Polymer analysis

& Characterization

6/7/2021 1
 Characterization
• For the characterization of a low-molecular-
weight compound, it is sufficient to specify a few
physical or chemical properties, for example,
• boiling point, melting point, angle of optical
rotation, refractive index, elemental analysis, IR
and NMR spectra.
• If two low-molecular-weight samples have the
same characteristic properties, they may be
considered as identical.
6/7/2021 2
 Polymer characterization
• The characterization of macromolecular substances is considerably more
difficult.
1. Owing to the high intermolecular forces, macromolecules are not
volatile without decomposition so, no boiling point can be determined.
2. The melting points of partially crystalline polymers are generally not
sharp.
3. Amorphous polymers frequently show only sintering or softening,
often accompanied by decomposition.
4. In addition to elemental analysis, other data must be determined, for
example,
• solubility,
• viscosity of the solution
• mean molecular weight,
• molecular weight distribution and degree of crystallinity.

6/7/2021 3
• The fundamental difficulty is that polymeric substances
cannot be obtained in a structurally and molecularly
uniform state, unlike low-molecular-weight
compounds.
• Because of polydispersity, the term ‘identical’ can not
be used for the polymers.

• Characterization methods suitable for low-molecular-

weight compounds are frequently not applicable or
only applicable in a substantially modified form; often
completely new methods of investigation must be
employed.

6/7/2021 4
 Polymer Characterization
• Chemical Characterization
• Thermal Characterization
• Mechanical Characterization
• Morphological Characterization
• Electrical Characterization

6/7/2021 5
6/7/2021 6
6/7/2021 7
6/7/2021 8
6/7/2021 9
 Chemical Characterization
• FTIR
• NMR
• GC
• GC/MS
• HPLC
• GPC
• Elemental Combustion Analyser
• Wet Analysis

6/7/2021 10
 Thermal Analysis
• Differential Scanning Calorimetry
• Dynamic Mechanical Analysis
• Thermomechanical Analysis
• Thermogravimetric Analysis
• Differential Thermal Analysis
• Dilatometry
• Optical Dilatometry
• Dielectric Thermal Analysis
• ViCat Softening
6/7/2021 11
 Mechanical Analysis
• Universal Testing Machine/ Tensometer
• Dynamic Mechanical Analysis (DMA)
• Izod Charpy Testing
• Impact Testing
• Hardness Testing
• Fatigue Testing
• Stress Relaxation
• Creep

6/7/2021 12
 Morphological Characterization
• Optical Microscopy
• Scanning Electron Microscopy
• Field Emission Gun Scanning Electron
Microscopy
• Atomic Force Microscopy
• Transmission Electron Microscopy
• X-Ray Diffraction

6/7/2021 13
 Electrical Testing
• Resistivity
• Conductivity
• Dielectric constants
• Impedance

6/7/2021 14
 Spectroscopy
the study of interaction of light with matter

• IR spectroscopy has been one of the most widely

used material analysis technique for over 70
years.
• It represents a fingerprint of sample with
absorption peaks that corresponds to the
frequencies of vibration between the bonds of
the atoms.
• No two compounds produce the same result
because each material is a combination of atoms
6/7/2021 15
 Fourier transform infra-red
spectroscopy (FTIR)

6/7/2021 16
 FT-IR
• It overcomes the limitations offered by the
traditional spectroscopy.
• Traditional spectroscopy used to measure
each frequency individually, making it a very
slow process
• FT-IR is fast, precise and simple
• IR radiation is passed through the sample,
some of the radiation is passed, some is
absorbed by the sample
6/7/2021 17
 IR range
• Electromagnetic radiation having wavelengths
from approx.  = 760 nm near visible light)
down to  = 1 mm where the microwaves
begin, is usually called infrared (IR) light

6/7/2021 18
 Infrared region

6/7/2021 19
• Infrared waves have wavelengths longer than visible and shorter than
microwaves and have frequencies which are lower than visible and higher
than microwaves.
• The Infrared region is divided into: near, mid and far-infrared.
– Near-infrared refers to the part of the infrared spectrum that is closest
to visible light and far-infrared refers to the part that is closer to the
microwave region.
– Mid-infrared is the region between these two.
• The primary source of infrared radiation is thermal radiation. (heat)
• It is the radiation produced by the motion of atoms and molecules in an
object. The higher the temperature, the more the atoms and molecules
move and the more infrared radiation they produce.

6/7/2021 20
 IR spectroscopy
• These energies are insufficient to induce
electronic transitions but are able to excite
vibration motions of molecules and therefore
IR spectroscopy is a well established method
as a vibrational spectroscopy.

6/7/2021 21
 Molecular vibrations
• Stretching
– Change in inter-atomic distance along bond axis

• Bending
– Change in angle between two bonds. There are four
types of bend
• Rocking
• Scissoring
• Wagging
• Twisting

6/7/2021 22
 Stretching

Symmetric Stretch Antisymmetric Stretch

6/7/2021 23
 Bending

Bend

6/7/2021 24
 Molecular vibration

6/7/2021 25
 6/7/2021

• A source - which provides the

electromagnetic energy
required for the analysis

• A signal sorter (a dispersion or

interference device for
resolving the frequencies from
Instrumentation each other).
/ Hardware
• A sample compartment

• A signal detector

• A computer (for data

acquisition and analysis).

26
 Instrumentation / Hardware
Older Generation Instrument- A Dispersive IR Spectrometer

Takes  10 – 20
minutes to scan entire
range

• Scanning instrument uses a frequency separation device (grating)

to resolve the IR radiation into individual frequencies.
• An exit slit isolates a specific frequency for passage to the sample

6/7/2021 27
Modern IR Spectrometer – Optical Design

Light He-Ne gas laser

source

Beam splitter Interferogram

Movable mirror

Sample chamber

Fixed mirror
Detector
Interferometer
6/7/2021 28
 There are
two steps
in the The first step is to
analysis
of
identify the specific type
polymers of polymer in a given
sample. This may be
complicated in a
Identification formulated sample by
of polymer the presence of
additives. IR
spectroscopy will usually
provide information on
both

6/7/2021 29
2. The second step, if possible, is to determine
details of the chemical and physical
characteristics, which define the quality and
properties of the polymer.

6/7/2021 30
• IR spectroscopy is an important technique in
polymer characterization.
• The intensity of interaction between IR radiation
and a molecule depends on the
✓ molecule's structure,
✓ on the symmetry of the molecule's skeleton,
✓ and on its electron distribution.
• This is because a vibration transition of a
molecule is IR active only if the dipole moment
changes during the excited vibration motion.
6/7/2021 31
 IR Spectroscopy is used for
qualitative identification of organic
and inorganic compounds.
IR Spectroscopy is used for checking
presence of functional groups in
organic compounds.
Wavenumber with units of cm-1 is
commonly used

Wavenumber = number of waves of

radiation per centimeter

6/7/2021 32
• It allows the analysis of soluble polymers but also of insoluble
(crosslinked) materials.
• It is sensitive towards structural features like
1. functional groups (carbonyl, aromatics,...),
2. chain constitution (1,2- vs. 1,4- and cis-trans isomerism in polymeric
dienes,
3. head-to-tail vs. head-head-tail-tail placements in vinyl polymers or
branches in polymers like polyethylene, for example),
4. end groups and copolymer composition (in PE/PP copolymers, for
example).
• Moreover, it is very useful in determining the components and
compositions of blended, filled, or modified polymer compounds and
composites and, in some special cases to determine the crystallinity of
a solid polymer sample.

6/7/2021 33
6/7/2021 34
 What is an infrared spectrum?

• A plot of measured infrared light intensity

versus a property of light is called an infrared
spectrum

6/7/2021 35
• Note in Figure shown previously, that 4000
cm−1 is to the left and 500 cm−1 is to the
right, and that the spectrum is plotted in
Absorbance units, which measure the amount
of light absorbed by a sample.
• The absorbance spectrum of a sample is
calculated from the following equation:

6/7/2021 36
 How to calculate absorbance
• Absorbance is also related to the concentration of
molecules in a sample via an equation called
Beer’s Law.

• The height or area of a peak in an absorbance

spectrum is proportional to concentration, which
is why Beer’s Law can be used to determine the
concentrations of molecules in samples.
6/7/2021 37
 Beer lambert’s law

6/7/2021 38
• The y-axis of an infrared spectrum can also be
plotted in units called percent transmittance
(%T), which measures the percentage of light
transmitted by a sample.
• %T spectra are calculated as follows:

6/7/2021 39
 40

Mathematically related and can be

easily converted.
Difference
between The size of spectra in absorbance-
absorbance based graph is linearly proportional
to concentration. So, good for
and quantitative analysis
transmittance
But, not in the case of transmittance.
Can be used for qualitative analysis

6/7/2021
6/7/2021 41
6/7/2021 42
 How to record an FT-IR spectrum
• FT-IR spectroscopy is experimentally much
simpler as compared to other methods of
vibrational spectroscopy.

6/7/2021 43
 Preparation of sample
• In order to record an IR spectrum, in most cases the
polymer is brought onto discs of KBr either as a thin solid
film (made from polymer solution in a volatile solvent or -
for low-Tg polymers - from the melt; film thicknesses are
typically 30 to 300 microns) or as a fine and homogeneous
suspension in, for example, paraffin oil.
• Alternatively, solid polymers can be milled together with a
large excess of KBr, and the resulting powder can be
compressed to a (homogeneous, transparent) disc.
• Then, IR radiation is transmitted through the sample, and
the absorbance (extinction) is measured as a function of
the wavelength X or of the wave number v using a detector
placed at the opposite site of the sample.

6/7/2021 44
 Transmission Mode
Preparing a KBr Disk for solid samples

1 2 3

5
4

45
 Size of sample is crucial
• FTIRs are very sensitive, it takes only a
milligram of a sample to obtain a good
spectrum.

6/7/2021 46
6/7/2021 47
6/7/2021 48
6/7/2021 49
 Constructive interference

6/7/2021 50
 Destructive interference

6/7/2021 51
6/7/2021 52
6/7/2021 53
 Fourier Transform of an Interferogram yields a Spectrum
Relative Intensity

Optical Path Difference Wavenumbers cm-1

6/7/2021 54
 Measuring a typical IR Spectra

% T = 100 x I/I0

6/7/2021 55
 IR Absorption in 2-Hexanone

6/7/2021 56
IR Absorption & Bond Vibration in 2 - Hexanone

The vibrations of a 2-hexanone molecule are not, of course,

limited to the simple stretching of the carbonyl bond. The
various carbon-carbon bonds also stretch and bend, as do
the carbon-hydrogen bonds.
6/7/2021 57
 IR Spectra of 2 - Hexanone

Functional Group Region

6/7/2021 58
6/7/2021 59
 Sampling Methods
Available with our instrument

• Transmission
• ATR

6/7/2021 60
 Infrared Sampling Methods

detector source

Internal Reflection
Transmission
Attenuated Total Reflection (ATR)

61
 sample
sample
•
radiation
• radiation

Transmission Mode Reflection Mode

62
 Transmission Method
• Thin Films

• Solids (pellet Technique)

6/7/2021 63
 Sample criteria
for Transmission Method
For Analyzing Thin Films:
• Film should be in the free-standing condition
and thickness should be ≤ 50μm.
For Analyzing Solids by Pellet Technique:
• In this technique, a small amount of finely
ground solid sample is mixed with 100 times
its weight of potassium bromide and
compressed into a thin transparent pellet
using a hydraulic press.
6/7/2021 64
 ATR Sampling Method

• The infrared radiation interacts with the sample through a

series of standing waves called evanescent waves.
• An evanescent wave is produced each time the infrared beam
is reflected from the inside surface of the crystal
• The evanescent waves penetrate the sample at each
reflection point.
6/7/2021 65
Transmission Mode
Preparing a “Neat” IR liquid Sample

66
Transmission Mode

67
Transmission Mode

68
Transmission Mode

69
Transmission Mode

70
 How ATR method works ?
• IR beam is directed into a crystal of relatively higher
refractive index (mostly  2).

• IR beam reflects from the internal surface of the crystal

and creates an evanescent wave which projects
orthogonally into the sample in an intimate contact with
the ATR crystal.

• Some of the energy of evanescent wave is absorbed by

the sample and reflected radiation is returned to the
detector.

6/7/2021 71
 Sample criteria for ATR Method
We can analyze following type of samples
• Soft polymers
• Rubbers
• Soft powders
• Pastes
• Gels
• Surface coatings
• Aqueous liquids

6/7/2021 72
 Sample criteria for ATR Method
We can Not analyze following type of samples
• Hard polymers
• Fibers
• Powders
• Films on Metals
• Brittle / Grindable solids
• Acidic liquids
• Caustic liquids

6/7/2021 73
FT-ATR (Attenuated Total Reflection)

 Solves problem of achieving high resolution of solid

samples with little or no sample preparation
 Sample – wide variety of types
▫ Solids of limited solubility
▫ Films
▫ Threads
▫ Pastes
▫ Adhesives
▫ Powders

6/7/2021 74
 FT-ATR
• IR beam is directed onto
an optically dense crystal
with a high refractive index
at a certain angle.

• Internal reflectance creates

an evanescent wave.

• Wave protrudes only a few

microns (0.5 μ - 5 μ < )
beyond the crystal surface
and into the sample.

6/7/2021 75
6/7/2021 76
 FTIR of alkanes
• C-H stretch occurs at 3000 – 2840 cm-1
• CH2 bending modes at 1465 cm-1
• CH3 bending absorption at 1375 cm-1
• CH2 (four or more CH2 groups) rocking at
720cm-1 .
• cm-1

6/7/2021 77
• C-H stretch occurs in region of 3095 – 3010
cm-1
• C=C stretch occurs in region of 1670 – 1640
cm-1

6/7/2021 78
 FTIR of C=C double bonds
• It is well known that the out-of-plane CH
bending vibration frequencies of olefins, and
in particular ethylene derivatives, are
indicative of the double-bond configuration of
the olefin species.

6/7/2021 79
6/7/2021 80
6/7/2021 81
6/7/2021 82
6/7/2021 83
6/7/2021 84
6/7/2021 85
6/7/2021 86
 What is DBE?

• DBE=double bond equivalent. It is also called

degree of unsaturation. From the structure of the
chemicals, each pi bond or ring will generate one
DBE.
• For example:
i. Ethylene, C2H6, is a saturated acyclic alkane and
it does not have any pi bond or ring, so DBE=0.
ii. Propylene, C3H6, contains a pi bond, so DBE=1.
iii. Cyclohexane, C6H12, contains a ring, so DBE=1.

6/7/2021 87
6/7/2021 88
6/7/2021 89
 How to Read / Interpret an IR Spectra ??

1. Which is the material

under test ?
2. What Functional Groups (identifying unknown
are Present in the material)
material under test ?

Functional Group Region Fingerprint Region

6/7/2021 90
 What do we mean by Functional Groups ??
• A functional group is a group of atoms with specific physical
& chemical properties. It is reactive part of the molecule.
• Most organic compounds have C – C and C – H bonds.
• However many organic compound possess other structural
features such as;
❑ Contains heteroatoms (atoms other than C / H)
❑ Contains  bonds
These specific structural features are responsible for chemical
reactivity of a molecule ; hence these structures are known as
‘functional groups’.
6/7/2021 91
 How functional groups make the molecule reactive ?

Ethane contains only C- C and C-H bonds; hence it has no heteroatoms

/  bonds and so no reactive sites – Non Reactive Nature

Ethanol contains –OH molecule attached. It contains heteroatoms

which has two lone pairs of electrons which make it Reactive in nature.

6/7/2021 92
 How to identify unknown material ??
The region to the right-hand side of the diagram (from about 1500 to 500 cm-1)
usually contains a very complicated series of absorptions. These are mainly due
to all manner of stretching & bending vibrations within the molecule. This is
called the fingerprint region.

It is much more difficult to pick out individual bonds in this region than it is in
the "cleaner" region at higher wavenumbers. The importance of the fingerprint
region is that each different compound produces a different pattern of peaks in
this part of the spectrum.

Fingerprint Region
How fingerprint region is important in identifying unknowns ?
6/7/2021 95
 How to know what kind of functional groups are
present in material under test ??
Functional group region is divided in to 5 zones for better understanding

• Alcohols ( -- OH group)
Zone - 1
• Alkynes ( C – H)
• N-H Stretching (N – H)
3200 – 3700 cm -1

Functional Group Region

6/7/2021 96
 Zone 1

6/7/2021 97
6/7/2021 98
6/7/2021 99
6/7/2021 100
6/7/2021 101
 How to know what kind of functional groups are
present in material under test ??

• Aldehydes ( -- CHO)
• Carboxylic acids (-- COOH)
Zone - 2

2700 – 3200 cm -1

Functional Group Region

6/7/2021 102
 Zone 2

6/7/2021 103
6/7/2021 104
6/7/2021 105
6/7/2021 106
6/7/2021 107
 How to know what kind of functional groups are
present in material under test ??

• Alkynes ( C C)
• Nitriles(C N)
Zone - 3

2000 – 2300 cm -1

Functional Group Region

6/7/2021 108
6/7/2021 109
6/7/2021 110
6/7/2021 111
How to know what kind of functional groups are
present in material under test ??

Zone - 4

• Carbonyls (--C=O)

1650 – 1800 cm -1

Functional Group Region

6/7/2021 113
6/7/2021 114
6/7/2021 115
6/7/2021 116
6/7/2021 117
6/7/2021 118
How to know what kind of functional groups are
present in material under test ??

• Alkenes ( C=C) Zone - 5

1680 – 1620 cm -1

Functional Group Region

6/7/2021 120
6/7/2021 121
6/7/2021 122
6/7/2021 123
6/7/2021 124
 Case study of PE

6/7/2021 125
 Characterization of PE
• If we consider the total macromolecule as a single
linear chain, we are theoretically dealing with a
long chain of methylene groups, -(CH2)n- , with
two terminating groups (usually a methyl group).
• The main stretching vibrations appear in IR
spectrum at 2927 cm-1 (asymmetric CH2 stretch)
and 2852 cm-1 (symmetric CH2 stretch). The CH
stretching vibrations in the Raman spectrum of the
reference sample appear at 2920 and 2882 cm-1
(asymmetric), and at 2848 cm-1 (symmetric).

6/7/2021 126
• The occurrence of ‘‘impurities’’ and structural deviations,
such as branching and double-bond formation, depend on
the method of polymerization.
• The degree of branching is related to the crystallinity and
consequently influences the density of the polyethylene.
The more branching the PE has, the more amorphous (i.e.,
the lower the density) and the more transparent the PE
becomes.
• Three types of polyethylene are differentiated: low-
density polyethylene (LDPE), linear low-density
polyethylene (LLDPE), and high-density
polyethylene(HDPE).

6/7/2021 127
6/7/2021 128
• The main difference between spectra of LDPE and
HDPE lies at 1380cm-1.
• In the case of LDPE, the band in the region 1400–1330
cm-1 consists of three peaks, while that of the HDPE
consists of two peaks.
• A peak at 1377 cm-1 is assigned to the CH3 groups
terminating the short- and long-chain branching, and
the main polyethylene chain. If no individual peak is
observed at 1377 cm-1, then the material is a HDPE.
LDPE and LLDPE both produce this peak, although the
intensity is generally higher for LDPE than for LLDPE.

6/7/2021 129
 To differentiate LDPE and LLDPE
• The next step is to differentiate LDPE from LLDPE.
• In order to do this, it is necessary to examine the
peaks in the region from 990 to 890 cm-1 to
determine the presence and nature of residual
unsaturation. A pair of the absorbance at 990 and
910 cm-1 (the 910 cm-1 peak is approximately
four times more intense than the 990 cm-1 peak)
are assigned to a terminal vinyl group; CH3-
(CH2)n-CH=CH2

6/7/2021 130
• In the case of LLDPE, the intensities of the
vinylidene and the terminal vinyl group (910
cm-1) are almost identical, and both are weak
as indicated in Fig. 10a.
• As noted in Fig. 10b, the vinylidene group is
the most prominent group in the case of LDPE

6/7/2021 131
6/7/2021 132
 Assigned task
• To study
Different forms of HDPE and LLDPE

6/7/2021 133
6/7/2021 134
 Symmetric and asymmetric stretch

6/7/2021 135
 Sensitivity of FTIR results on its
sampling

6/7/2021 136
6/7/2021 137
 Applications in Polymer Materials
1. Qualitative analysis
✓Positions of characteristic peaks = type of
functional groups present
✓Peak shapes = symmetry, isomer, and
association

6/7/2021 138
1. A functional group exhibits more than one vibrational mode
corresponding to more than one characteristic peak. Hence,
a functional group cannot be determined by only one
characteristic peak.
2. Peak position depends not only on the functional group
itself but also on its chemical environment.

6/7/2021 139
 Yes–No method
• Is used for qualitative analysis

6/7/2021 140
 Some basic info regarding qualitative
analysis
1. The strongest absorption peaks of carbonyl-containing polymers,
such as polyesters, polycarboxylic acids, and polyamide, are
observed in the 1800–1650 cm−1 range, corresponding to the
stretching vibration of C=O groups.
2. The strongest absorption peaks of saturated polyolefins and
polyolefins substituted by polar functional groups are observed in
the 1500–1300 cm−1 range, corresponding to the bending
vibration of the C–H group.
3. The strongest absorption peaks of polymers containing
substituted benzene, unsaturated double bonds, and halogen
atoms are observed in the 1000– 600 cm−1 range.
4. The strongest absorption peaks of polyethers, polysulfones, and
polyalcohols are observed in the 1300–1000 cm−1 range,
corresponding to the stretching vibrations of C–O.

6/7/2021 141
6/7/2021 142
 Quantitative Analysis
• It’s a relative method. Absorbance, sample thickness and molar
absorption coefficient must be known to do this calculation.
• Peak intensity (generally represented as absorbance) is typically
utilized for quantitative analysis.
• Quantitative analysis is conducted as follows.
1. Choose the characteristic peak for quantitative analysis.
2. Determine absorbance
3. Select an appropriate quantitative method.

6/7/2021 143
• Peak absorbance is related to its concentration & thickness.
Also to its molar absorption coefficient.
• characteristic peak must correspond to the peaks that
respond sensitively to the concentration change.
• It should be distant from other peaks to avoid interference
• Its intensity should not be very strong or very weak.
• If more than two peaks are chosen, it is better to choose
peaks with comparable intensities to decrease the error.
• Peak absorbance can be expressed by peak height or peak
area

6/7/2021 144
6/7/2021 145
• ε is affected by the chemical structure and
environment; hence, it is typically unknown
and must be determined by standard samples
with known concentrations.
• With standard samples, a calibration curve can
be determined to calculate the unknown
sample concentration.

6/7/2021 146
• For obtaining a calibration curve, a series of standard samples
with known concentrations are required, and then their
absorbance values are determined.
• Calibration curve of A versus c is plotted, and the unknown
sample concentration can be easily calculated.
• If it is a linear curve, the slope is ε, which is a constant.
Otherwise, the curve is nonlinear, and ε is not a constant.

6/7/2021 147