy
Srolovitz, D. J.
Department of Materials Science and Engineering
University of Michigan
Ann Arbor, MI 48109-2136
USA
Microstructural Evolution: Computer Simulation
Stone, D. E. W.
MS6 Division
Royal Aerospace Establishment
Farnborough
Hampshire
GU14 6TD
UK
^Composite Materials: Nondestructive
Evaluation
Stoneham, A. M.
AEA Industrial Technology
Harwell Laboratory
Didcot
Oxfordshire
OX11 0RA
UK
*Solid State: Study Using Muon Beams
Stupin, D. M.
MST Division
Los Alamos National Laboratory
Mail Stop 549
Los Alamos, NM 87545
USA
*Microengineering
of Materials:
Characterization
Siegel, R. W.
Materials Science and Technology Division
Argonne National Laboratory
9700 South Cass Avenue
Argonne, IL 60439
USA
Positron Annihilation Spectroscopy of Defects in Metals
Smith, A. L.
Dow Corning
Midland, MI 48640
USA
Sutton, M.
Centre for the Physics of Materials and Department of
Physics
3600 University Street
McGill University
Montreal
Qu6bec
H3A 2T8
Canada
Infrared
X-Ray Diffraction,
Spectroscopy
Smith, D. W.
Department of Metallurgical Engineering
Michigan Technological University
Houghton, MI 49931
596
Time-Resolved
Szarowski, D. H.
Wadsworth Center for Laboratories and Research
New York State Department of Health
PO Box 509
Albany, NY 12201-0509
List of
USA
*Confocal Optical
Contributors
Wunderlich
UK
*Laser Microprobe
Microscopy
Mass
Spectrometry
Wells, O. C.
IBM
Thomas J Watson Research Center
PO Box 218
Yorktown Heights, NY 10598
USA
Scanning Electron Microscopy
Tate, D. R.
11415 Farmland Drive
Rockville, M D 20852
USA
Hardness
Characterization
Tatro, C. A.
L-342
Lawrence Livermore National Laboratory
PO Box 808
Livermore, CA 94550
USA
Weyher, J. L.
MASPEC
Consiglio Nazionale delle Ricerche
ViaChiavari 18/A16/D
1-43100 Parma
Italy
Acoustic
Semiconducting
Emission
Tulin, V. A.
Institute of Solid State Physics
Chernogclovka
Moscowskaya Oblasit
142432
Russia
Electron Spin Resonance
Turner, J. N.
Wadsworth Center for Laboratories and Research
New York State Department of Health
PO Box 509
Albany, NY 12201-0509
USA
*Confocal Optical Microscopy
Veal, B. W.
Argonne National Laboratory
9700 South Cass Street
Argonne, IL 60439
USA
*X-Ray Absorption Spectroscopy:
Techniques
Vesely, D.
Department of Materials Technology
Brunei University
Uxbridge
UB8 3PH
UK
Polymers: Electron Microscopy
Wallach, E. R.
Department of Materials Science and Metallurgy
University of Cambridge
Pembroke Street
Cambridge
CB2 3QZ
Materials: Characterization
by Etching
Williams, D. B.
Department of Materials Science and Engineering
Whitaker Laboratory
Lehigh University
Bethlehem, PA 18015-3195
USA
Electron Diffraction
Electron Energy-Loss
Spectrometry
Electron Microscopy,
Analytical
Williams, E. A.
General Electric Corporate Research and Development
PO Box 8
Schenectady, NY 12301
USA
*Nuclear Magnetic Resonance
Spectroscopy
Wong, A. K.
Aircraft Structures Division
Aeronautical Research Laboratory
506 Lorimer Street
Fishermens Bend
Victoria 3207
Australia
Stress Distribution:
Effect
Wright, A. C.
J J Thomson Physical Laboratory
Whiteknights
Reading
RG6 2AF
UK
X-Ray and Neutron Diffraction Studies of Amorphous
Solids
Wunderlich, B.
Department of Chemistry
Rensselaer Polytechnic Institute
Troy, NY 12181
USA
Thermal Analysis: An Overview
597
SUBJECT INDEX
The Subject Index has been compiled to assist the reader in locating all references to a particular topic in the
Encyclopedia. Entries m a y have up to three levels of heading. W h e r e there is a substantive discussion of the topic, the
page numbers appear in bold italic type. As a further aid to the reader, cross-references have also been given to terms
of related interest. These can be found at the bottom of the entry for the first-level term to which they apply. Every effort
has been m a d e to m a k e the index as comprehensive as possible and to standardize the terms used.
ABS (acrylonitrile-butadiene-styrene)
copolymers 332
specific heat 376
transmission electron microscopy 332
Absorption coefficients
bulk absorption 279
optical calorimetry 279
surface absorption 279
thin films 280
AC losses
superconducting materials
calorimetric methods 494
electrical methods 494
Accelerated tests
corrosion 80
polymer stability 357
Acheson method 433
Acoustic emission 1
analog instrumentation 2
composites 64
vibroacoustic emission 64
digital instrumentation 2
fatigue tests 2
fiber-reinforced plastics 551
inspection 3
piezoelectric transducers 2
response characteristics 1
root-mean-square meters 2
scanning electron microscopy 424
signal processing 2
stresses 1
welds 3
wood 551
adhesives 553
applications 552
biological degradation 553
composites 553
cutting 553
defects 552
drying 553
fracture 552
mechanical testing 552
piezoelectric transducers 551
quality control 552
Acoustic microscopy 4
biological materials 4
chemical bonding 4
elastic properties 4
electron acoustic microscopy 7
history 4
photoacoustic microscopy 6
piezoelectric transducers 7
quality assurance 9
scanning acoustic microscopy 4
scanning laser acoustic microscopy 8
surface deformation 4
Acoustic properties
wood 551
Acoustoelastic constants 421
Acoustooptical devices
confocal optical microscopy 69
Acoustoultrasonics
wood 551
applications 552
Activity see Thermodynamic activity
Additives
fluorescence microscopy 342
Adhesive bonding 9
bond lines 64
bond strength 10
peel tests 13
composites 64
creep-compliance curves 10
fatigue 10
hygroscopic expansion 10
mechanical properties 9
nondestructive evaluation 64
powders 399
test methodology 13
test specimens 10
butt joint 12
double lap joint 13
evaluation criteria 10
Iosipescu specimen 13
napkin-ring specimen 13
scarf joint 12
single lap joint 10
thick-adherend symmetric lap joint 11
thermal expansion 10
viscoelastic response 10
Adhesives 9
acoustic emission 553
deformation 14
mechanical properties 9
viscoelastic response 10
wood 553
Adiabatic calorimetry 371
adiabatic thermocouple calorimetry 279
calorimeters 503
Adsorption
gases
particle size distribution 393
porosity 385
porosity 385
599
Adsorption
Brunauer-Emmett-Teller equation 385
flow methods 386
gravimetric methods 386
Langmuir equation 386
vapors 385
volumetric methods 386
scanning tunnelling microscopy 433
solutions 386
vapors 385
ZnO 433
Air pollution
particle-induced x-ray emission 313
Alloys
binary equilibrium 523
defects
amorphous materials 190
crystalline materials 190
see also Metallurgy, specific alloys
- phase transformations 189
Alpha-particle effects 122
Alternating-gradient magnetometers 226
Alumina
optical microscopy 291
packing characterization 48, 49
Aluminum
defects 518, 566
diffuse x-ray scattering 566
electron energy-loss spectroscopy 113
scanning electron microscopy 425
thermal wave imaging 517
Aluminum alloys
Al-Ag alloys 125
Al-Cu alloys 131, 138
Al-Cu-Mg-Ag alloys 133
Al-Li alloys 316
Al-Li-Be alloys 235, 236
Al-Li-Cu-Mg alloys 106
Al-Si alloys 136
Al-Zn alloys 465
high-voltage electron microscopy 139
hydrogen embrittlement 139
optical microscopy 291
phase diagrams 316
small-angle neutron scattering 465
Aluminum carbide
Auger electron spectroscopy 32
Amorphous materials
alloys
hydrogen probes 190
Ni-Ti alloys 190
Ni-Zr alloys 190
Pd-Si alloys 190
electron diffraction 108
metals 263
Mossbauer spectroscopy 263
neutron diffraction 558
interpretation 562
model calculations 562, 563
neutron magnetic diffraction 564
peak fitting 562
real-space correlation functions 559
scattering vector 559
polymers
glass-transition temperature 380
small-angle neutron scattering 351
600
Subject
Index
small-angle x-ray scattering 379, 380
structure 379
x-ray diffraction 558
Compton scattering 560
dispersion technique 560
fluorescent-foil x-ray diffraction 560, 563
interpretation 562
model calculations 562, 563
peak fitting 562
quantitative analysis 560
real-space correlation functions 559
scattering vector 559
x-ray powder diffraction 581, 585
Amyl alcohol
differential thermal analysis 501
Analog instrumentation
acoustic emission 2
Analytical electron microscopy 123
Al-Ag alloys 125
electron energy-loss spectroscopy 125
quantification 126
electron scattering 123, 125
instrumentation 123
scanning transmission electron microscopes 123
Ni-Cr-Fe alloys 125
on-line data manipulation 126
stainless steel 127
transmission electron microscopy 123
x-ray emission 124
x-ray microanalysis 124, 578
Aneroid calorimeters 503
bomb calorimeters 503
Angular correlation
positron annihilation spectroscopy 390
Angular distribution Auger microscopy 34
angular distribution measurement 35
applications 37
Auger electron emission 35
bulk crystals 38
depth profiling 36
iodine 37, 40
monolayers 34
iodine 40
silver 37
multielemental samples 36
multiple Auger transitions 35
platinum 38, 40
real-space imaging 36
single crystals 38
platinum 38
specimen requirements 36
surfaces 34
thin films 34
see also Auger electron spectroscopy
Anisotropy see Magnetic properties
Anodization spectroscopy 14
applications 15
buried layers 16
chemical composition 14
depth profiling 14
GaAs 15
layer uniformity 16
microstructure 14
multilayers 15
Nb-Ta 15
Subject
sample preparation 15
IIIV semiconductors 15
structure 15
theory 14
ionic hopping conduction 14
thin films 14
Antiferromagnetic phases
muon probes 477
Archaeology
particle-induced x-ray emission 313
thermoluminescence dating 528
Art forgeries 16
bronze statuary 21
metallography 22
ceramics 17
Etruscan art 17
history 17
paintings 19
particle-induced x-ray emission 313
radiography 19
particle-induced x-ray emission 313
silver coinage 20
corrosion potential polarography 21
stamps 313
thermoluminescence dating 18
radiography 19
Ash
nondestructive evaluation 303
ASTM tests
flammability 361
ozone resistance 359
polymers 361
weatherability 360
Atmospheric tests
corrosion 80
Atom-probe microanalysis 151
imaging atom-probe mass spectroscopy 153
mass-to-charge ratio 151
microstructure 152
pulsed-laser atom-probe field-ion microscope 153
radiation effects 154
advantages 154
time-of-flight field-ion microscope 152
Atomic force microscopy 23, 436
applications 23, 27
ball bearings 27
brittle materials 27
compact disk 25
computer processing 25
growth processes 28
image display 25
limitations 26
microstructure 27
Ni-based superalloys 27
piezoelectric transducers 23, 24
polymers 28
qualitative analysis 25
quantitative analysis 26
calibration 26
scanning 23, 24
surface defects 26
surface forces 23
thin films 28
Atomic number
mass attenuation coefficients 267
Index
Austenitic
stainless
steel
601
Austenitic
stainless
steel
Subject
602
Index
electron spectroscopy for chemical analysis 140
Mylar 141
organic compounds 294
scanning tunnelling microscopy 427
Borides
laser microprobe mass spectrometry 211
Boron nitride
electron energy-loss spectroscopy 115
electron microprobe analysis 119
Bragg's law
convergent-beam transmission electron microscopy 540
electron diffraction 105
gamma-ray diffractometry 166
neutron diffraction 413
texture 498
single-crystal x-ray diffraction 568
x-ray crystallography 116, 458
x-ray diffraction 418
x-ray powder diffraction 568, 581
Bridges
dielectric measurements 327
General Radio Company capacitance bridge 327
Harris low-frequency bridge 327
Brinell hardness test 183
Brittle materials
atomic force microscopy 27
Bromobutane
mass spectrometry 294
Bronze statuary
art forgeries 21
metallography 22
Brunauer-Emmett-Teller equation 385
Bubbles
helium 122
molybdenum 122
neutron effects 122
transmission electron microscopy 122
Building materials
flammability tests 363
Bunsen ice calorimeter 502
Bursting strength
destructive mechanical testing 301
2-Butanone
mass spectrometry 295
Calcium oxalate
thermogravimetry 505
Calibration
atomic force microscopy 26
infrared spectrometers 195, 196, 199
ion sputtering 84
laser sampling inductively coupled plasma mass
spectrometry 218
nondestructive evaluation 308
scanning tunnelling microscopy 435
x-ray fluorescence spectrometry 577
x-ray microanalysis 580
Caliper
nondestructive evaluation 307
Calorimeters
adiabatic calorimeters 503
aneroid calorimeters 503
compensating calorimeters 503
isothermal calorimeters 502
laser calorimeters 279
Subject
Ohio State University calorimeter 364
scanning calorimeters 503
Calorimetry 502
adiabatic calorimetry 371
thermocouple calorimetry 279
differential scanning calorimetry 508
applications 509
measuring cell 500
polymers 371, 375
qualitative analysis 375
thermal degradation 359
thermosetting resins 376
dynamic calorimetry 371
flammability of polymers 364
optical calorimetry 279
Peltier effect 503
specific heat 371
superconducting materials 494
thermodynamic properties 503
see also Thermal analysis
Capillarity
capillary condensation 388
contact angle 387
imbibition rate 389
Kelvin equation 387
Laplace equation 387
mercury porosimetry 387
pore size 387
porosity 387
specific surface 389
suction porosimetry 388
Washburn equation 389
wetting 387
Carbon
carbon-13 nuclear magnetic resonance spectroscopy 101,
270
Carbon-fiber-reinforced composites
impact damage 60, 62
nondestructive evaluation 58
Carbon monoxide
Auger electron spectroscopy 57
chemical analysis 54
differential thermal analysis 509
ultraviolet photoelectron spectroscopy 56
Carbon steel
low-carbon steel 323
texture 323
Castings
gamma radiography 163
Catalysts
Auger electron spectroscopy 33
differential thermal analysis 509
gas detectors 178
Cathodoluminescence
band structure mapping 43
ceramics 43
defect densities 43, 45
diamond 46
dislocation array 45
electron-hole recombination 43, 45
imaging mode 44
impurity levels 43
instrumentation 44
MgO 45
microstructure 43
Index
Chemical
analysis
A1 20 - Z r 0 2 45
Zr0 2 45
phase distributions 45
photon emission mechanisms 43
sample preparation 44
scanning electron microscopy 424
semiconducting materials 43
SiC fiber 46
spatial resolution 44
spectroscopy 44
Ceramics
Al 20 3-water mixtures 48
A l 2 0 3 - Z r 0 2 45
art forgeries 17
Auger electron spectroscopy 34
cathodoluminescence 43
dating
thermoluminescence 528
defect densities 43, 45
diamond 46
dynamic mechanical analysis 513
gas sensors 175
impurities 43
MgO 45
microstructure 43, 45
particle-induced x-ray emission 313
phase distributions 45
powders
density 47, 48
mixtures 48
packing characterization 47
particulate system 47
porosity 48, 49
specific volume 47, 48
voids 48
volume 47
volume fraction 48
SiC fiber 46
solid electrolyte gas sensors 175
terracotta 17
Ti0 2-coated A1 20 3 513
Zr0 2 45
see also specific compounds
Channelling
ion backscattering
analysis 203
+
Si-BF 2 203
selected-area channelling patterns 257
see also Electron channelling
Channelling-enhanced microanalysis 50
applications 50
atomic structure 51
axial channelling 51
beam convergence 53
electron energy-loss spectroscopy 51
electron scattering 50
planar channelling 50
probe size 53
sensitivity 53
Charpy impact test 369
Chemical analysis
CO chemisorption 54
electron energy-loss spectroscopy 125
electron microprobe analysis 115
electron microscopy 123
electron spectroscopy 139
603
Chemical
analysis
Subject
604
Index
boron epoxy 549
carbon-fiber-reinforced materials 58
defects 59
delamination 59, 61, 547, 548
dynamic mechanical analysis 511
electron energy-loss spectroscopy 114
fiber-reinforced plastics 551
graphite-epoxy prepreg 511
nondestructive evaluation 58
adhesive-bonded joints 64
defects 59
delamination 59, 61, 547, 548
fabrication processes 59
laminates 59
porosity 59
residual stresses
neutron diffraction 416
SiC-Al 20 3 416
SPATE 484
thermal wave imaging 515
vibrothermography 547
wood-based composites 553
Compressive strength
polymers 368
Compton scattering 65
amorphous solids 560
concrete 66
densitometry 67
electronic properties 67
gamma-ray scattering 65
line shape analysis 66, 67
synchrotron sources 66, 67
theory 65
Compton profiles 66
Klein-Nishina cross sections 65
voids 67
x-ray diffraction 560
x-ray scattering 65
Computer-aided tomography
composites 62
voids 63
Computer applications
confocal optical microscopy 68, 72
dielectric measurements
transient methods 326
differential scanning calorimetry 371
inertial-confinement fusion
electron beam characterization 243
x-ray inspection 244
mechanical testing 370
nondestructive evaluation 302
Raman spectroscopy 355
secondary-ion mass spectrometry 442
SPATE 484
x-ray crystallography 457
x-ray powder diffraction 582
phase identification 583
Computer simulation
microstructural evolution 246
continuum models 246
equation-of-motion methods 252
Monte Carlo methods 247
Concentration
Raman spectroscopy 404
Concrete
Subject
mass attenuation 66
Conductive polymers
scanning tunnelling microscopy 433
Confocal optical microscopy 68
beam scanning instruments 69
acoustooptical devices 69
specimen scanning systems 69
computer systems 68, 72
graphics workstations 68, 72
confocal imaging 68
fluorescence microscopy 69
plexiglass 71
polarization 69
three-dimensional visualization 69
fibers 71
inside transparent materials 71
integrated circuits 72
photoresists 72
surfaces 70
see also Optical microscopy
Contact area
mechanical properties microprobe 233
Convergent-beam electron diffraction 107
copper 108
garnet 107
microscopy 537
Convergent-beam transmission electron microscopy 537
applications 538
Bragg's law 537
crystal symmetry 539
electron probes 541
film thickness 538
higher-order Laue zones 539, 541
lattice parameters 539
phase analysis 538
strain 539
unit cells 541
V 3Si 541
zone-axis patterns 538
Conversion electron Mossbauer spectroscopy 263
Copolymers
ABS copolymers
transmission electron microscopy 332
small-angle neutron scattering 352
Copper
convergent-beam electron diffraction 108
crystal growth 167
gamma-ray diffractometry 167
hardness 237
ion implantation 237
texture 498
direct pole figures 323
Copper alloys
Cu-Fe alloys 261
Cu-Ni alloys 118
Corrosion 75
aqueous corrosion 74, 77
Auger electron microscopy 76
chemistry 76, 78
Ellingham diagrams 76
classification 74
electrochemical methods 77, 79, 80
polarography 77
potentiometry 77
ellipsometry 76
Index
Crystal
growth
film thickness 76
gaseous corrosion 74
gravimetry 75
kinetics 74, 77
microtextural analysis 258
morphology 76, 78
resistance 258
Rutherford backscattering 77
steel 508
stress-corrosion cracking 78
structure 76
test methods 78
accelerated tests 80
corrosion resistance 79
corrosivity 79
electrical resistance 79
field tests 79
immersion tests 80
laboratory tests 79
objectives 79
quality assurance 79
service tests 79
simulated atmospheric tests 80
standards 79, 80
thermomagnetometry 508
volumetric methods 75
weight gain 75
x-ray electron probe microanalyzer 76
x-ray excited photoelectron spectroscopy 76
Young's modulus 77
see also Oxidation
Corrosion potential polarography 21
Cottrell atmospheres 448
Counterfeiting see Art forgeries
Cracking
aluminum 518
autofrettaged tubing 415
neutron diffraction 415
polymers
polyethylene 330
small-angle x-ray scattering 380
scanning electron microscopy 330
thermal wave imaging 517
Creep
polymers 368
Creep-compliance curves 10
Critical current density 487
dc hysteresis 493
direct measurements 492
inductive techniques 493
Critical field 490
resistive measurements 491
Critical temperature 487, 489
inductive measurements 489
resistive measurements 489
Cryogenics
inertial-confinement fusion 239
Crystal-diffraction spectrometers
electron microprobe analysis 116
flow proportional counters 117
Crystal growth
gamma-ray diffractometry 166
copper 167
scanning tunnelling microscopy 432
SiC 432
605
Crystal
orientation
Subject
Crystal orientation
scanning electron microscopy 423
Crystal structure
convergent-beam transmission electron microscopy 537
symmetry 539
gamma-ray diffractometry 165
imperfections 586
lattice constants 457
muon probes 473
phase angle 459
semiconducting materials 452
space groups 457
structure factors 459
symmetry 539
transmission electron microscopy 452
unit cells 457
x-ray absorption spectroscopy
extended x-ray absorption fine structure 555
x-ray absorption near-edge fine structure 555
x-ray crystallography 457
x-ray powder diffraction 581
see also Structure
Crystalline materials
alloys
Nb-V alloys 190
hydrogen probes 190
angular distribution Auger microscopy 38
electron spin resonance 147
polymers
small-angle neutron scattering 352
solid-state nuclear track detection 468
Crystallinity
Raman spectroscopy 404
Crystallites
orientation distribution functions
texture 322, 325
Euler angles 325
size
x-ray powder diffraction 581, 587
Crystallization
*VA. 263
Fe 7 8Mo 263
metals 263
polymers 380
Cuprous chloride
defects 474
Curie method 225
Curie temperature 229
Curing
thermosetting resins 376
Current imaging tunnelling spectroscopy 429
silicon 429, 430
Cutting
wood
acoustic emission 553
Damage
vibrothermography 547
Darcy's law 384
Dating
solid-state nuclear track detectors 471
Debye-Waller factors
low-energy electron diffraction 110
Mossbauer spectroscopy 259
Deep-level transient spectroscopy 205
606
Index
applications 207
GaAs 207
hydrogen passivation 207
InP 207
semiconductor devices 207
silicon 205, 206
theory 206
Defects
aluminum
diffuse x-ray scattering 566
electron-irradiated 566
alloys
amorphous materials 190
crystalline materials 190
Nb-V alloys 190
Ni-Ti alloys 190
Ni-Zr alloys 190
Pd-Si alloys 190
atomic force microscopy 26
ceramics
cathodoluminescence 43, 45
composites
nondestructive evaluation 59
convergent-beam transmission electron microscopy 537
CuCl 474
deep-level transient spectroscopy 205
electron diffraction 107
high-voltage electron microscopy 137
inertial-confinement fusion 238
electron beam characterization 241
x-ray inspection 244
junction transient spectroscopy 205
metals
diffuse x-ray scattering 565
dislocation density 188
electronic states 390
field-ion microscopy 154
grain boundaries 188
hydrogen probes 187
interstitials 187
neutron diffuse elastic scattering 566
positron annihilation spectroscopy 390
vacancies 188
muon probes 474
radiation-induced defects
diffuse x-ray scattering 565
diffuse elastic scattering 566
reflection electron microscopy 410
scanning electron microscopy 423
scanning tunnelling microscopy 432
semiconducting materials
etching 445
GaAs 207
InP 207
silicon 205
transmission electron microscopy 120, 452
wood
acoustic emission 552
x-ray powder diffraction 581, 586
see also Disorder
Deformation
polymers 380
Degradation
polymers 357
autofluorescence 342
Subject
thermal degradation 357
Delamination
nondestructive evaluation 59
ultrasonic inspection 61
vibrothermography 547, 548
Dendritic growth
equations-of-motion simulation 252
Densitometry 67
Density
packing characterization 47, 48
porosity 384
powders 395
ceramics 47, 48
Depth profiling 83
anodization spectroscopy 14
Auger electron spectroscopy 32, 83
angular distribution Auger microscopy 36
GaAs-AlGaAs superlattices 442, 443
GaAs:Be441,443
ion backscattering analysis 200
ion sputtering 83
laser microprobe mass spectrometry 213
laser sampling inductively coupled plasma mass
spectrometry 217
Rutherford backscattering 96
secondary-ion mass spectrometry 83
GaAs-AlGaAs superlattices 442, 443
GaAs:Be441,443
secondary-ion mass spectroscopy 95
thermal wave imaging 516
x-ray photoelectron spectrometry 83
Destructive mechanical testing
paper and paperboard 299
bond failure 301
bursting strength 301
fiber pullout 301
load-elongation characteristics 299
sheet failure 301
shrinkage 299
tearing strength 301
tensile strength 301
see also Mechanical testing, Nondestructive evaluation
Dew point 521
Diamond
cathodoluminescence 46
x-ray powder diffraction 582
Dielectric constant see Permittivity
Dielectric loss tangent
polymers 326
Dielectric measurements
bridges 327
electrode systems 328
microwave techniques 328
polymers 325
resonant methods 327
capacitance variation method 327
re-entrant cavity 327
solid-state nuclear track detection 468
transient methods 326
computer processing 326
permittivity 326
transmission lines 326, 328
Dielectric properties
polymers 325
theory 325
Index
Dilatometry
admittance 326
dielectric loss tangent 326
permittivity 326
Differential interference-contrast microscopy
polymers 341
epoxy resins 341
fracture 341
polypropylene 342
quantitative analysis 341
spherulitic morphology 342
surface roughness 341
Differential scanning calorimetry 508
applications 509
measuring cell 500
polymers 371, 375
polymer blends 375
thermal degradation 359
thermosetting resins 376
quantitative analysis 375
see also Differential thermal analysis
Differential thermal analysis 499, 508
amyl alcohol 501
applications 509
BaCl 501
heat flow 499
iron 501
metastable systems 500
polyoxymethylene 501
oxidation of CO 509
phase diagrams 500
polymers
poly (ethylene terephthalate) 501
thermal degradation 359
quantitative analysis 499
see also Differential scanning calorimetry
Differential interference-contrast microscopy 290
Diffuse x-ray scattering
electron-irradiated aluminum 566
metals
aluminum 566
nickel 566
radiation-induced defects 565
Diffusion
diffusion coefficients 92
Fick's laws 445
hydrogen
in palladium 189
metallurgical probe 187, 189
Mossbauer spectroscopy 94, 264
nuclear magnetic resonance 93
nuclear reaction analysis 95
polymers
molecular weight distribution 350
thermogravimetric analysis 377
quasielastic neutron scattering 92
coherent scattering function 93
incoherent scattering function 92
radiotracer techniques 92
Rutherford backscattering analysis 96
secondary-ion mass spectroscopy 95
self-diffusion coefficients
lithium 94
Digital instrumentation
acoustic emission 2
Dilatometry 503
607
Dilatometry
thermodilatometry 511
Discharges
optical emission spectroscopy 285
Discontinuities
acoustic emission /
Dislocations
dislocation loops
nickel 121
diffuse x-ray scattering 566
etching
dislocation density 448
etch hillocks 447, 448
etch pits 447, 449
GaAs 447
InP 448, 449
semiconducting materials 445
junction transient spectroscopy 205
metals
hydrogen probes 188
MgO 45
reflection electron microscopy 410
screw dislocations 410
semiconducting materials 445
GaAs 447, 454
InP 448, 449, 453
substructure
equations of motion simulation 253
transmission electron microscopy 453
Disorder
low-energy electron diffraction 109
see also Defects
Dispersive spectrophotometers 304
Dopants
etching 450
junction transient spectroscopy 205
semiconducting materials
ion implantation 443
molecular-beam epitaxy 443
secondary-ion mass spectrometry 443
Doppler broadening
positron annihilation spectroscopy 390
Dosimetry
archeological ceramics 528
geological 528
solid-state nuclear track detectors 471
thermoluminescence 527
Drying
wood
acoustic emission 553
Ductility
microtextural analysis 258
Dyes
rhodamine-B 213
Dynamic calorimetry 371
Dynamic mechanical analysis 511
applications 511
ceramics 513
composites 511
graphite-epoxy prepreg 511
instrumentation 513
thermal expansion 511
see also Thermodilatometry
Eddy current inspection 64
Effusion
608
Subject
Index
vapor pressure
gamma-ray spectrometry 522
mass spectrometry 522
thermodynamic activity 521
Elastic properties
acoustic emission 4
elastic deformation 418
nondestructive evaluation 308
paper and paperboard 308
polymers 368
powders 399
x-ray powder diffraction 418, 587
Elastic scattering
concrete 67
Elastomers
applications 103
carbon-13 nuclear magnetic resonance 101
fabrication 102
infrared spectroscopy 99, 101
mechanical properties 101
microstructure 99
molecular structure 99
plasticity 102
polybutadiene 99
polyisoprene 101
proton nuclear magnetic resonance 100, 101
quality control 102
specifications 103
spectroscopy 99
viscoelasticity 102
Electric admittance
polymers 326
Electric quadrupole interactions
Mossbauer spectroscopy 261
Electrical conductivity
solid-state gas sensors 177
humidity 177
superconducting materials 487
Electrical resistance 79
Electrochemistry
corrosion 77, 79, 80
etching 446
gas sensors 175
hydrogen 176
Nernst equation 175
oxygen 176
sulfur-containing gases 176
liquid chromatography 173
particle size distribution 393
thermodynamic activity 524
Electrode systems
dielectric measurements 328
three-terminal electrode systems 328
Electron acoustic microscopy 7
Electron backscattering patterns
microtextural analysis 257
Electron beam characterization
inertial-confinement fusion 240
thermal wave imaging 518
Electron beam damage
transmission electron microscopy
energy-loss analysis 333
polymer thin films 332
x-ray analysis 333
Electron channelling
Subject
scanning electron microscopy 425
see also Channelling
Electron diffraction 104
Al-Li-Cu-Mg alloys 106
amorphous materials 108
atomic structure 104
convergent-beam electron diffraction 107
defects 107
diffraction patterns 104
indexing 105
Kikuchi lines 108
low-energy electron diffraction 108
reflection high-energy electron diffraction 409
second-phase particles 107
theory 104
Bragg's law 105
Ewald spheres 105
Laue equations 104
Electron energy-loss spectroscopy 112
aluminum 113
Al-SiC composites 114
analytical electron microscopy 125
BN 115
channelling-enhanced microanalysis 51
detection limits 113
energy-loss spectrum 112
deconvolution 113
plasmon peak shifts 113
quantification 113
fine-structure effects 114, 126
imaging 114
instrumentation 112
limitations 114
lithium 112
low-energy-electron loss spectroscopy 54, 55
phase analysis 538
signal-to-noise ratio 127
spatial resolution 113
stainless steel 127
Electron energy states
electron microprobe analysis 116
emeraldine hydrochloride 434
scanning tunnelling microscopy 428, 434
silicon 429, 430
ZnO 433, 435
see also Vibrational states
Electron-hole recombination
cathodoluminescence 43, 45
scanning electron microscopy 424
Electron irradiation
aluminum
diffuse x-ray scattering 566
Electron microprobe analysis 115
BN 119
Cu-Ni alloys 118
electron energy level transitions 116
electron microprobe analyzers 115
applications 118
crystal-diffraction spectrometers 116
energy-dispersive spectrometers 117
operating principles 115
quantitative analysis 118
microstructure 119
molecular structure 406
Moseley's law 115
Index
Electron
spin
resonance
609
Electron
spin
resonance
610
Subject
Index
analytical electron microscopy 124
electron microprobe analysis 117
signal-to-noise ratio 127
x-ray diffraction 569
Energy-loss analysis
electron beam damage 333
Enthalpy
polymers 373
Entropy
phase diagram calculations
first-principle calculations 321
semiempirical relationships 319
Epitaxial films
x-ray powder diffraction 585
Epoxy resins
differential interference-contrast microscopy 341
Epstein test 231
Equation of motion methods
microstructural evolution 252
dendritic growth 252
dislocation substructure 253
front tracking 252
grain growth 253, 254
particle methods 253
Etching
chemical inhomogeneities 445, 450
defects 445
dislocations
dissolution kinetics 447
etch hillocks 447, 448
etch pits 447, 449
GaAs 447
InP 448, 449
thermodynamics 447
electrochemical reactions 446
etch rate 445
photoetching 446, 449, 451
selective etching 445
semiconducting materials 445
GaAs 447
InP 448, 449
solid-state nuclear track detection 468
wet chemical etching 445
Ethyl chloride
mass spectrometry 293
Ethylbenzene
carbon-13 nuclear magnetic resonance spectroscopy 272
proton nuclear magnetic resonance spectroscopy 270
Euler angles 325
Evolved gas analysis 509
applications 510
emanation thermal analysis 510
Novolac epoxies 510
TaSi2 thin films 511
Ewald spheres 105
Extended energy-loss fine-structure spectroscopy 114, 126
Extended x-ray absorption fine structure 535, 555
advantages 558
fluorescence detection 536
Fourier transforms 556
instrumentation 557
limitations 558
nickel 555
radial distribution functions 556
reflections 535
Subject
theory 555
uranium 556
x-ray sources 557
Fabrication see Processing
Faraday balance 488, 506
Faraday method 225
Faraday-Mossbauer effect 264
Fast atom bombardment
liquid chromatography mass spectrometry 224
Fatigue
acoustic emission 2
adhesive bonds 10
composites 548
neutron diffraction 415
vibrothermography 548
Feedback
thermal analysis 513
Femtosecond time resolution
thermophysical measurements 531
Fermi levels
electron spin resonance 146
electron tunnelling spectroscopy 149
hydrogen 187
metallurgical probes 187
Ferrites
nickel zinc ferrite 506
Ferromagnetic resonance frequency 230
Fiber-reinforced plastics
acoustic emission 551
Fibers
confocal optical microscopy 71
paper and paperboard
destructive mechanical testing 299
fiber pullout 301
polyesters 503
polyethylene 71
SiC 46
Fick's laws 445
Field-ion microscopy
atom-probe microanalysis 151
microstructure 152
defects
metals 154
field evaporation 151
ionic model 152
pulse-field evaporation 152
field-ion microscopes 151
resolution 152
time-of-flight atom-probe field-ion microscopes 152
field ionization 151
gold 151
radiation effects 154
advantages 154
applications 155
contrast effects 154
displacement cascades 154
monovacancies 154
voids 155
Films see Foils, Thin films
Filter colorimeters 304
Finite-element analysis
SPATE 484
Fire see Flammability
First-principle calculations
Index
Foner
magnetometer
611
Forgeries
Forgeries see Art forgeries
Fourier transform spectroscopy
extended x-ray absorption fine structure 556
infrared spectroscopy 195
nuclear magnetic resonance spectroscopy 271
free-induction decay 271
Fractals 156
fractal dimension
Brunauer-Emmett-Teller measurement 159
Feret's diameter 158
Koch islands 156
linear least-squares fit 158
measurement 157
raster-scanned images 159
Richardson plots 156
self-similarity 157
shape analysis 156
applications 160
fracture 160
liquid droplets 160
mammalian brains 160
particle aggregation 160
river systems 160
surfaces 156, 159
Fracture
acoustic emission 552
Auger electron spectroscopy 33
confocal optical microscopy 70
fractals 160
microtextural analysis 258
polymers
differential interference-contrast microscopy 341
polyethylene 330
scanning electron microscopy 330
SPATE 484
steels 33
wood 552
Free energy
phase diagram calculations 315
Free radicals
electron spin resonance
crystalline materials 147
organic materials 146
Friction 399, 401
Fugacity 520
Fusion
laser sampling inductively coupled plasma mass
spectrometry 217
see also Inertial-confinement fusion
Gallium arsenide
anodization spectroscopy 15
defects
deep-level transient spectroscopy 207
muon probes 475
dislocations
etch hillocks 448, 450
etch pits 447
transmission electron microscopy 454
etching
chemical inhomogeneities 450
photoetching 446, 451
GaAs-AlGaAs superlattices 442, 443
precipitates 451
transmission electron microscopy 454
612
Subject
Index
secondary-ion mass spectrometry
depth profiling 441, 443
GaAs-AlGaAs superlattices 442, 443
transmission electron microscopy 454
see also III-V Semiconductors
Gamma radiography 163
exposure techniques 164
inspection 163
radioactive sources 163
steel 163
Gamma-ray diffractometry 165
applications 166
crystal growth 166
copper 167
crystal structure 165
gamma-ray diffractometers 165
multilayers
Ta-Si multilayers 168
phase transformations 165
Ni 3Al 167
order-disorder transformations 167
rocking curves 166
stress
TaSi2 thin films 168
theory
Bragg's law 166
Darwin's mosaic model 166
Gamma-ray emission
particle-induced gamma-ray emission 310
positron annihilation spectroscopy 390
Gamma-ray scattering 65
Gamma-ray spectroscopy
effusion 522
Mossbauer spectroscopy 259
Garnets
convergent-beam electron diffraction 107
Gd 3Ga 5O u
x-ray powder diffraction 584
Gas analysis
evolved gas analysis 509
Gas chromatography 169
detectors 171
flame photometric detectors 171
flame-ionization detectors 171
Hall electrolytic-conductivity detectors 172
infrared detectors 172
mass spectrometers 172
thermal-conductivity detectors 171
gas chromatograms 170
gas chromatographs 169
gas-liquid chromatography 170
gas-solid chromatography 170
infrared spectroscopy 197
mass spectrometry 172, 296
poly chlorinated biphenyl mixture 172
sample introduction 172
separating columns 170
capillary columns 171
packing materials 170
volatile materials 169
see also Chromatography
Gas sensors
catalytic gas detectors 178
electrical conductivity changes 177
electrochemical sensors 175
Subject
Index
High-resolution
electron
microscopy
613
High-resolution
electron
microscopy
instrumentation 128
electron optics 128
microscope resolution 130
silicon 131
transmission electron microscopy 452
zeolites 128, 131
High-resolution mass spectrometry 296
High-resolution optical microscopy
laser microprobe mass spectrometry 209
High-temperature measurements
thermophysical properties 525
High-voltage electron microscopy 127
Al-Cu alloys 138
Al-Si alloys 136
diffraction patterns 135
foils 126
high-resolution high-voltage electron microscopy 136
image formation 135
in situ experiments 138
electron-beam-enhanced reactivity 139
gas-solid reactions 138
hydrogen embrittlement 139
oxidation 138
phase transformations 138
reduction 138
instrumentation 135
electron optics 135
magnetite 138
microstructure 136
Ni ?Al 137
point-defect clusters 137
radiation damage 135, 136, 139
Holographic interferometry
inertial-confinement fusion 240
Homoepitaxial growth
InP 453
Hooke's law 418
Hopkinson effect 229
Huang scattering
diffuse x-ray scattering 565
Humidity
solid-state gas sensors 177
Hydrogen
diffusion in palladium 189
embrittlement 187, 188
aluminum alloys 139
gas sensors 176
metallurgical probes 187
chemical potential 187
density of sites 187
diffusivity 187, 189
Fermi level 187
hydrogen distribution 187
statistical mechanics 187
trap concentration 189
passivation 207
segregation 443, 444
Hygroscopic expansion
adhesive bonds 10
Hyperfine field interactions
electron spin resonance 146
Mossbauer spectroscopy 260
texture 264
Hysteresis
porosimetry 388
614
Subject
Index
see also Magnetic properties
Imaging see specific techniques
Imaging atom-probe mass spectroscopy 153
Immersion testing
composites 60
corrosion 80
Impact strength
carbon-fiber-reinforced composites 60, 62
polymers 369
Impurities
ceramics 43
junction transient spectroscopy 205
In situ techniques
time-resolved x-ray diffraction 567
x-ray powder diffraction 581
Inclusions
polymer films
laser microprobe mass spectrometry 212
poly (vinyl chloride) 212
Inconel
scanning acoustic microscopy 5
Indene
infrared spectroscopy 195
Indentation
mechanical properties microprobe 233
Indium phosphide
deep-level transient spectroscopy 207
defects 207
dislocations
etch pits 448, 449
homoepitaxial growth 453
transmission electron microscopy 453
see also IIIV Semiconductors
Inductively coupled plasma
laser sampling inductively coupled plasma mass
spectrometry 215
optical emission spectroscopy 283
Inelastic tunnelling spectroscopy 149
Inert-ion sputtering 32
Inertial-confinement fusion 238
defects 238
electron beam characterization 240
computer analysis 243
defects 241
microradiography 242
quantitative analysis 242
scanning electron microscopy 240
surface roughness 242
thickness 241
optical methods 239
interferometry 239
optical microscopy 239
transparent materials 239
targets 238
cryogenic materials 239
thickness 238
x-ray inspection 243
computer analysis 244
defects 244
gas fill pressures 244
microfocus digital radiography 244
microradiography 243
microtomography 244
thickness 243
Subject
see also Fusion
Infrared detection
thermal wave imaging 517
vibrothermography 548
see also Infrared sensors
Infrared radiometry
SPATE 484
thermometric stress analysis 483
Infrared sensors
nondestructive evaluation
limitations 306
paper and paperboard 305
see also Infrared detection
Infrared sources
thermal wave imaging 516
Infrared spectroscopy 193, 405
applications 198, 199
atoms 193
attenuated total reflectance 197
chemical composition 193
Fe 2(CO) 9 54
gas chromatography 197
indene 195
infrared spectrometers 193
calibration 195, 196, 199
dispersive spectrometers 193
Fourier-transform spectrometers 195
interferometer spectrometers 196
optical-null grating spectrometers 194
ratio-recording spectrometers 195
standardization 195
tunable laser spectrometers 195
window materials 193
liquid chromatography 197
mixtures 193, 199
molecules 193
nuclear magnetic resonance 198
polybutadiene 99
polyisoprene 101
polystyrene 196
qualitative analysis 197, 198
sampling
attenuated total reflectance 197
grindable solids 197
liquid films 196
microsamples 197
powdered solids 197
pyrolysis 197
solutions 196, 198
thin layers 195
solid surfaces 54
specimen preparation 405
structure 193
theory 193
vibrational frequencies 193, 194, 405
Inks
particle-induced x-ray emission 313
Inorganic materials
solid-state nuclear track detectors 469
Inspection
acoustic emission 3
composites 58
gamma radiography 163
laser-beam devices 305
neutron radiography 267
Index
Ion backscattering
analysis
615
Ion backscattering
analysis
40
N i
40 20
32
Fe 7 8Mo 2B 20 263
Mossbauer spectroscopy 263
ISO standards
particle-shape classifications 394
Isomer shift
Mossbauer spectroscopy 260
Isothermal calorimeters 502
Bunsen ice calorimeter 502
Isotopes
gold-197 261
iron-57 259
laser sampling inductively coupled plasma mass
spectrometry 215
Mossbauer spectroscopy 259
616
Subject
Index
nuclear magnetic resonance spectroscopy 273, 277
carbon-13 nuclear magnetic resonance spectroscopy 270,
271, 275
radon-222 473
solid-state nuclear track detection 471
Jamin-Lebevedev interferometer 239
Joining see Adhesive bonding
Josephson effect 150
Junction transient spectroscopy 205
defects 205
semiconductor materials 205, 206
Kelvin equation 387
Kelvin's law 483
Kiessig fringes 534
Kikuchi lines 108
Kinetic rate theory 247
Klein-Nishina cross section 65
Knoop hardness test 185
Koch islands 156
Kohler illumination
optical microscopes 288
Kossel method 257
Kozeny equations 385
Kramers-Kronig analysis 113
Laminates
nondestructive evaluation 59
Langmuir equation 386
Laplace equation 387
Larmor frequency 269
Laser interferometry
inertial-confinement fusion 239
Laser microprobe mass spectrometry 209
applications 211
borides in Ni-based superalloys 211
depth resolution 213
inclusions 211
instrumentation 209
ion detection 209, 210
laser ablation 210
mass resolution 211
mass-to-charge ratio 209
microstructure 211
Nd-YAG laser 210
Ni-based superalloys 211
optical microscopy system 209
organic materials 211, 213
polymer films 212
quantification 214
rhodamine-B dye 213
spatial resolution 210
surfaces 209
see also Lasers, Mass spectroscopy
Laser sampling inductively coupled plasma mass spectrometry
275
calibration 218
depth profiling 217
glass 218
instrumentation 215
ionization 216
isotopes 215
laser-solid interaction 217
fusion 217
Subject
laser ablation 217
vaporization 217
Nd-YAG lasers 216
pulsed lasers 217
quantitative analysis 218
sensitivity 217
spatial resolution 217
standardization 218
trace element analysis 215
see also Lasers, Mass spectroscopy
Lasers
ablation 210
confocal optical microscopy 69
infrared spectrometers 195
interferometry 239
microprobe mass spectrometry 209
Nd-YAG lasers 210, 216, 529
nondestructive evaluation 305
optical calorimetry 279
particle size distribution 393
photoacoustic microscopy 6
pulsed lasers 217
atom-probe field-ion microscope 153
subsecond thermophysical measurements 529
Raman spectrometers 355
Raman spectroscopy 404
scanning laser acoustic microscopy 8
semiconductor diode lasers 195
subsecond thermophysical measurements 529
thermal wave imaging 517
thermoreflectance 517
see also Laser microprobe mass spectrometry, Laser
sampling inductively coupled plasma mass
spectrometry
Lattice dynamics
Mossbauer spectroscopy 259
Lattice parameters
convergent-beam transmission electron microscopy 539
glancing angle x-ray diffraction 536
x-ray crystallography 457
x-ray powder diffraction 581
Lattice stabilities
phase diagram calculations 315
first-principle calculations 320
Laue equations 104
Laue method
microtextural analysis 257
Layered structures see Multilayers
Lenses
optical microscopes 286
Light microscopy see Optical microscopy
Light scattering
polymers
molecular weight distribution 346
photon correlation light scattering 349
Rayleigh scattering 346
small-angle light scattering 338
Raman spectroscopy 403
Linear variable differential transformers 230, 503
Liquid chromatography 169, 173
detectors 173
derivitization detectors 173
differential-refractive-index detectors 173
electrochemical detectors 173
infrared detectors 173
Index
Machining
617
Machining
acoustic emission 553
Magic-angle spinning
nuclear magnetic resonance spectroscopy 275
Magnesium oxide
Auger electron spectroscopy 34
cathodoluminescence 45
dislocation arrays 45
grain size 249
Monte Carlo simulation 249
Magnetic domains
scanning electron microscopy 423
Magnetic prism spectrometers
analytical electron microscopy 126
electron energy-loss spectroscopy 112, 126
Magnetic properties 225
antiferromagnetic phases 477
Curie temperature 229
Hopkinson effect 229
ferromagnetic resonance frequency 230
flux density 226
grain size evaluation 180
Barkhausen effect 181
image effect 229
magnetic fields 228
Hall effect 228
nuclear magnetic resonance 228
magnetic losses
Epstein test 231
magnetic moments 225
magnetic susceptibility 226
thermomagnetometry 506
magnetization 225
coercive force 232
Curie method 225
demagnetizing fields 228
Faraday method 225
force methods 225
induction methods 226
magnetic anisotropy 229
magnetic hysteresis 228
remanent induction 232
sample field measurement 226
saturation magnetization 225
small-angle neutron scattering 464, 467
superconducting materials 487
superconducting quantum interference device
measurements 227
magnetostriction 230
maximum energy product 232
Neel temperature 229
neutron magnetic diffraction 564
phase diagram calculations 318
first-principle calculations 321
permanent magnetic materials 231
scanning electron microscopy 426
soft magnetic materials 231
superconductors 226, 231
thermomagnetometry 506
see also Hysteresis
Magnetic recording heads
scanning electron microscopy 426
Magnetic techniques 225
alternating-gradient magnetometers 226
electronic fluxmeters 226
fluxgate magnetometers 228
618
Subject
Index
Foner magnetometer 227
gaussmeters 228
rotating-coil gaussmeters 228
linear variable differential transformers 230
magnetic balances 225
muon probes 475
antiferromagnetic phases 477
SQUID magnetometers 227, 488, 494
torque magnetometers 229
vibrating-sample magnetometers 227, 488
Magnetite
high-voltage electron microscopy 138
reduction 138
Magnetometers see Magnetic techniques
Magnets
Bitter magnets 230
superconducting magnets 230
see also Permanent magnet materials
Mass attenuation
concrete 66
neutron radiography 267
Mass spectroscopy
atom-probe microanalysis 151
bromobutane 294
2-butanone 295
effusion 522
ethyl chloride 293
gas chromatography 172, 296
2-hexamone 295
high-resolution mass spectrometry 296
imaging atom-probe mass spectroscopy 153
ionization 293
bond energy 294
exact mass 293
fragmentation 293
mass spectra 29
mass spectrometers 292
organic materials 292
phenetole 295
pyrolysis 297
quantitative analysis 297
subsecond thermophysical measurements 530
time-of-flight spectrometers 209
see also Laser microprobe mass spectrometry, Laser
sampling inductively coupled plasma mass
spectrometry, Liquid chromatography mass
spectrometry, Secondary-ion mass spectroscopy,
Spark-source mass spectrography
Mass-to-charge ratio
atom-probe microanalysis 151
laser microprobe mass spectrometry 209
Mathematical analysis
fractals 156
Mattauch-Herzog analyzer 480
Mechanical impedance
nondestructive evaluation 63
Mechanical properties
adhesives 9
Al-Li-Be alloys 235, 236
copper 237
elastomers 101
fractals 160
hardness 183
microindentation tests 233
integrated circuits 234
Subject
nickel 234, 236
microprobes 232
microtextural analysis 257
nickel 234, 236
paper and paperboard 308
polymers 366
amorphous polymers 367
flexural properties 368
impact properties 369
tensile properties 366
time-dependent properties 368
rapidly solidified materials
Al-Li-Be alloys 235, 236
rubber 367
sapphire 235, 236
texturing 497
Mechanical properties microprobe 232
applications 232, 235
descriptive models 236
hardness 235, 236
microhardness 233
microindentation tests 233
contact area 233
nanoindenters 233
microstructure 236
rapidly solidified materials 235
wear 235
weld embrittlement 235
Young's modulus 235
Mechanical testing
elastomers 101
dynamic tests 102
quality control 102
reproducibility 103
standards 104
static tests 102
hardness 183
Brinell test 183
conversion tables 186
indentation tests 183, 185
Knoop test 185
microhardness tests 185
portable testers 186
rebound tests 185
Rockwell test 184
Scleroscope test 185
standardization 183, 186
Vickers test 184, 185
paper and paperboard
destructive testing 299
nondestructive evaluation 302
polymers 366
Charpy impact test 369
computer processing 370
tensile testing 301
wood 552
see also Destructive mechanical testing, Nondestructive
evaluation
Medicine
particle-induced x-ray emission 312, 313
Meissner fraction 490
Melting
polymers 372
polyethylene 372
small-angle x-ray scattering 380
Index
Microindentation
619
Microindentation
nickel 234, 236
Microprobe analysis
ion backscattering analysis 203
gold 204
microelectronics 203
laser microprobe mass spectrometry 209
mechanical properties 232
see also Electron microprobe analysis
Microradiography
inertial-confinement fusion
electron beam characterization 242
x-ray inspection 243
see also Radiography
Microscopy see specific techniques
Microsecond time resolution
thermophysical measurements 528
Microstructural evolution
computer simulation 246
equation-of-motion methods 252
Monte Carlo methods 247
dislocation substructure 253
grain boundaries 247
grain growth 153, 154, 247
dendritic growth 252
grain size 249
grain structure 246
Ostwald ripening 250, 253
primary recrystallization 249
processing conditions 246
second-phase particles 250, 253
secondary recrystallization 249
sintering 250
vacancy diffusion 247
see also Microstructure
Microstructure
Al-Si alloys 136
A l 2 O r Z r 0 2 45
anodization spectroscopy 14
atom-probe microanalysis 152
atomic force microscopy 27
Ni-based superalloys 27
austenitic stainless steel 235
cathodoluminescence 43, 45
elastomers 99
electron energy-loss spectroscopy 112
electron microprobe analysis 119
high-voltage electron microscopy 136
laser microprobe mass spectrometry 21
mechanical properties microprobe 235
metals
positron annihilation spectroscopy 391
Ni-based superalloys 27, 211
polymers
light microscopy 336
polarized-light microscopy 337, 338
polyethylene 337
polypropylene 338, 342
small-angle light-scattering 338
semiconducting materials
transmission electron microscopy 452
small-angle neutron scattering 462
decomposing alloys 464
spherulitic morphology, 331, 337
polyethylene 334
polypropylene 338, 342
620
Subject
Index
transmission electron microscopy 120
ZK) 2 45
see also Grain boundaries, Grain size, Grain structure,
Microstructural evolution, Surface morphology
Microtextural analysis 255
austenitic stainless steel 256
electron backscattering patterns 257
Kossel method 257
Laue method 257
mechanical properties 257
grain-boundary design 257
representation 256
Rodrigues-Frank method 256
scanning electron microscopy 257
selected-area channelling patterns 257
silicon steels 257
Microtomography
inertial-confinement fusion 244
Microwave heating
plexiglass 71
Microwave spectroscopy
electron spin resonance 145
Microwave techniques
dielectric measurements 328
nondestructive evaluation 306
Miedema's method 319
Milling tests
polymers 357
Millisecond time resolution
thermophysical measurements 528, 539
Miscibility gap
Cr-W alloys 321
Mixtures
alumina-water 48
ceramic powders 48
infrared spectroscopy 193, 199
liquid chromatography mass spectrometry 220
x-ray powder diffraction 581
Moisture
nondestructive evaluation 305, 306
Molecular-beam epitaxy
semiconducting materials
GaAs-AlGaAs superlattices 443
secondary-ion mass spectrometry 443
Molecular configurations
polymers
amorphous polymers 351
polymer dynamics 353
Raman spectroscopy 356
small-angle scattering 351
tacticity 356
Molecular structure
elastomers
carbon-13 nuclear magnetic resonance 101
infrared spectroscopy 99
polybutadiene 99
polyisoprene 101
proton nuclear magnetic resonance 100, 101
liquid chromatography mass spectrometry 220
muon probes 473
Raman spectroscopy 403
x-ray crystallography 457
see also Structure
Molecular weight distribution 349
distribution functions 344, 346, 348
Subject
applications 345
intrinsic viscosity, 348
light scattering 346
osmotic pressure 346
photon correlation light scattering 349
physical properties 345
size-exclusion chromatography 348, 350
liquid chromatography mass spectrometry 220
measurement
chromatography 350
diffusion methods 350
discrete methods 350
one-parameter functions 344
exponential functions 345
Flory-Schulz distribution 344
Poisson distribution 345
polymers 343
chromatography 350
coefficient of skewness 344
diffusion 350
measurement 349
polydispersity index 343
sedimentation 349
size-exclusion chromatography 348, 350
three-parameter functions 345
two-parameter functions 345
logarithmic normal distribution 345
normal functions 345
Schulz-Zimm distribution 345
Molecules
electron spin resonance 147
electron tunnelling spectroscopy 149
infrared spectroscopy 193
Molybdenum
alpha-particle bombardment 122
helium bubbles 122
transmission electron microscopy 122
Monolayers
angular distribution Auger microscopy 34
corrosion 76
corrugated 41
iodine 40
silver 37
Monovacancies
positron annihilation spectroscopy 391
Monte Carlo methods
inertial-confinement fusion 243
microstructural evolution 247
grain boundaries 247
grain growth 247
grain size 247
Ostwald ripening 250, 253
primary recrystallization 249
second-phase particles 250, 253
secondary recrystallization 249
sintering 250
two-phase structure 250
vacancy diffusion 247
x-ray microanalysis 579
Morphology see Surface morphology
Moseley's law 115
Mossbauer spectroscopy 259
amorphous metals 263
applications 261
conversion electron Mossbauer spectroscopy 263
Index
Muon
crystallization 263
* 2 263
F
2 0
32
probes
621
Muon
probes
622
Subject
Index
neutron-nucleus scattering 267
neutron sources 267
Neutron scattering
neutron diffuse elastic scattering 566
polymers 351
amorphous polymers 351
copolymers 352
crystalline polymers 352
networks 352
neutron spin echo spectrometers 353
phonons 351
polyelectrolytes 352
polymer dynamics 353
small-angle scattering 351
thermal-neutron scattering 351
vibrational states 351
quasielastic neutron scattering 92
see also Small-angle neutron scattering
Neutron spin echo spectrometers 353
Nickel
dislocation loops 121
diffuse x-ray scattering 566
extended x-ray absorption fine structure 555
microindentation tests 234, 236
neutron irradiation 121
transmission electron microscopy 121
voids 121
Nickel alloys
atomic force microscopy 27
laser microprobe mass spectrometry 211
hydrogen segregation 443, 444
neutron diffraction 416
Ni-Al alloys 465, 466
Ni Al 137, 167
Ni-Cr-Fe alloys 90, 125
Ni-In alloys 89, 90
Ni-Ti alloys 190
Ni-Zr alloys 190
secondary-ion mass spectrometry 443, 444
small-angle neutron scattering 465
superalloys 416
atomic force microscopy 27
neutron diffraction 416
Nickel zinc ferrite
thermogravimetry 506
van't Hoff diagram 506
Niobium
ion irradiation 122
transmission electron microscopy 122
voids 122
Niobium alloys
Nb-Ta alloys 15
Nb-V alloys 190
Niobium suicide 202
Nondestructive evaluation
acoustic emission / , 64
composites 58
acoustic emission 64
adhesive-bonded joints 64
defects 59
delamination 59, 61
eddy current inspection 64
mechanical impedance 63
optical methods 63
porosity 59
Subject
qualitative analysis 59
quality assurance 59
quantitative analysis 59
radiography 61
thermography 63
ultrasonic inspection 59
vibration techniques 63
visual inspection 59
grain size 179
magnetic methods 180
ultrasonic techniques 179
hardness testing 183
portable testers 186
paper and paperboard 302
ash measurement 303
basis weight 302
caliper 307
color 304
computer processing 302
correlation techniques 308
energy-coupling subsystem
head-positioning subsystem 307
infrared sensors 305
mechanical properties 308
microwave sensors 305
moisture 305, 306
opacity 304
optical techniques 304
piezoelectric transducers 308
quality control 308
radio-frequency sensors 306
sensors 302
signal processing 302
ultrasonic techniques 308
verification 308
x-ray sensors 303
particle-induced x-ray emission 312
polymers 497
residual stresses 417
Barkhausen noise analysis 421
limitations 418
neutron diffraction 412
ultrasonic techniques 419
x-ray diffraction 418
scanning tunnelling microscopy 435
SPATE 484
texture 497
neutron diffraction 497
polymers 497
x-ray diffraction 497
thin films 532
vibrothermography 547
wood 551
x-ray fluorescence spectrometry 570
x-ray powder diffraction 581
see also Destructive mechanical testing, Mechanical
testing, specific techniques
Novolac epoxies
evolved gas analysis 510
Nuclear magnetic resonance
classical mechanics 269
diffusion 93
lithium 94
spin-lattice relaxation 93
spin-spin relaxation 93
Index
Optical
emission
spectroscopy
623
Optical
emission
spectroscopy
flames 283
gas discharges 285
glow-discharge lamps 285
hot hollow-cathode lamps 285
inductively coupled plasma 283
line spectra 281
quantitative analysis 281
spectrometers 281
Czerny-Turner mounting 282
multichannel spectrometers 282
Paschen-Runge mounting 282
photodiode array detectors 282
photomultiplier tube detectors 282
reflection gratings 281
sequential spectrometers 282
Optical materials
infrared windows 193
reflection loss 194
transmission range 194
Optical microscopy 286
aluminum alloys 291
aluminum oxide 291
applications 289
bright-field illumination 289
dark-field illumination 289
inertial-confinement fusion 239
interference microscopy 289
interference-contrast microscopy 291, 340
interference-fringe microscopy 289
laser microprobe mass spectrometry 209
optical microscopes 286
aberrations 287
aperture diaphragm 288
depth of field 288
field diaphragm 288
Kohler illumination 288
magnification 287
numerical aperture 286
objective lenses 286
resolution 286
particle size distribution 392
polarized-light illumination 289, 337
polymers 336
specimen preparation 336
reflected-light methods
differential interference-contrast microscopy 341
fluorescence microscopy 342
resolution 341
transmitted light methods 337
interference-contrast microscopy 340
phase-contrast microscopy 340
polarized-light microscopy 337
see also Confocal optical microscopy
Optical path length
optical calorimetry 280
Optical properties
composites 63
nondestructive evaluation 63
paper and paperboard 304
Order-disorder transformations
gamma-ray diffractometry 167
Ni3Al 167
phase diagram calculations 318
Organic materials
bond energy 294
624
Subject
Index
electron spin resonance 146
gas chromatography 169
laser microprobe mass spectrometry 211, 213
mass spectrometry 292
nuclear magnetic resonance spectroscopy 269
particle-induced x-ray emission 313
solid-state nuclear track detectors 470
x-ray crystallography 461
Orientation distribution functions
texture 497
neutron diffraction 497
x-ray diffraction 497
Oscilloscopes 60
Osmotic pressure 346
Ostwald ripening 250, 253
Oven aging tests 357
Oxidation 74
CO 509
differential thermal analysis 509
ion backscattering analysis 202
NbSi 2 202
palladium alloys 189
polymers 357
reflection electron microscopy 411
thermal degradation
differential scanning calorimetry 359
differential thermal analysis 359
polymers 357
thermogravimetric analysis 359
see also Corrosion
Oxygen
gas sensors 176, 177
Oxygen coefficients 506
Oxygen index test
flammability 362
Ozone resistance
polymers 359
ASTM test methods 359
Packing density
ceramic powders 47
Paintings
art forgeries 19
particle-induced x-ray emission 313
pigment analysis 19
radiography 19
Pair-potential theory 319
Palladium
nanocrystalline
- phase transformations 189
grain boundary segregation 189
hydrogen diffusion 189
oxidation 189
strain
x-ray powder diffraction 587
Palladium alloys
oxidation 189
Pd-Si alloys 190
Paper and paperboard
destructive mechanical testing 299
bond failure 301
bursting strength 301
fiber pullout 301
load-elongation characteristics 299
sheet failure 301
Subject
shrinkage 299
tearing strength 301
tensile strength 301
nondestructive evaluation 302
ash measurement 303
basis weight 302
caliper 307
color 304
computer processing 302
correlation techniques 308
infrared sensors 305
mechanical properties 308
microwave sensors 306
moisture 305, 306
opacity 304
optical techniques 304
particle-induced x-ray emission 313
piezoelectric transducers 308
quality control 308
radio-frequency sensors 306
ultrasonic techniques 308
verification 308
x-ray attenuation 303
Paramagnetic resonance 144
Particle-induced gamma-ray emission 310
Particle-induced x-ray emission 309
advantages 312
air pollution
aerosols 313
applications 313
art forgeries
paintings 313
stamps 313
biological materials 312, 313
tissue 312
ceramics 313
detection limits 311
elemental analysis 309
external beam techniques 310
instrumentation 309
light elements 310
medical applications 312, 313
microbeam techniques 311
detection limits 312
spatial resolution 311, 312
nondestructive evaluation 312
paper 313
printing inks 313
proton elastic scattering analysis 310
quantitative analysis 309
sampling 310
sensitivity 312
water 314
wood 314
Particles
fractals 160
shape 394
morphology 394
stereological analysis 394
size 392
x-ray powder diffraction 587
small-angle neutron scattering 462
sources
thermal wave imaging 518
see also Powders
Index
Phase
stability
Passivation
deep-level transient spectroscopy 207
Peel tests 13
Peltier effect 503
Penetrant enhanced radiography
composites 62
Peptides
electrospray liquid chromatography mass spectrometry 223
Permanent magnet materials 231
coercive force 232
maximum energy product 232
remanent induction 232
see also Magnets
Permeability
particle size distribution 393
porosity 384
Darcy's law 384
Kozeny equations 385
Permittivity
electron energy-loss spectroscopy 113
Kramers-Kronig analysis 113
polymers 326, 328
microwave techniques 328
transient methods 326
Phase analysis
cathodoluminescence 45
ceramics 45
convergent-beam transmission electron microscopy 538
Mossbauer spectroscopy 262
Ti-Fe alloys 262
x-ray powder diffraction 581, 583
Phase angles
x-ray crystallography 459
Phase-contrast microscopy 340
Phase diagrams
Al-Li alloys 316
calculations 315
Miedema's method 319
empirical relationships 317
first-principle calculations 320
magnetic terms 318, 321
modelling 317
pair-potential theory 319
semiempirical relationships 319
differential thermal analysis 500
entropy 319, 321
heat of formation 319
interaction energies 315, 320
Cr-W alloys 321
lattice stabilities 315
metastable phases 316
Al-Li alloys 316
multicomponent systems 316
Cr-Fe-Si alloys 317
ordering 318
thermodynamics 315
free energy 315
thermometry 499
x-ray powder diffraction 584
Phase separation
small-angle neutron scattering 465
Phase stability
calculations 315
Miedema's method 319
empirical relationships 317
625
Phase
stability
626
Subject
Index
spectrometry 215
Plastic deformation
elastomers 102
polymers 380
residual stresses 419
small-angle x-ray scattering 380
x-ray diffraction 419
Plastics
flammability 361
Platinum
angular distribution Auger microscopy 38, 40
Platinum alloys
Pt-Si alloys 202
Plexiglass
confocal optical microscopy 71
Point defects
high-voltage electron microscopy 137
junction transient spectroscopy 205
Point spectroscopy
scanning tunnelling microscopy 428
Poisson's ratio
Auger electron spectrometry 90
neutron diffraction 414
x-ray diffraction 418
Polarimetry
Mossbauer spectroscopy 264
Polarized confocal optical microscopy 69
Polarized-light microscopy
Becke line test 339
birefringence 338
identification 338
liquid crystals 339
microhotstage 338
polymers 337
polyethylene 337
quantitative analysis 339
refractive index 339
small-angle light scattering 338
spherulite morphology 337
thermal effects 338
Polaron defects
muon probes 477, 478
Pole figures
copper 498
direct pole figures 323
interpretation 325
inverse pole figures 324
normalization factors 324
texture 322
x-ray goniometry 323
Polyamides
thermal degradation 359
Polybutadiene
carbon-13 nuclear magnetic resonance 101
infrared spectroscopy 99
molecular structure 99
proton nuclear magnetic resonance 100
Polychlorinated biphenyl mixture
gas chromatography 172
Polycrystalline materials
grain size 179
microtextural analysis 255
neutron diffraction 413
texture 322
Polydispersity index 343
Subject
Polyelectrolytes
small-angle neutron scattering 352
Polyesters
thermomechanical analysis 503
Polyethylene
confocal optical microscopy 71
crack propagation 330
fracture 330
melting 372
microstructure 337
polarized-light microscopy 337
scanning electron microscopy 330, 331
scanning transmission electron microscopy 334, 335
thermal degradation 359
thermodynamic properties 372
transmission electron microscopy 332
Poly(ethylene terephthalate)
differential thermal analysis 501
Polyisocyanurate
flammability 364
Polyisoprene
infrared spectroscopy 101
proton nuclear magnetic resonance 101
Polymer blends
compatibility 375
differential scanning calorimetry 375
polyethylene-polycarbonate 330
scanning electron microscopy 330
Polymer films
inclusions 212
laser microprobe mass spectrometry 212
poly(vinyl chloride) 212
transmission electron microscopy 331
Polymers
additives
fluorescence microscopy 342
amorphous polymers
glass-transition temperature 380
mechanical properties 367
small-angle neutron scattering 351
small-angle x-ray scattering 379, 380
structure 379
atomic force microscopy 28
birefringence 338
compressive strength 368
conductive polymers 433
copolymers 352
crazes 380
creep 368
crystalline polymers
small-angle neutron scattering 352
small-angle x-ray scattering 380
deformation 380
degradation 357
autofluorescence 342
thermal degradation 357
dielectric properties 325
differential interference-contrast microscopy 341
diffusion
molecular weight distribution 350
thermogravimetric analysis 377
elasticity 368
electron microscopy 329
replica techniques 330
scanning electron microscopy 329
Index
Polymers
627
Polymers
semicrystalline polymers
small-angle x-ray scattering 379
structure 379
size-exclusion chromatography 348, 350
small-angle neutron scattering 351
small-angle x-ray scattering 378
solid-state nuclear track detection 468
specific heat 371
stabilization 357
stress relaxation 368
structure
degree of regularity 356
Raman spectroscopy 354
secondary structure 356
small-angle x-ray scattering 378
surface roughness 341
texture 497
thermal analysis 358, 371, 375
thermal properties 371
thermodynamic properties 372
thermogravimetric analysis 377
thermosetting resins 376
voids 380
water absorption 377
weatherability 360
x-ray scattering 378
small-angle x-ray scattering 378
yield strength 366
Young's modulus 367
see also specific materials
Poly(methyl methacrylate)
Raman spectroscopy 408
Polyoxymethylene
differential thermal analysis 501
Polypropylene
differential interference-contrast microscopy 342
polarized-light microscopy 338, 339
Polystyrene
gel-permeation chromatography 174
infrared spectroscopy, standard 195
interference-contrast microscopy 340
phase-contrast microscopy 340
specific heat 374
Polyurethane
flammability 364
Polyvinyl chloride)
laser microprobe mass spectrometry 212
thermal degradation 359
Poly(vinylidene chloride)
fluorescence microscopy 342
Porod approximation
small-angle neutron scattering 463
Porosity 381
ceramic powders
packing characterization 48, 49
composites
nondestructive evaluation 59
pore size 381
pore structure 381
adsorption 385
capillarity 387
density 384
direct methods 382
indirect methods 384, 389
permeability to fluids 384
628
Subject
Index
stereological analysis 383
porosimetry
capillary condensation 388
hysteresis 388
mercury porosimetry 387
suction porosimetry 388
specific surface 381
Position-sensitive detectors 413
Positron annihilation spectroscopy 390
defect states 390
microstructure 391
positron lifetime 390
vacancies 391
Potassium chloride
spin-lattice relaxation 475
Potassium hydrogen carbonate
thermogravimetry 513
Powders 392
bulk properties 394
apparent density 395
compaction 396
flowability 396
ceramics
density 47, 48
packing characterization 47
particulate system 47
porosity 48, 49
voids 48
volume 47
specific volume 47, 48
volume fraction 48
infrared spectroscopy 197
packing 47, 397
particle shape 394
particle size distribution 392
adsorption of gases 393
electrolyte resistance 393
elutriation 392
laser scattering 393
microscopy 392
permeametry 393
sedimentation 392
sieving 392
turbidimetry 393
powder mechanics 397
adhesion 399
cohesive powders 399, 400
contact 398
elastic properties 399
friction 399, 401
noncohesive powders 399, 400
packing 397
soil 400
stress effects 400
van der Waals attraction 398
Young's modulus 400
specific surface 393
x-ray diffraction 581
Bragg's law 568
x-ray fluorescence spectrometry 576
see also Particles
Precipitates
etching 450
GaAs 454
Ni-Al alloys 466
Subject
silicon device structure 453
small-angle neutron scattering 466
transmission electron microscopy 453
thermogravimetry 506
thermomagnetometry 506
see also Second-phase particles
Preferred orientation see Texture
Printing inks
particle-induced x-ray emission 313
Processing
composites 59
destructive mechanical testing 299
elastomers 102
microstructural evolution 246
nondestructive evaluation 59
nuclear magnetic resonance spectroscopy 276
paper and paperboard 299
scanning tunnelling microscopy 435
solid-state gas sensors 175
time-resolved x-ray diffraction 567
x-ray fluorescence spectrometry 575
Proton elastic scattering analysis 310
Proton nuclear magnetic resonance
ethylbenzene 270
polybutadiene 100
polyisoprene 101
tetramethylsilane 270
Pulse heating
subsecond thermophysical measurements 525
Pulse-height analyzers 583
Pulsed-laser atom-probe field-ion microscopes 153
Pyrolysis
infrared spectroscopy 197
mass spectrometry 297
Pyrometry
subsecond thermophysical measurements 528
Quadrupole interactions
Mossbauer spectroscopy 261
Quadrupole mass filters 441
Qualitative analysis see specific techniques
Quality control
acoustic emission 9
wood 552
corrosion tests 79
elastomers 102
ion backscattering analysis 200
nondestructive evaluation 59
paper and paperboard 308
Quantitative analysis
atomic force microscopy 26
Auger electron spectroscopy 32
differential interference-contrast microscopy 341
differential scanning calorimetry 508
differential thermal analysis 499
electron probe analysis 118
electron spectroscopy for chemical analysis 142
inductive measurements 488
inertial-confinement fusion 242
interference-fringe microscopy 341
ion backscattering analysis 201
laser sampling inductively coupled plasma mass
spectrometry 218
mass spectrometry 297
nondestructive evaluation 59
Index
Raman
spectroscopy
629
Raman
spectroscopy
630
Subject
Index
fatigue cycling 415
Hooke's law 418
nondestructive evaluation 417
Barkhausen noise analysis 421
neutron diffraction 412
ultrasonic techniques 420
x-ray diffraction 418
plastic deformation 419
Poisson's ratio 414, 418
railroad rails 414
shot-peening 415
superalloys 416
thermoelastic effect 486
weldments 414
Young's modulus 414, 418
see also Stresses
Resistivity see Electrical conductivity
Resistors
solid-state gas sensors 177
Resonance absorption spectroscopy 521
Resonance Raman spectroscopy 408
Rhodamine-B
laser microprobe mass spectrometry 213
Richardson plots 156
Rocking curves 166
Rockwell hardness test 184
Rodrigues-Frank method 256
Root-mean-square meters
acoustic emission 2
Rotating-coil gaussmeters 228
Rubbers
mechanical properties 367
Rutherford backscattering
corrosion 77
diffusion 96
depth profiling 96
high-voltage electron microscopy 137
ion backscattering analysis 200
applications 202
channelling 203
differential scattering cross sections 201
energy loss 200
film thickness measurement 202
gold 204
kinematic factor 200
limitations 202
mass analysis 200
microprobe analysis 203
NbSi 2 202
Pt-Si alloys 202
quantitative analysis 201
S i - B F / 202
4
Sampling
inertial-confinement fusion 238
infrared spectroscopy 195
laser sampling inductively coupled plasma mass
spectrometry 275
nuclear magnetic resonance spectroscopy 276
particle-induced x-ray emission 310
see also Specimen preparation
Sapphire
hardness 235
ion implantation 235, 236
wear 235
Subject
Young's modulus 235, 236
Scanning acoustic microscopy 4
grain structure 5
Inconel 5
US penny 6
Scanning calorimeters 503
Scanning electron acoustic microscopy 518
applications 518
integrated circuits 520
Scanning electron microscopy 423
acoustic emission 424
aluminum films 425
Auger electron spectroscopy 423
backscattered electrons 423
cathodoluminescence 424
electron-hole pairs 424
electron-specimen interactions 423
image contrasts 424
electron-channelling-pattern contrast 425
magnetic contrast 426
topographic contrast 424
voltage contrast 425
contrast 425
inertial-confinement fusion 240
absorbed current electrons 241
backscattered electrons 241
secondary electrons 241
signal detection 240
x-ray emission 242
integrated circuits 425, 520
microtextural analysis 257
polymers 329
polyethylene 330, 331
polyethylene-polycarbonate blend 330
resolution range 341
quantitative analysis 425
secondary electron emission 423
silicon 425
TmSr, Se424
x
1 -x
Index
Sedimentation
631
Sedimentation
Subject
polymers
molecular weight distribution 349
Seeman-Bohlin focusing geometry 534
Segregation
hydrogen
metals 188
secondary-ion mass spectrometry 443, 444
Semiconducting materials
Auger electron spectroscopy 33
cathodoluminescence 43
crystal structure 452
defects 452
depth profiling 443
dislocations
etch hillocks 447, 448
etch pits 447, 449
doping 443
electron tunnelling spectroscopy 149
etching 445
dislocations 445
electrochemical reactions 446
GaAs 446
photoetching 446, 449, 451
interfaces
InGaAs-InP 454
transmission electron microscopy 454
x-ray microanalysis 456
junction transient spectroscopy 205, 206
microstructure 452
multilayers 452
muon probes 474
scanning tunnelling microscopy 427
secondary-ion mass spectroscopy 443
thermal wave imaging 519
transmission electron microscopy 452
see also III-V Semiconductors, specific compounds and
elements
Semiconductor devices
diode lasers 195
gas sensors 175
III-V Semiconductors
anodization spectroscopy 15
see also Semiconducting materials, specific compounds
Semiempirical relationships
phase diagram calculations 319
Sensors
beta sensors 302
gas sensors 175
infrared sensors 305
microwave sensors 305
nondestructive evaluation 302
paper and paperboard 302
optical properties 304
radio-frequency sensors 306
x-ray sensors 303
Shape analysis
fractals 156
Shear strength
adhesive bonds 10
Shear waves
ultrasonics 421
Shore Durometer
portable hardness tester 186
Shot-peening
residual stresses 415
632
Index
Shrinkage
destructive mechanical testing 299
Sieving
particle size distribution 392
Signal processing
acoustic emission 2
nondestructive evaluation
paper and paperboard 302
Silicon
defects
deep-level transient spectroscopy 205, 206
scanning tunnelling microscopy 432
device structure 453
high-resolution electron microscopy 131
interstitials 481
ionization 481
Raman spectroscopy 408
reflection electron microscopy 411
scanning electron microscopy 425
spark-source mass spectrography 481
structure 131
surfaces
inverse photoemission 429
scanning tunnelling microscopy 429, 431
ultraviolet photoemission 429
transmission electron microscopy 453
x-ray powder diffraction 582
see also Semiconducting materials
Silicon carbide
Acheson method 433
cathodoluminescence 46
fibers 46
growth facets 432
scanning tunnelling microscopy 433
tunnelling spectroscopy 434
Silicon steels
microtextural analysis 257
Silver
angular distribution Auger microscopy 37
Auger electron spectroscopy 31
coinage
art forgeries 20
corrosion potential polarography 21
Single crystals
angular distribution Auger microscopy 38
platinum 38
x-ray diffraction 457
Bragg's law 568
Sintering
dynamic mechanical analysis 513
microstructural evolution 250
Monte Carlo simulation 250
Ti0 2-coated A1 20 3 513
Size-exclusion chromatography
polymers 348
molecular weight distribution 350
see also Chromatography
Slurries
x-ray fluorescence spectrometry 576
Small-angle light scattering 338
Small-angle neutron scattering
Al-Zn alloys 465
amorphous polymers 351
molecular configurations 351
applications 464
Subject
copolymers 352
crystalline polymers 352
metallurgy 462
second-phase particles 462
microstructure
decomposing alloys 464
neutron scattering 462
Guinier approximation 463
magnetization distribution 464, 467
Porod approximation 463
Ni-Al alloys 466
phase separation 465
scaling analysis 465
polyelectrolytes 352
polymer networks 352
precipitates 466
procedure 464
see also Neutron scattering
Small-angle x-ray scattering 378
instrumentation 378
polymers
amorphous polymers 379
crazes 380
deformations 380
glass-transition temperature 380
phase transformations 380
semicrystalline polymers 279
voids 380
see also X-ray scattering
Smoke
flammability of polymers 363
National Bureau of Standards smoke chamber 365
Soft magnetic materials
power loss 231
Soil mechanics 400
Solid solutions
x-ray powder diffraction 581, 584
Solid-state gas sensors 175
Solid-state nuclear track detectors
applications 468
dosimetry 471
etching 468
geological samples 471
hole engineering 472
inorganic 469
ionization 469
Nuclepore filters 472
organic 470
particle identification 469
radon-222 mapping 473
sensitivity 469
track production 468
uranium mapping 471
Solidification
mechanical properties microprobes 235
Solids
infrared spectroscopy 196, 199
muon probes 473
nuclear magnetic resonance spectroscopy 273
x-ray fluorescence spectrometry 576
Solutions
infrared spectroscopy 196, 198
nuclear magnetic resonance spectroscopy 269, 273
Space groups 457
Spark-source mass spectrography 480
Index
Specimen
preparation
applications 483
instrumentation 480
interpretation 482
ion production 480
mass spectra 481
quantitative analysis 482
silicon 481
specimen preparation 481
see also Mass spectroscopy
SPATE 484
applications 484
composites 484
computer processing 484
fracture 484
instrumentation 484
numerical model validation 484
quantitative analysis 484
spanner and bolt 485
structural dynamics 484
see also Stresses
Specific heat
ABS resin 376
polymers 371
calorimetry 371
polystyrene 374
superconducting materials 489, 490
Specific surface
porosity 381
adsorption from solution 386
adsorption of gases and vapors 385, 393
capillarity 387
stereological analysis 383
powders
adsorption of gases 393
Specific volume
ceramic powders
mixtures 48
packing characterization 47
Specifications
elastomers 103
Specimen preparation
infrared spectroscopy 405
polymers
cutting 331
electron microscopy 329
light microscopy 336
solvent casting 332
transmission electron microscopy 331
Raman spectroscopy 405
reflection electron microscopy 411
scanning tunnelling microscopy 431
semiconducting materials 452
spark-source mass spectrography 481
transmission electron microscopy
polymer thin films 331
semiconducting materials 452
x-ray crystallography 461
x-ray fluorescence spectrometry 571, 576
fabricated parts 577
glass 576
liquids 576
powders 576
slurries 576
solids 576
supported specimens 576
633
Specimen
preparation
634
Subject
Index
corrosion 508
fracture 33
gamma radiography 163
silicon steels 257
stainless steel 127
texture 324
thermomagnetometry 508
X210Crl2 steel 264
see also Stainless steel
Steiner tunnel furnace 363
Stereological analysis
particle shape 394
porosity 383
Stokes equation 392
Stokes lines
Raman spectroscopy 403
Strain
convergent-beam transmission electron microscopy 539
neutron diffraction 412
palladium 587
tungsten 587
x-ray powder diffraction 581, 587
Stress analysis
thermoelastic effects 483
higher-order thermoelastic effects 486
infrared radiometry 484
Kelvin's law 483
mean-stress effects 486
residual stresses 486
SPATE 484
thermometric stress analysis 483
vibrothermography 548
Stress-corrosion cracking 78
Stress pattern analysis by measurement of thermal emission
see SPATE
Stress relaxation
polymers 368
Stress-strain relationships
polymers 366
powders 400
Stresses
acoustic emission 1
gamma-ray diffractometry 168
TaSi2 thin films 168
see also Residual stresses, SPATE
Stroboscopic techniques 567, 569
Structural dynamics
SPATE 484
Structure
amorphous solids
neutron diffraction 558
scattering vector 559
x-ray diffraction 558
angular distribution Auger microscopy 34
anodization spectroscopy 15
channelling-enhanced microanalysis 51
corrosion 76
N i
F4o 4o 2o
263
Subject
degree of regularity 356
Raman spectroscopy 354
secondary structure 356
small-angle x-ray scattering 378
silicon 131
surfaces
atomic force microscopy 23
low-energy electron diffraction 111
thin films 534
time-resolved x-ray diffraction 567
see also Atomic structure, Crystal structure, Molecular
structure
Subsecond thermophysical measurements 525
laser pulse heating 527, 529
femtosecond time resolution 531
high-speed photography 530
mass spectrometry 530
millisecond time resolution 530
nanosecond time resolution 531
refractive index 530
spectroscopic temperature measurements 530
metals 526
microgravity experiments 528
pulse heating 525
pyrometry 528
resistive pulse heating 526
microsecond time resolution 528
millisecond time resolution 528
submicrosecond time resolution 529
Sulfur
gas sensors 176
Superalloys
Ni-based alloys 416
Superconducting materials 487
ac losses 494
critical current density 487, 492
critical temperature 487
electron tunnelling spectroscopy 149
Josephson effect 150
flux creep 493
flux flow resistivity 491
Ginzburg-Landau theory 487
coherence length
inductive measurements 487
ac techniques 488
critical current density 493
critical temperature 489
dc magnetization 487, 493
quantitative analysis 488
irreversibility line 494
La 2Cu0 4 476
lower critical field 491
magnetic properties 226, 231
field effects 489, 491
magnetization 487
magnets 230
penetration depth 490
Meissner fraction 490
muon probes 476
internal field mapping 477
nickel zinc ferrite 506
oxygen content 506
pinning interaction distance 492
pinning penetration depth 492
resistive measurements 487
Index
Surfaces
635
Surfaces
scanning tunnelling microscopy 427
silicon 411, 429
structure 111
vibrational spectroscopy 54
Auger electron spectroscopy 54, 57
infrared spectroscopy 54
low-energy-electron loss spectroscopy 54, 55
photoelectron spectroscopy 55
ultraviolet photoelectron spectroscopy 54, 55
x-ray photoelectron spectroscopy 54, 55
x-ray characterization 533
Synchrotron radiation
Compton scattering 66, 67
time-resolved x-ray diffraction 568
x-ray absorption spectroscopy 557
x-ray powder diffraction 583
Tacticity
Raman spectroscopy 356
Tantalum oxide
depth profiling 85, 87
Tantalum silicide
evolved gas analysis 511
gamma-ray diffractometry 168
Tearing strength
destructive mechanical testing 301
Temperature see Thermal analysis
Tensile strength
adhesive bonds 10
destructive mechanical testing 301
paper and paperboard 301
polymers 366
Terracotta
art forgeries 17
Testing see specific methods
Tetramethylsilane
proton nuclear magnetic resonance spectroscopy 270
Texture
crystallite orientation distribution functions 322, 497
copper 498
killed steel 324
low-carbon steel 323
microtextural analysis 255
Mossbauer spectroscopy 264
neutron diffraction 497
nondestructive evaluation 497
pole figures, 322
copper 498
direct pole figures 323
inverse pole figures 324
x-ray goniometry 323
polymers 497
x-ray diffraction 497
x-ray powder diffraction 581, 586
see also Grain orientation
Thermal analysis
calorimetry 502
optical calorimetry 279
differential scanning calorimetry 359, 499, 508
differential thermal analysis 359, 508
dilatometry 503
thermodilatometry 511
dynamic mechanical analysis 511
evolved gas analysis 509
emanation thermal analysis 510
636
Subject
Index
feedback 513
overview 498
polymers 358, 371, 375
recent developments 506
thermogravimetry 358, 504, 506
thermomagnetometry 506
thermomechanical analysis 503
thermometry 499
see also Calorimetry
Thermal conductivity
composites 63
gas chromatography 171
thermography 63
vibrothermography 547
Thermal degradation
chemiluminescence 359
differential scanning calorimetry 359
differential thermal analysis 359
milling tests 357
oven aging tests 358
oxidation 357
oxygen uptake 358
ozone resistance 359
polymers 357
polyamides 359
polyethylene 359
polyvinyl chloride) 359
thermal analysis 358
thermogravimetric analysis 358
weatherability 360
Thermal diffusion
thermal wave imaging 515
Thermal emission see SPATE
Thermal expansion
adhesive bonds 10
dynamic mechanical analysis 511
LiNb0 3511
thermodilatometry 511
x-ray powder diffraction 581
Thermal gradients
vibrothermography 547
Thermal properties
polymers 371
extrapolation techniques 372
Thermal wave imaging 575
detection methods 517
imaging 516
generalized source imaging 516
localized source imaging 516
infrared sources 516
particle sources 518
electron injection 519
thermalization 519
photothermal radiometry 517
scanning electron acoustic microscopy 518
semiconducting materials 519
temperature distribution 515
thermal depth profiling 516
thermal diffusion 515
thermal spectroscopy 516
x-ray sources 516
Thermal-neutron scattering
polymers 351
Thermobalances 377
thermogravimetry 507
Subject
Thermodilatometry 511
applications 511
LiNb0 3511
see also Dynamic mechanical analysis
Thermodynamic activity 520
electrochemical measurements 524
fugacity 520
heterogeneous equilibrium 522
binary alloys 523
binary eutectic system 522
partitioning 522
gas-metal equilibrium 523
gas mixture 522
gas-three condensed phases equilibrium 524
gas-two condensed phases equilibrium 523
vapor pressure 520
dew point 521
effusion 521
resonance absorption spectroscopy 521
transpiration 521
Thermodynamic critical field 490
Thermodynamic properties
activity 520
calorimetry 503
polymers 372
polyethylene 372
Thermodynamics
etch pit formation 447
Gibbs-Duhem equation 520
phase diagram calculations 315
Thermoelasticity
stress analysis 483
higher-order thermoelastic effects 486
infrared radiometry 484
Kelvin's law 483
mean-stress effects 486
residual stresses 486
SPATE 484
Thermography
composites 63
thermal conductivity 63
real-time video thermography 547
vibrothermography 547
Thermogravimetry 504, 506
applications 506
calcium oxalate 505
coal 508
KHC0 3513
polymers 377
polyamides 359
polyethylene 359
polyvinyl chloride) 359
thermal degradation 358
thermal oxidation 359
precipitates 506
quantitative analysis 505
superconducting materials 506
nickel zinc ferrite 506
thermobalances 377, 507
thermomagnetometry 506
Thermoluminescence 525
art forgeries 18
atomic processes 526
dating
archeological ceramics 528
Index
Time
resolution
dosimetry 527
Thermomagnetometry 506
applications 506
coal 508
corrosion 508
magnetic susceptibility 506
precipitates 506
steel 508
Thermomechanical analysis 503
drawn polyester fibers 504
Thermometric stress analysis 483
infrared radiometry 483
SPATE 484
Thermometry 499
Thermophysical properties
subsecond measurements 525
Thermoreflectance 517
Thermosetting resins 376
Thermospray method
liquid chromatography mass spectrometry 222
Thick films see Foils
Thin films
angular distribution Auger microscopy 34
anodization spectroscopy 14
atomic force microscopy 28
buried layers 16
depth profiling 83
electron diffraction 104
epitaxial films
x-ray powder diffraction 585
NbSi 2
ion backscattering analysis 202
oxidation 202
optical calorimetry 280
polymers 331
Pt-Si 202
TaSi2
evolved gas analysis 511
gamma-ray diffractometry 168
thickness 76
convergent-beam transmission electron microscopy 538
corrosion product films 76
inertial-confinement fusion 238
infrared spectroscopy 195
ion backscattering analysis 202
transmission electron microscopy 331
x-ray characterization 537
extended x-ray absorption fine structure 535
glancing angle x-ray diffraction 534
glancing incidence x-ray scattering 534
grazing x-ray reflectometry 534
surface x-ray absorption spectroscopy 535
total-reflection x-ray fluorescence 534
x-ray fluorescence spectrometry 577
x-ray microanalysis 579
x-ray powder diffraction 585
Thomson-Gibbs equation 372
Tian-Calvet calorimeters 503
Time-of-flight techniques
atom-probe field-ion microscopes 152
laser microprobe mass spectrometry 209
neutron diffraction 560, 562
Time resolution
subsecond thermophysical measurements 528
x-ray diffraction 567
637
Time-resolved
x-ray
diffraction
Subject
638
Index
specimen preparation 452
stainless steel 127
superlattices 454
see also Electron microscopy, Scanning transmission
electron microscopy
Transmission lines
dielectric measurements 326, 328
Transparent materials
confocal optical microscopy 71
inertial-confinement fusion 239
Transpiration 521
Tungsten
x-ray powder diffraction 587
Tunnelling spectroscopy 428
current imaging tunnelling spectroscopy 429
electron energy states 428
point spectroscopy 428
SiC 434
ZnO 435
see also Electron tunnelling spectroscopy, Scanning
tunnelling microscopy
Turbidimetry
particle size distribution 393
Ultrasonic properties
wood 551
Ultrasonic techniques
acoustoultrasonics 551
grain size evaluation 179
backscatter technique 180
single-frequency technique 180
two-frequency technique 180
inspection
A-scan 60
B-scan 60
C-scan 60
composites 59
delamination 61
imaging systems 61
immersion testing 60
impact damage 60, 62
jet probes 61
roller probes 61
nondestructive evaluation 308
residual stresses 419
acoustoelastic constants 421
Rayleigh waves 421
shear waves 421
vibrothermography 547
wave propagation 179
Ultraviolet photoelectron spectroscopy
CO 56
Pd-CO 56
Rh^(CO)]6 56
solid surfaces 54, 55
Ultraviolet photoemission
silicon 429
Unit cells
convergent-beam transmission electron microscopy 541
electron diffraction 105
phase analysis 538
x-ray crystallography 457
Uranium
extended x-ray absorption fine structure 556
solid-state nuclear track detection 471
Subject
Vacancies
field-ion microscopy
displacement cascades 154
monovacancies 154
junction transient spectroscopy 205
metals
hydrogen probes 188
monovacancies 391
positron annihilation spectroscopy 391
microstructural evolution 247
reflection electron microscopy 411
transmission electron microscopy 121
Vacuum tunnelling 150
Valence levels
Auger electron spectroscopy 57
photoelectron spectroscopy 56
van der Waals attraction
powders 398
van't Hoff diagrams
nickel zinc ferrite 506
Vanadium suicide
convergent-beam transmission electron microscopy 541
Vapor pressure
Beer's law 521
thermodynamic activity 520
dew point 521
effusion 521
resonance absorption spectroscopy 521
transpiration 521
Vaporization
laser sampling inductively coupled plasma mass
spectrometry 217
Vibrating-sample magnetometers 227
Vibrational states
infrared spectroscopy 405
polymers
neutron scattering 351
Raman spectroscopy 354
Raman spectroscopy 354, 405
solid surfaces 54
see also Electron energy states
Vibroacoustic emission
composites 64
Vibrothermography 547
applications 548
composites
boron epoxy 549
delamination 547, 548
fatigue testing 548
high-amplitude low-frequency mechanical vibrations 547
high-frequency ultrasound 547
infrared detection 547, 548
low-amplitude high-frequency mechanical vibrations 547
methyl methacrylate 549
real-time video thermography 547
stress distribution 548
thermal conductivity 547
Vickers hardness test 184, 185
Video techniques
real-time video thermography 547
Viscoelasticity
adhesives 10
elastomers 102
Viscosity
polymers 348
Index
X-ray
absorption
spectroscopy
Visual inspection
composites 59
Voids
ceramic powders 48
composites 63
Compton scattering 67
computer-aided tomography 63
field-ion microscopy 155
nickel 121
niobium 122
polymers 380
small-angle x-ray scattering 380
transmission electron microscopy 121
Volatile materials
gas chromatography 169
Volumetric methods
ceramic powders 47
corrosion 75
Washburn equation 389
Water
absorption in polymers 377
particle-induced x-ray emission 314
Waveguides see Transmission lines
Wavelength-dispersive x-ray fluorescence spectrometry 570
Wear
mechanical properties microprobe 235
sapphire 235
Weatherability
ASTM test methods 360
laboratory tests 360
outdoor exposure 360
polymers 360
weatherometers 360
Welds
acoustic emission 3
austenitic stainless steel 235, 237
gamma radiography 163
neutron diffraction 414
Wetting 387
Wood
acoustic emission 551
adhesives 553
biological degradation 553
composites 553
cutting 553
defects 552
drying 553
fracture 552
particle-induced x-ray emission 314
quality control 552
X radiography
art forgeries 19
composites 61
penetrant enhanced radiography 62
X-ray absorption spectroscopy
extended x-ray absorption fine structure 535, 555
advantages 558
Fourier transforms 556
instrumentation 557
limitations 558
nickel 555
radial distribution function 556
639
X-ray absorption
spectroscopy
theory 555
uranium 556
x-ray sources 557
surfaces 535
x-ray absorption near edge fine structure 535, 5 5 5
advantages 558
instrumentation 557
limitations 558
theory 555
transition metal oxides 557
x-ray sources 557
X-ray analysis
electron-beam damage 333
index of refraction 533
thin films 531
x-ray fluorescence spectrometry 577
x-ray microanalysis 5 7 7
x-ray reflection 533
Kiessig fringes 534
see also X-ray microanalysis, specific techniques
X-ray crystallography 457
Bragg's law 458
computer processing 457
instrumentation 459
goniometers 460
lattice constants 457
organic materials 461
phase angle 459
procedure 460
space groups 457
specimen preparation 461
structure factor 459
unit cells 457
X-ray diffraction 458
amorphous solids 558
accuracy 564
Compton scattering 560
corrections 560
dispersion technique 560
fluorescent-foil x-ray diffraction 560, 563
instrumentation 559
interpretation 562
limitations 564
model calculations 563
peak fitting 562
quantitative analysis 560
real-space correlation function 559
scattering vector 559
theory 561
crystal symmetry 539
glancing angle x-ray diffraction 534
residual stresses 418
elastic deformation 418
plastic deformation 419
x-ray sources 419
single crystals 457
Bragg's law 568
texture 497
time-resolved x-ray diffraction 567
see also X-ray powder diffraction
X-ray electron microanalyzers 76
X-ray emission
analytical electron microscopy 124
crystal-diffraction spectrometers 116
electron microprobe analysis 115
640
Subject
Index
Bragg's law 116
x-ray maps 119
energy-dispersive spectrometers 117, 124
flow proportional counter 117
particle-induced x-ray emission 309
scanning electron microscopy 242, 423
X-ray fluorescence spectrometry 570
absorption-enhancement effects 577
analytical methods 577
calibration 577
mathematical methods 577
matrix-dilution methods 577
standard addition and dilution 577
standardization 577
thin films 577
x-ray scattering 577
dispersion 572
instrumentation 572
automation 571, 575
electronic detection 574
readout components 574
spectrogoniometers 573
x-ray generators 572
matrix effects 576
nondestructive evaluation 303
paper and paperboard 303
quantitative analysis 576
specimen preparation 571, 576
spectral excitation 572
total-reflection 534
x-ray sources 572
see also Fluorescence
X-ray inspection
inertial-confinement fusion 243
X-ray microanalysis
Al-Ag alloys 125
analytical electron microscopy 124
InGaAs-InP 456
Ni-Cr-Fe alloys 125
quantitative analysis 125, 5 7 7
calibration 580
Cliff-Lorimer equation 125
dimensions of analysis 580
energy-dispersive 577
Monte Carlo modelling 579
specimen geometry 579
wavelength-dispersive 577
ZAF corrections 578
see also X-ray analysis
X-ray photoelectron spectroscopy 139
corrosion 76
depth profiling 83
Ni-Cr alloys 88
solid surfaces 54, 55
see also Electron spectroscopy for chemical analysis
X-ray powder diffraction 581
amorphous materials 581, 585
applications 584
Bragg's law 568, 581
computer processing 583
crystal imperfections 581, 586
crystallite size 581, 587
diamond 582
epitaxial films 585
Gd 3Ga 50 12 garnet 584
Subject
in situ measurements 581
instrumentation 582
focusing x-ray diffractometers 582
pulse-height analyzer 583
lattice parameters 581, 585
mixtures 581
particle size 587
phase diagrams 584
phase identification 581, 583
computer matching 583
quantitative analysis 584
quartz 585
reflections 581
silicon 582
solid solutions 581, 584
specimen preparation 583
synchrotron radiation 583
texture 581, 586
thermal expansion 581
ZnS 582
see also X-ray diffraction
X-ray reflectometry 533
grazing x-ray reflectometry 534
Kiessig fringes 534
X-ray scattering
Compton scattering 65
diffuse x-ray scattering 565
Huang scattering 565
glancing incidence x-ray scattering 534
polymers 378
x-ray fluorescence spectrometry 577
see also Small-angle x-ray scattering
X-ray sensors
nondestructive evaluation 303
x-ray fluorescence spectrometry 574
X-ray sources
electron spectroscopy for chemical analysis 143
synchrotron radiation
time-resolved x-ray diffraction 568
x-ray absorption spectroscopy 557
x-ray powder diffraction 583
thermal wave imaging 516
Index
Zone-axis
patterns
641