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Metallic and Ceramic Materials
(MS3001) (MS3001)
Kong Ling Bing
School of Materials Science and Engineering
Nanyang Technological University y g g y
N4.1-01-25, Tel: 67905032
Email: elbkong@ntu.edu.sg
Outline
Introduction 1 h
Crystal Structure of Ceramics 2 h y
Defects in Ceramics 2 h
Phase Diagramof Ceramics 2 h Phase Diagram of Ceramics 2 h
Ceramic Processing 4 h
El t i l P ti f C i 4 h Electrical Properties of Ceramics 4 h
Magnetic Properties of Ceramics 4 h
Four Tutorials
CA (mid) + Final Exam ( )
Metallic and Ceramic Materials Metallic and Ceramic Materials
(MS3001) ( )
2. Crystal Structure of Ceramics
Objectives
Understand chemical bonds in ceramics.
Understand the concept of crystal structures in ceramics. Understand the concept of crystal structures in ceramics.
Calculate the minimum cation-to-anion radius ratio for the
coordination number 3 4 6 and 8 coordination number 3, 4, 6, and 8.
Understand the crystal structure of perovskite.
Understand the crystal structure of spinel.
5
Structures at Different Levels
6
Structures at Different Levels
Subatomic level electronic structure of
individual atoms that defines interaction
among atoms (bonding).
Atomic level arrangement of atoms in Atomic level arrangement of atoms in
materials (same atoms can have different
properties, e.g. graphite and diamond).
Microscopic structure arrangement of
small grains of materials that can be g
identified by microscopy.
Macroscopic structure structural p
elements that may be viewed with the naked
eye.
7
Review Electron Configurations
L shell with
two subshells
Nucleus
2s
1s
K
2s
2p
K
L
1s
2
2s
2
2p
2
or [He]2s
2
2p
2
1s
2
2s
2
2p
2
or [He]2s
2
2p
2
p [ ] p
The shell model of atom in which the electrons are confined to stay
p [ ] p
8
within certain shells and in subshells within shells.
Review Electron Configurations
I
1s
I
n
c
r
e
a
s
i
2s 2p
3s 3p 3d i
n
g

e
n
e
r
p
4s 4p 4d 4f
5s 5p 5d 5f
r
g
y
5s 5p 5d 5f
6s 6p 6d
7 7 7s 7p
Electron configurations of the neutral
gaseous atoms in the ground state.
9
Order: 1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4f 5d 6p 7s 5f 6d 7p
Chemical Bonds in Ceramics
Underlying many of the properties found in ceramics are the strong
primary bonds that hold the atoms together and form the ceramic
i l materials.
These chemical bonds are of two types:
ionic in character, involving a transfer of bonding electrons from
electropositive atoms (cations) to electronegative atoms e ect opos t ve ato s (cat o s) to e ect o egat ve ato s
(anions), and
covalent in character involving orbital sharing of electrons covalent in character, involving orbital sharing of electrons
between the constituent atoms or ions.
%i i h [1 ( 0 25{X X }
2
)] 100% %ionic character = [1 exp(-0.25{X
a
X
b
}
2
)] 100%
X
a
and X
b
are called electronegativity.
10
Gi l l R dil l
Chemical Bonds in Ceramics
Give up valence electrons Readily accept electrons
h l i d f Electronegativity: The relative tendency of an atom to accept an
electron and become an anion.
Strongly electronegative atoms readily accept electrons Strongly electronegative atoms readily accept electrons.
11
Ionic Bonding
Occurs between positive
and negative ions.
Requires electron transfer.
Large difference in
electronegativity required.
Example: NaCl
12
Covalent Bounding
Requires shared electrons
Example: CH4
C: has 4 valence e needs 4 C: has 4 valence e, needs 4
more
H: has 1 valence e needs 1 H: has 1 valence e, needs 1
more
Electronegativities are Electronegativities are
comparable
13
Metallic Bonding
Free valence
l t
Positive
Close Free valence
l f i
Positive
Close packing
f lli i
electrons
forming an
electron gas
Positive
metal ion
cores
packing of
metallic ions
(atoms)
electrons forming
an electron gas
metal ion
cores
of metallic ions
(atoms)
In metallic bonding, the valence electrons from the metal atoms
form a cloud of electrons, which fills in the space between the
l i d l h i h h h C l bi metal ions and glues the ions together through Coulombic
attraction between the electron gas and the positive metal ions.
F P i i l f El i M i l d D i 2 d Editi
14
From Principles of Electronic Materials and Devices, 2nd Edition,
S.O. Kasap( McGraw-Hill, 2002), http://Materials.Usask.Ca
Chemical Bonds - Summary
Type Bond energy Comments
Ionic Large Nondirectional (ceramics)
V i bl Di ti l Variable Directional
Covalent large: Diamond (semiconductors, ceramics
small: Bismuth polymer chains) small: Bismuth polymer chains)
Variable
Metallic large: Tungsten Nondirectional (metals)
small: Mercury
Directional
Secondary Smallest inter-chain (polymer)
15
Secondary Smallest inter chain (polymer)
inter-molecular
Crystal Structure in Ceramics
Most of the primary chemical bonds found in ceramic materials are
Chemical Bonding in Ceramics
Most of the primary chemical bonds found in ceramic materials are
actually a mixture of ionic and covalent types.
It is therefore only a convenient (but quite successful)
approximation to treat most ceramics as ionic solids.
Ionic bonds are non-directional in nature, that is the attractive
forces occur formall directions. forces occur form all directions.
This non-directional nature allows for hard-sphere packing
arrangements of the ions into a variety of crystal structures, with
two limitations.
16
Crystal Structure in Ceramics
The first limitation involves the relative size of the anions and the
First Limitation
The first limitation involves the relative size of the anions and the
cations.
Anions are usually larger and close-packed, similar to the face-
centered cubic or hexagonal close-packed crystal structures found
i t l in metals.
Cations on the other hand are usually smaller occupying space Cations, on the other hand, are usually smaller, occupying space
(interstices) in the crystal lattice between/among the anions.
17
Crystal Structure in Ceramics
The second limitation on the types of crystal structure that can be
Second Limitation
The second limitation on the types of crystal structure that can be
adopted by ionically bonded atoms is based on a law of physics -
the crystal must remain electrical neutrality.
This law of electroneutrality results in the formation of very
ifi t i hi t i i ifi ti f ti t i th t specific stoichiometries; i.e, specific ratios of cations to anions that
maintain a net balance between positive and negative charges.
In fact, anions are known to pack around cations, and cations
around anions, in order to eliminate local charge imbalance.
This phenomenon is referred to as coordination (number).
18
Packing and Energy
Non dense, random packing
Energy
typical neighbor
Energy
typical neighbor
r
typical neighbor
bond length
typical neighbor
yp g
bond length
typical neighbor r
typical neighbor
bond energy
E
typical neighbor
bond energy
r
Dense, regular packing
Energy
typical neighbor
b d le th
Energy
typical neighbor
bond length
r
bond length
typical neighbor
bond length
typical neighbor
r
D d l k d t t t d t h l !
typical neighbor
bond energy
yp g
bond energy
r
19
Dense and regular-packed structures tend to have lower energy!
Packing and Energy
Non dense, random packing
Energy
typical neighbor
bond length
r
typical neighbor
bond energy
Energy
typical neighbor
bond length
Dense, ordered packing
r
bond length
typical neighbor
Dense ordered packed structures tend to have lower energies and
typical neighbor
bond energy
Dense, ordered packed structures tend to have lower energies and
thus are more stable!
Packing and Structure
Noncrystalline (amorphous) materials...
atoms have no periodic packing
occurs for: -complex structures
-rapid cooling p g
noncrystalline SiO2
Crystalline materials...
Si Oxygen
Si Oxygen
y
atoms pack in periodic, 3D arrays
typical of: -metals typical of: metals
-many ceramics
-some polymers
21
some polymers
crystalline SiO2
N d d ki
Packing and Structure
Non dense, random packing
Noncrystalline (amorphous)
materials materials
Energy is higher, or
metastable metastable
Ceramics are (poly-)
crystalline solids!
Dense, regular packing
crystalline solids!
Crystalline materials
Energy is lower, or more gy ,
stable
Crystalline solids have C ysta e so ds ave
periodic structure!
Crystal Structure in Ceramics
Periodic Structures
Periodic structures can be represented by periodicity unit cell.
23
Crystal Structure in Ceramics
Unit Cells of Crystals
Lattice parameters
axial lengths: a, b, c
interaxial angles: , ,
c

g , ,
unit vectors: , , a

In general: a b c

a All period unit cells can
be described with these
vectors and angles vectors and angles.
24
Crystal Structure in Ceramics
S (7) C t l S t
D / k?
Seven (7) Crystal Systems
Days/week?
Colors/rainbow?
Simple cubic
a = b = c
90
Tetragonal
a = b c
Orthorhombic
a b c
Rhombohedral
a = b = c
Simple cubic
a = b = c
90
Tetragonal
a = b c
Orthorhombic
a b c
Rhombohedral
a = b = c
= = = 90
= = = 90
a b c
= = = 90
a b c
= = 90
= = = 90
= = = 90
a b c
= = = 90
a b c
= = 90
Monoclinic
T i li i H l
Monoclinic
T i li i H l
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Monoclinic
a b c
= = 90
Triclinic
a b c
90
Hexagonal
a = b c
= = 90, = 120
Monoclinic
a b c
= = 90
Triclinic
a b c
90
Hexagonal
a = b c
= = 90, = 120
Crystal Structure in Ceramics
Th (3) T f P ki f C bi C t l S t Three (3) Types of Packing of Cubic Crystal System
Primitive
Face-centered
Body-centered
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cubic
cubic
y
cubic
S (7) C t l S t + F t (14) C t l L tti
Crystal Structure in Ceramics
Seven (7) Crystal Systems + Fourteen (14) Crystal Lattices
27
Crystal Structure in Ceramics
C t l Pl Crystal Planes
Planes in a crystal can be specified
b i i ll d Mill by using a notation called Miller
indices.
Miller indices were introduced in
1839 by the British mineralogist
WilliamHallowes Miller (6 Apr William Hallowes Miller (6 Apr
1801 20 May 1880, British
mineralogist and crystallographer). g y g p )
The Miller index is indicated by the
notation [hkl] where h, k, and l are [ ] , ,
reciprocals of the plane with the x,
y, and z axes.
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Crystal Structure in Ceramics
C t l Pl Crystal Planes
To obtain the Miller indices of a given plane requires the following
ffour steps:
Step 1. The plane in question is placed on a unit cell. p p q p
Step 2. Its intercepts with each of the crystal axes are then
found found.
Step 3. The reciprocal of the intercepts are taken.
Step 4. These are multiplied by a scalar to insure that is in the
simple ratio of whole numbers.
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Crystal Structure in Ceramics
Crystallographic Planes
Miller Indices:
[001]
x y z
Intercepts: 1 infinite infinite
Reciprocals 1 0 0 Reciprocals 1 0 0
Lowest integers 1 0 0
[010]
Plane: (100)
[100]
Crystal Structure in Ceramics
Crystallographic Planes
Miller Indices:
[001]
x y z
Intercepts: -1 infinite infinite
Reciprocals 1 0 0
[001]
?
Reciprocals -1 0 0
Lowest integers -1 0 0
?
Plane: (100)
[010]
[100]
Crystal Structure in Ceramics
Crystallographic Planes
Miller Indices:
[001]
x y z
Intercepts: 1 1 infinite
Reciprocals 1 1 0 Reciprocals 1 1 0
Lowest integers 1 1 0
[010]
Plane (110)
[100]
Crystal Structure in Ceramics
Crystallographic Planes
Miller Indices:
[001]
x y z
Intercepts: 1 1 1
Reciprocals 1 1 1 Reciprocals 1 1 1
Lowest integers 1 1 1
[010]
Plane: (111)
[100]
Mill I di
C t ll hi l
Crystal Structure in Ceramics
Miller Indices:
x y z
Intercepts: -1/2 infinite 1
Crystallographic planes
[001]
Intercepts: 1/2 infinite 1
Reciprocals -2 0 1
Lowest integers -2 0 1
Plane: (201)
[010]
[100]
[010]
[001]
[010]
[100]
Crystal Structure in Ceramics
Example: to determine plane (112)
Miller Indices:
x y z
z
x y z
Intercepts: 1 1 1/2
R i l 1 1 2
1/2
Reciprocals 1 1 2
Lowest integers 1 1 2
1
1/2
Plane: (112)
y
1
x
Crystal Structure in Ceramics
Example: to determine plane (234)
Miller Indices:
x y z
z
x y z
Intercepts: 1/2 1/3 1/4
R i l 2 3 4 Reciprocals 2 3 4
Lowest integers 2 3 4
1/3
1/4
Plane: (234)
y
1/2
1/3
x
Crystal Structure in Ceramics
Why anions are larger than cations?
How many crystal systems are there?
7
How many crystal systems are there?
How many lattice types are there?
7
14

How many steps used to determine Miller indices

of crystal planes?
4
37
Mill I di
C t ll hi l
Crystal Structure in Ceramics
Miller Indices:
x y z
Intercepts: -1/2 infinite 1
Crystallographic planes
[001]
Intercepts: 1/2 infinite 1
Reciprocals -2 0 1
Lowest integers -2 0 1
Plane: (201)
[010]
[100]
[010]
[001]
[010]
[100]
Crystal Structure in Ceramics
Crystallographic planes
Miller Indices:
[001]
x y z
Intercepts: 1/2 infinite 1
Reciprocals 2 0 1 Reciprocals 2 0 1
Lowest integers 2 0 1
[010]
Plane: (201)
[100]
Crystal Structure in Ceramics
Families of Planes
Afamily of planes is represented by{hkl} A family of planes is represented by{hkl}
Thus, indices {hkl} represent all the planes equivalent to the
l (hkl) i l
) 00 1 ( ), 1 00 ( ), 0 1 0 ( ), 001 ( ), 010 ( ), 100 ( } 100 {
plane (hkl) in a crystal.
) 1 1 1 ( ), 1 1 1 ( ), 1 1 1 ( ), 1 1 1 ( ), 11 1 ( ), 1 1 1 ( ), 1 11 ( ), 111 ( } 111 {
) 00 1 ( ), 1 00 ( ), 0 1 0 ( ), 001 ( ), 010 ( ), 100 ( } 100 {

There are many other families of planes in a crystal.

Crystal Structure in Ceramics
Crystallographic Directions
[001] [001]
[101]
[011]
[111]
<100> cube edges
[ ]
<011> face diagonals
[010]
<111> cube diagonals
[100]
[110]
Th ll hi di i di l h i The crystallographic directions are perpendicular to their
corresponding planes.
Crystal Structure in Ceramics
Summary
Because a crystal is periodic, there exist families of equivalent
directions and planes.
Notations allow for distinction between a specific direction or
l d f ili f h i di i
Miller conventions - { } vs ( ) and [ ] vs < >
plane and families of such periodicity.
Use the ( ) notation to identify a specific plane, e.g. (113).
Use the { } notation to identify a family of equivalent planes,
e.g. {311}.
Use the [ ] notation to identify a specific direction, e.g. [101].
U th t ti t id tif f il f i l t Use the < > notation to identify a family of equivalent
directions, e.g. <110>.
Abar above a index is equivalent to a minus sign
42
A bar above a index is equivalent to a minus sign.
Crystal Structure in Ceramics
Terminology
Summary
gy
Planes ( )
Families of equivalent planes { } q p { }
Directions [ ]
Families of directions < > Families of directions
(100)=bar one zero zero and NOT one bar zero zero ( )
Crystal Structure in Ceramics
Spacing between Planes in a Cubic Crystal
(100) (110) (111)
a
=
d
(100) (110) (111)
1
l
+
k
+
h
=
2 2 2
l
+
k
+
h
=
d
2 2 2
hkl
2 2
a
=
d
hkl
where d
hkl
= inter-planar spacing between planes with Miller
indices h, k and l.
l tti t t ( d f th b ) a = lattice constant (edge of the cube)
h, k, l = Miller indices of cubic planes being considered.
Crystal Structure in Ceramics
Spacing between planes in a cubic crystal
Calculate plane spacing of (100), (110), (111), (112) and (234) p p g ( ), ( ), ( ), ( ) ( )
planes, of a crystal of cubic structure, with a = 4.05 .
0 4

A = 05 . 4
0 0 1
05 . 4
100
2 2 2
+ +
=
d
l
+
k
+
h
a
=
d
2 2 2
hkl

A = = 571 . 3
2
05 . 4
0 1 1
05 . 4
110
2 2 2
+ +
=
d

A = = 643 . 1
6
05 . 4
2 1 1
05 . 4
112
2 2 2
+ +
=
d
0 1 1

A = = 338 . 2
3
05 . 4 05 . 4
111
2 2 2
=
d

A = = 432 . 0
29
05 . 4 05 . 4
234
2 2 2
=
d
3
1 1 1
2 2 2
+ +
29
4 3 2
2 2 2
+ +
The larger the values of the Miller indices, the smaller the spacing
45
of the planes will be.
Ionic Radii and Coordination Number
C.N.=2 Linear R
C
/R
A
: <0.155
C.N.=3 Triangular R
C
/R
A
: 0.225-0.155
C.N.=4 Tetrahedral R
C
/R
A
: 0.414-0.225
C.N.=6 Octahedral R
C
/R
A
: 0.732-0.414
C N =8 Cubic R /R : 1 0 0 732
46
C.N.=8 Cubic R
C
/R
A
: 1.0-0.732
Ionic Radii and Coordination Number
Stable ceramic crystal structures require that anions surrounding a
cation are all in contact with that cation.
For a specific coordination number, there is a critical or minimum
cation-anion radius ratio, r
C
/r
A
, for which this contact can be
i t i d maintained.
Unstable
Stable
Stable
47
U stab e
Ionic Radii and Coordination Number
Example
D t t th t th i i ti t i di ti f Demonstrate that the minimum cation-to-anion radius ratio for
the coordination number 8 is 0.732 for stable ceramic crystal
structures. structures.
In stable ceramic crystal structures, anions surrounding a cation are
all in contact with that cation.
For a specific coordination number, there is a critical or minimum
cation-anion radius ratio r
C
/r
A
, for which this contact can be
maintained.
This problem asks us to show that the minimum cation-to-anion
48
radius ratio for a coordination number of 8 is 0.732.
Ionic Radii and Coordination Number
From the cubic unit cell shown below (Ions are reduced in size for
the sake of clarity.)
Anion
Q
Anion
M
Q
M
N
P
Cation
2r
A
Q
Cation
y
M
x
2r
A
49
2r
A
N
P
Ionic Radii and Coordination Number
The unit cell edge length is 2r
A
, and from the base of the unit cell,
there is
2r
Q
( ) ( ) r 8 = r 2 + r 2 = x
2
A
2
A
2
A
2
2r
A
y
M
( ) ( )
x
2r
y
M
so
2 r 2 = x
A
x
2r
A
P
A
No from the triangle that in ol es and the nit cell edge can
2r
A
N
P
Now from the triangle that involves x and y, the unit cell edge can
be calculated.
50
Ionic Radii and Coordination Number
Q
( ) ( )
2
C A
2
2
A
2
2r + r 2 = y = r 2 + x
2r
A
Q
( ) ( )
2
C A
2
A
2
A
r 2 + r 2 = r 4 + 2 r 2
y
M
( ) ( )
C A A A
x
2r
A
( )
2
2
r 2 + r 2 = r 2 1
2r
A
( )
C A A
r 2 + r 2 = r 2 1
N
P
0 732 1 3
C
r
C A A
r 2 + r 2 = r 3 2
( )
C
r = 1 3 r
A

0.732 = 1 3 =
A
C
r
51
( )
C A
A
Perovskite Structure
Number of Atoms/Ions of a Given Unit
Corner Edge Face
Shared by eight
units

g
Shared by four
units

Shared by two
units
1/8 1/4 1/2
52
Perovskite Structure
Corner atom: 1/8
Edge atom: 1/4
Corner atom: 1/8
g
Edge atom: 1/4
Face atom: 1/2
Face atom: 1/2
Body atom: 1
Body atom: 1
Body atom: 1
y
Corner Edge Face
N N N N N
8
1
4
1
2
1
Body
= + + +
53
Corner Edge Face
8 4 2
Body
Crystal Structure in Ceramics
Terminologies regarding Miller indices:
Review
g g g
Planes ( )
Families of equivalent planes { }
Directions [ ] Directions [ ]
Families of directions < >
Perovskite Structure
Corner atom: 1/8
Edge atom: 1/4
Corner atom: 1/8
Review
g
Edge atom: 1/4
Face atom: 1/2
Face atom: 1/2
Body atom: 1
Body atom: 1
Body atom: 1
y
Corner Edge Face
N N N N N
8
1
4
1
2
1
Body
= + + +
55
Corner Edge Face
8 4 2
Body
Perovskite Structure
Ca (A)
Calcium Titanate
Ca (A)
Ti (B) Ti (B) ( )
O
2-
(O)
( )
O
2-
(O) ( )
Ca (A) = 8 1/8 = 1
( )
( )
Ti (B) = 1 1 = 1
O
2-
(O) = 6 1/2 = 3
Chemical formula: CaTiO
3
(ABO
3
)
Lattice parameter: a = 3.8967
56
p
Mineral name: Perovskite
Perovskite Structure
Barium Titanate
Ba (A) Ba (A)
Ti (B) Ti (B)
O
2-
(O)
Ba (A) = 8 1/8 = 1
( )
Ba (A) 8 1/8 1
Ti (B) = 1 1 = 1
O
2-
(O) = 6 1/2 = 3
BaTiO
3
(Perovskite type) (ABO
3
)
a = 4.0185
57
a 4.0185
Perovskite Structure
Brief Summary
General formula: ABO
33
General valency: A
2+
B
4+
O
3
CaTiO
3
, SrTiO
3
, BaTiO
3
, PbTiO
3
Alternative (i): A
3+
B
3+
O
3
LaFeO
3
, LaNiO
3
Al i (ii) A
1+
B
5+
O LiNbO N NbO KNbO Alternative (ii): A
1+
B
5+
O
3
LiNbO
3
, NaNbO
3
, KNbO
3
Alternative (iii): A(B
1-x
B
x
)O
3
Pb(Zr
1-x
Ti
x
)O
3
( ) (
1 x x
)
3
(
1 x x
)
3
Alternative (iv): (A
1-x
A
x
) BO
3
(Ba
1-x
Sr
x
)TiO
3
Alternative (v): (A
1-x
A
x
) (B
1-y
B
y
)O
3
(Pb
1-x
Ba
x
)(Zr
1-y
Ti
y
)O
3
58
Spinel Structure
A site: tetragonal,
General Formula
A site
B site
64(1/8) = 8
B site: octahedral,
32(1/2) = 16
A site
B site
O
2-
32(1/2) = 16
O
2-
site: 32
Formula: AB
2
O
4
(8)
O
2-
2 4
( )
A
2+
, B
3+
, O
2-
Charge neutrality

W. H. Bragg, The structure of the spinel group of crystals, Philos.

21+32=|-24|
W. H. Bragg, The structure of the spinel group of crystals, Philos.
Mag., 30, 305-315 (1915).
S. Nishikawa, Structure of some crystals of the spinel group, Proc.
59
Math. Phys. Soc. Tokyo, 8, 199-209 (1915).
Spinel Structure
Spinel structure is named after the mineral spinel (MgAl
2
O
4
).
Brief Summary
p p ( g
2 4
)
Their general formula is AB
2
O
4
.
It i ti ll bi ith O
2
i f i f (f t It is essentially cubic, with O
2-
ions forming a fcc (face center
cubic) lattice.
Th ti ( ll t l ) 1/8 f th t t h d l it d The cations (usually metals) occupy 1/8 of the tetrahedral sites and
1/2 of the octahedral sites and there are 32 O
2-
ions in the unit cell.
Thi d li d b i i b d i ld b l k This sounds complicated, but it is not as bad as it could be; look at
the drawing.
We simply have two types of cubic building units inside a big fcc
O-ion lattice, filling all 8 octants.
60
Spinel Structure
All spinels
Normal, Inverse and Mixed Spinel
p
AB
2
O
4
(8)
Unit cell: 32 fcc O Inverse spinels Unit cell: 32 fcc O
64 tetrahedral sites: 8
filled (ratio = 1/8)
Normal spinels
8 A on tetrahedral sites
p
8 B on tetrahedral
sites,
32 octahedral sites: 16
filled (ratio = 1/2)
16 B on octahedral sites
(A
2+
)
T
[B
3+
B
3+
]
O
O
2-
4
8 B on octahedral sites,
and
(1 cation)
T
[2 cations]
O
O
2-
4
(x8)
(x8)
8 A on octahedral sites
A and B randomly
d i arranged on oct sites
(B
3+
)
T
[A
2+
B
3+
]
O
O
2-
4
(x8)
The general formula for mixed spinel is
(A B ) [A B ] O (8)
61
(x8) (A
1-x
B
x
)
T
[A
x
B
2-x
]
O
O
4
(8)
Determination of Crystal Structures
X-Ray Diffraction - XRD
XRD can be used to text powder, bulk, thin film samples.
Diffraction patterns are obtained after a scanning over a certain
range of angles.
The patterns are used to identify the crystal structure of the
samples tested.
Transmission Electron Microscope (TEM)
p
TEM samples for powders are made by dispersing the powders
in a certain liquid and then deposit on sample holder.
Preparation of bulk samples is a challenging work.
TEMcan be used to observe sample morphology and determine
62
TEM can be used to observe sample morphology and determine
crystal structure.
Determination of Crystal Structures
X-Ray Diffraction - XRD Wilhelm Rntgen
Diffraction occurs when gratings have spacings
Nobel
Diffraction occurs when gratings have spacings
comparable to the wavelength of diffracted radiation.
For crystals, spacing is the distance between parallel
Prize in
Physics in
1901
y , p g p
planes of atoms.
Determination of Crystal Structures
iff i ( ) X-Ray Diffraction (XRD)
Sir William Henry Bragg
Diffraction!
Nobel
Prize in
Physics in
Diffraction!
Physics in
1915
Cancelled out!
64
Lawrence
Determination of Crystal Structures
iff i ( ) X-Ray Diffraction (XRD)
is the wavelength is the wavelength
of the X-ray.
u i d
QT SQ n + =
u u sin sin + =
hkl hkl
d d n
u i d
65
u sin 2 =
hkl
d n
Braggs law!
u sin 2 =
hkl
d
Determination of Crystal Structures
u sin 2 =
hkl
d
= 1.54 for copper target.
hkl

=
hkl
d
Plane spacing can be calculated by
the experimental diffraction angle
u sin 2
hkl
the experimental diffraction angle
from XRD pattern.
sin

u =
From plane spacing of a given
material diffraction angle can be
hkl
d 2
sinu =
material, diffraction angle can be
calculated or predicted, thus giving
out XRD pattern.
66
p
Determination of Crystal Structures
X-Ray Diffraction - XRD
X-ray source
X-ray detector
S l
Bragg angle =
2 = diffraction angle
Sample
67
Determination of Crystal Structures
iff i ( ) X-ray diffraction (XRD)
(100)
2=21.67,
12000
15000
(
1
1
0
)
P
S
)
2 21.67 ,
=10.84,
9000
1
)
n
s
i
t
y

(
C
P
) 84 10 sin( 2
54 . 1
100

A
=

d
3000
6000
(
2
1
2
1
0
)
(
2
0
0
)
(
1
1
1
)
I
n
t
e
n
(
1
0
0
)
) 84 . 10 sin( 2
54 1 A

20 30 40 50 60
(
2
2 (
o
)
188 . 0 2
54 . 1

A
=
2u (
o
)
XRD patter of a perovskite type

A = 096 . 4
68
polycrystal material.
Determination of Crystal Structures
iff i ( )
(100): 2=21.67, =10.84, d
100
=4.096
X-Ray Diffraction (XRD)
( ) , ,
100
(110): 2=30.86, =15.43, d
110
=2.894
(111): 2=38.13, =19.07, d
111
=2.357
(200) 2 44 35 22 18 d 2 040 (200): 2=44.35, =22.18, d
200
=2.040
(210): 2=49.86, =24.93, d
210
=1.827 ( )
210
(211): 2=55.04, =27.52, d
211
=1.666
The higher the diffraction angles, the smaller the plane spacings
will be
69
will be.
i i i ( )
Determination of Crystal Structures
Transmission Electron Microscope (TEM)
70
Summary
Most of the primary chemical bonds found in ceramic materials are
actually a mixture of ionic and covalent types.
Crystal structures of ceramics with predominantly ionic bonding are
based on:
The relative sizes of the cations and anions - cation tends to have
maximum possible number of anion nearest neighbors and vice-
versa.
Magnitude of the electrical charge on each ion, whose balance g g
dictates chemical formula.
X-ray diffraction (XRD) and transmission electron microscopy X-ray diffraction (XRD) and transmission electron microscopy
(TEM) are powerful tools to examine crystal structures of ceramics.
71