NIST

Polymers & Complex Fluids Group

Benefits of Combining Rheometry with Raman

Spectroscopy for Polymer Research

The world leader in serving science

Contents
Introduction and motivation
Why combine rheology with Raman?
Basics of rheology
Basics of Raman spectroscopy
The first commercially available integration of a rheometerRaman Spectrometer
Applications for polymer research
Polymer additives in cosmetic emulsions
Temperature induced crystallization in polyethylenes
Summary

Why combining Rheology with Raman Spectroscopy?

Rheology yields an integral answer for the visco-elastic
behavior of the tested sample
No information at the molecular level obtained!
Which complementary method to choose?
Molecular spectroscopy / Raman spectroscopy can:
Detect changes in the chemistry and conformation of a sample
Detect changes in molecular orientation as a
function of shear and deformation (probing for crystallization)

Raman Spectroscopy and Rheometry Status Quo

Correlating Raman and rheological data is not new
However until now the tests were usually conducted separately
Raman spectrum
before measurement

Raman spectrum
after measurement

0.0

0.0

0.1

0.1

0.2

0.2

Absorbance Units
0.3
0.4

Absorbance Units
0.3
0.4

0.5

0.5

0.6

0.6

0.7

0.7

Rheological Test

3500

3000

2500

2000
Wavenumber cm-1

1500

1000

500

3500

3000

2500

2000
Wavenumber cm-1

1500

No direct correlation between rheological data and spectra

No in-situ spectrum of sample under deformation or stress
Separate tests dramatically increase time demand when e.g.
monitoring long curing reaction

1000

500

Raman Spectroscopy and Rheometry Prior Work

Archer, Huang and Fuller, J Rheol. 1994

Raman + Birefringence
Melt orientation (Archer & Fuller,
1994)

Raman + Rotational Rheometry

Epoxy curing (Shaw, 2001)
Farquharson, Smith, Rose and Shaw,
J Process Anal Chem. 2001

Contents
Introduction and motivation
Why combining rheology with Raman?
Basics of rheology
Basics of Raman spectroscopy
The first commercially available combination of a rheometerRaman spectrometer
Applications for polymer research
Polymer additives in cosmetic emulsions
Temperature induced crystallization in polyethylenes
Summary

Basics of Rheology

The term rheology was proposed by E.C. Bingham

and M. Reiner in 1929 for an interdisciplinary field of
material sciences
It derives of the Greek terms for flow (rhei) and
(logos) for word (science)
Rheology is the science of the deformation and flow of
matter under controlled testing conditions

Basics of Rheology

Panta rhei! But does really everything flow?

Well, it depends!
How long do you want to wait?

Deborah* Number =

Time of Relaxation
Time of Observation

*after prophetess Deborah, Judges 5:5

http://www.rheology.org/sor
8

Basics of Rheology
Everything flows?
The glass windows of the Cathedral of Chartres in France

Gravity
or way of
mounting?

1200

2011
Images taken from wikipedia

Basics of Rheology

Viscosity

10

Elasticity

G* =

Basics of Rheology

Polymers

Cosmetics

Food

Die Swell

Spreadability

GMF

Texture

Entropy Elasticity
Fatigue

Inks & Coatings

Printing

Shelf Life
Stickiness

Mouth Feeling

Misting

Processing Behavior
Image taken from rheology.ro
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Thermo Scientific HAAKE MARS

12

Thermo Scientific HAAKE MARS

13

Thermo Scientific HAAKE MARS

14

Thermo Scientific HAAKE MARS

15

Thermo Scientific HAAKE MARS

16

Contents
Introduction and motivation
Why combine rheology with Raman?
Basics of rheology
Basics of Raman spectroscopy
The first commercially available combination of a rheometerRaman Spectrometer
Applications for polymer research
Polymer additives in cosmetic emulsions
Temperature induced crystallization in polyethylenes
Summary

17

What is Raman Spectroscopy?

Raman spectroscopy is a light scattering vibrational technique
Fast, noncontact, and nondestructive
Probes vibrations in covalently bonded molecules
Requires some degree of covalency in the molecule
A purely ionic compound will not be Raman active

The Raman spectrum of a molecule will be dependent upon

The atoms present
The chemical bonding in the molecule
The geometric structure of the molecule
The environment can also have an effect ( stress and or strain)

Raman gives important insight into your sample at the molecular level
Molecular identification spectral fingerprint unambiguous chemical signature
Morphology
Differentiate between crystalline and amorphous materials
Differentiate allotropes/polymorphs
18

What is Raman spectroscopy?

LASER

Rayleigh scattering

Raman scattering
(Stokes shift)

Raman scattering

~~~~~~~~~~~~
Excitation frequency

Rayleigh scattering
(filtered out)

V = virtual state

V=1

Blocking Filter

V=0

2000

19

1800

1600 1400

1200 1000 800

600
Raman shift (cm-1)

400

200

Visible monochromatic light is directed to material under

study
The light is both elastically scattered and in-elastically
scattered by the material. The two types of scattered light
are referred to as Rayleigh and Raman scatter,
respectively.
The Rayleigh scattered light is blocked by an optical filter
The Raman scattered photons are collected and analyzed
by a spectrograph and CCD detector
The differences in energy, E, between the incident
photons and the collected in-elastically scattered photons
are equal to the energies of vibrational transitions of the
material
A vibrational spectrum is constructed by plotting the
intensity of the scattered light against the difference in
energy of the incident and the in-elastically scattered
photons

DXR2 Raman Microscope from Thermo Fisher Scientific

Research grade performance meets ease of use operation

A true walk up Raman microscope
Intuitive interface and extensive automation
Gain instrument expertise quickly
Automated features On demand alignment and calibration
Spectral collection parameter optimization
Auto focus
Auto exposure

Multiple laser excitation sources

Easy access external beam port offers flexibility
Direct through space coupling to other instrumentation
AFM
Rheometer

Superior Raman performance

Highly sensitive, accurate and precise

20

Raman Spectroscopy - Distinguish Between Similar Materials

Pharmaceutical Polymorphs

Polymers

3273, 3254 cm-1

Nylon 6

Nylon 6/6

(monoclinic form)
3267cm-1

Anatase TiO2

(triclinic form)
Rutile TiO2

800 700 600 500 400 300

Raman shift (cm-1)

21

200

Raman Spectroscopy Evaluating Morphology and Physical State

Drug Form Stability

Hydrated Form

Anhydride Form

Nano-structured vs. Bulk

22

Crystalline vs. Amorphous Pharmaceutical

Contents
Introduction and motivation
Why combine rheology with Raman?
Basics of rheology
Basics of Raman spectroscopy
The first commercially available combination of a rheometer
and a Raman spectrometer
Applications for polymer research
Polymer additives in cosmetic emulsions
Temperature induced crystallization in polyethylenes
Summary

23

Coupling of a Rheometer and a Raman Spectrometer

24

Coupling of a Rheometer and a Raman Spectrometer

Setup at Polymers and Complex Fluids Group of NIST (Prof. Kalman Migler)

25

Contents
Introduction and motivation
Why combine rheology with Raman?
Basics of rheology
Basics of Raman spectroscopy
The first commercially available integrated of a rheometerRaman spectrometer
Applications for Polymer Research
Polymer additives in cosmetic emulsions
Temperature induced crystallization in polyethylenes
Summary

26

Applications for Polymer Research Cosmetic Emulsions

At which temperature does my emulsion become unstable?
intra-chain consecutive-trans in the
C-C

27

CH2 twist

2 highlighted
bands are representative of
crystalline vibrations of the polystearate in a
commercial
hand lotion

Applications for Polymer Research Cosmetic Emulsions

At which temperature does my emulsion become unstable?
Approaching 50C
sample becomes
more amorphous
Non-polymer
components are
untouched by the
polymer transition
If stored or shipped
at elevated T,
lotion can not be
used anymore!
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Applications for Polymer Research Polyethylene Crystallization

Raman vibrational modes in polyethylene (PE)
Asymmetric
C-C Stretch

Symmetric
C-C Stretch

CH2 Twist

Semi-crystalline 25 C

CH2 Bend

Orthorhombic
crystalline peak
Strobl and Hagedorn (1978)

Melt 155 C

Tasumi et al, J Mol Spectrosc. (1962); RG Snyder. J Chem Phys. (1967)

29

Boerio and Koenig (1970)

Applications for Polymer Research Polyethylene Crystallization

Raman vibrational modes in polyethylene (PE)

I ' ( ) =

Invariant

I ( )

I 1296 cm

) + I (1303 cm )

Intensity (a.u.)

Crystallizing @ 130C, ~250

s

1296 cm-1

1000

1100

1200

1303 cm-1

1300

1416 cm-1

1400

1500

Raman Shift (cm-1)

+
Amorphous
am = I ' (1303 cm

Consecutive
Trans

ct = I ' (1296 cm

Crystalline

KB Migler, AP Kotula, AR Hight Walker. Macromolecules. (2015)

30

cr =

I ' 1416 cm1

Nc

Non-crystalline
consecutive
trans
(NCCT)

=
ncc
ct cr
t

Applications for Polymer Research Polyethylene Crystallization

Polyethylene Comparison at Room Temperature

Intensity (a.u.)

SRM
APE

1000

1100

1200

1300

1400

1500

Raman Shift (cm-1)

Mw
(kg/mol)

SRM 1475
(SRM)

53.1

2.9

Aldrich PE
(APE)

109.9

9.9

System

31

Sample

Amorphous

NCCT

Crystalline

SRM

0.01

0.26

0.73

APE

0.16

0.28

0.56

Applications for Polymer Research Polyethylene Crystallization

Comparison of melt rheology at 140C
1/rep
10 7

G'
G''

G'
G''

SRM
Modulus (Pa)

10

10 5

10

1.0

aT

Modulus (Pa)

10 6

0.8

APE

10 5
1.2
1.0

10 4
aT

10

10

10

140

160

180

10 1

10 2

Frequency aT (rad/s)

G'

0.4
0.2
120

200

T (C)

10 0

10

0.4
0.2
120

0.8
0.6

0.6

10

10 3

10 0

140

160

180

10 1

Frequency aT (rad/s)

Probing crystallization rheology at 132C and 2 rad/s near APE

crossover

32

200

T (C)

10 2

Applications for Polymer Research Polyethylene Crystallization

Simultaneous Rheology and Raman of SRM

Modulus (Pa)

107

= 2

Avrami exponent
indicates spherulite
growth confirmed
via direct imaging

Tc = 132 C

106

50 m

105
200

G'
G''

104

150

Mass Fraction

Time (s)

0.1
50

cr > 0.001
G'(t) > 1.3G'(0)

3.2
0.01

am
cr
ncct

0.001
10

Surface growth
33

100

100
Time (s)

1000
Spherulite growth

0
127

128

129

130

131

132

133

Temperature (C)

G increases with crystallinity!

Applications for Polymer Research Polyethylene Crystallization

Comparison between SRM and APE
Tc = 132 C

SRM

107

Modulus (Pa)

Modulus (Pa)

107

106

105

G'
G''

104

106

105

G'
G''

104
1

0.1

0.01

am

Mass Fraction

Mass Fraction

APE

0.1

0.01

am
cr

cr

ncct

ncct
0.001

0.001
10

34

100

1000

10

100

1000

Time (s)

Time (s)

G increases with crystallinty

G increases with NCCT

Applications for Polymer Research Polyethylene Crystallization

What is the reason for the difference?
- Effect of polydispersity?

Leading to segregation effect?

1.0
SRM
APE

dwf /d(log M)

0.8

0.6

0.4

0.2

0.0
2

Log M

APE contains more short (alkane) and long

chains.

Segregation in PE
above 121C
(Bank and Krimm, 1969)

Modulus can correlate with conformational changes not always crystallinity

35

Contents
Introduction and Motivation
Why combining Rheology with Raman?
Basics of Rheology
Basics of Raman Spectroscopy
The First Commercially Available Combination of a Rheometer
and a Raman Spectrometer
Applications for Polymer Research
Polymer Additives in Cosmetic Emulsions
Temperature Induced Crystallization in Polyethylenes
Summary

36

Summary
The combination of a Thermo Scientifc HAAKE MARS and a
Thermo Scientific DXR Raman Microscope is the first
commercially available system for probing for Rheology with insitu Raman spectroscopy and optical microscopy

The presented setup can correlate molecular conformation with

rheological data during phase transitions in cosmetic emulsions

The presented setup can correlate the modulus increase during PE

crystallization with either NCCT or crystallinity

37

Thank you for your attention!

Questions?

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