FTIR

Selvakumar Murugesan
Assistant Professor,
Department of Metallurgical and Materials Engineering,
National Institute of Technology Karnataka Surathkal,
 Infrared spectroscopy (IR)
• Basic fundamentals
• Instrumentation (Classical vs. Fourier
Transform)
• Sample preparation and various modes of
operation
• IR for rubbers and rubber-like materials –
rubbers, blends, rubber-filler interaction,
milling, adhesion, degradation, reverse
engineering, chemical modification
 Introduction
• A branch of science & engineering that deals with the
inter-play between structure, properties and processing
of materials

Properties
“Materials Science” “Materials Engineering”

Structure Processing

• Materials Science: investigates relationship between

materials’ structure & properties
• Materials Engineering: On the basis of materials science,
designing and/or engineering the materials’ structure to
produce desired properties
 Structure

• Electronic level (subatomic)

• Atomic (molecular level, chemical
composition)
• Crystal (arrangement of atoms or ions wrt one
another)
• Microstructure (can study with microscopes)
• Macrostructure (can see with naked eye)

Electronic & Crystal Micro Macro

atomic structure structure structure structure
~1Å ~ 10 Å 10-106 Å 106 Å (0.1 mm) & up
(x-ray diffraction) (electron & optical (magnifying glass
microscopes) or naked eye)
Properties

Response to External
Stimulation

➢Mechanical
➢Electrical
➢Magnetic
➢Optical
➢Thermal
➢Chemical
 Infrared is Rovibrational Spectroscopy

• Wavelengths between 0.8 µm to 1 mm.

• Associated with changes in nuclear motion (vibrations and rotations).
• In gas phase, rotational transitions are resolved; in liquid phase, they are
broadened. Usually only focus on vibrational character.
• Energy is usually reported in wavenumbers (cm-1); also proportional to
frequency 1
ν= ν = cν
λ
Near IR 0.8 - 2.5 µm 12800 - 4000
cm-1
most
commonly Mid-IR 2.5 - 50 µm 4000 - 200 cm-1
studied
Far IR 50 - 1000 µm 200 - 10 cm-1
Molecular vibrations – vibrational
spectroscopy

m1 m2 equilibrium

m1 m2

X1 X2

d2 x
F = ma = −kx a= 2
dt
d2 x d2 x k
m 2 = −kx ⇒ = − x
dt d t2 m
 Types of Vibrations
• molecular dipole moment must change during a vibration to be IR active.
• this oscillating dipole interacts with the oscillating E-M field of the photon,
leading to absorption.
Stretching Vibrations Bending Vibrations
+ – + +

–
symmetric anti-symmetric rocking scissoring twisting wagging
In-Plane Out-of-Plane
Changes in bond length Changes in bond angle
 Group -frequencies
• Referring to correlation charts and tables
for infrared data –ref ‘Infrared
Characteristic Group Frequencies’ by G.
Socrates
Four regions:
 Factors Influencing IR Absorption
Frequency
• Masses of attached atoms: As masses increase, wave-
number decreases.
C-H C-C C-O
3000 cm-1 1200 cm-1 1100 cm-1
C-Cl C-Br C-I
750 cm-1 600 cm-1 500 cm-1

• Strength of chemical bond: As bond strength increases,

wavenumber increases.
C=C C=C C-C
2150 cm-1 1650 cm-1 1200 cm-1
 Factors Influencing IR Absorption
Frequency

Hybridization: Bonds are stronger in the order sp >

sp2 > sp3.

C-H (sp) C-H (sp2) C-H (sp3)

3300 cm-1 3100 cm-1 2900 cm-1
 Infrared Spectroscopy: Dipole Moments
Dipole
O C O C moment
O O vector is
non-zero
Bending Vibration

O O O
H H H H H H
Symmetric Asymmetric Bending
Stretching Stretching
IR Active
 Group frequencies

3700 - 2500 cm-1: X-H stretching (X = C, N, O, S)

2300 - 2000 cm-1: C = X stretching (X = C or N)
1900 - 1500 cm-1: C = X stretching (X = C, N, O)
1300 - 800 cm-1: C - X stretching (X = C, N, O)

Individual groups in polymer act as

independent oscillator
 IR Correlation Diagram
Region I Region II
3600-2700 cm-1 1800-1600 cm-1

100
O-H N-H C-H C=O
bond stretching
Abs or Trans (%)

80 Fingerprint
alcohols acid chlorides Region
60 phenols anhydrides (below 1500 cm-1)
carboxylic esters
acids ketones
40 aldehydes
amines carboxylic acids
amides amides
20
alkynes ≡C-H
alkenes =C-H
Frequency 0 alkanes -C-H
(cm-1)
4000 3500 3000 2500 2000 1500 1000
2.5 3.0 4.0 5.0 6.0 10.0
Wavelength
(µm)
 Instrumentation
• Sources: based on blackbody radiator and using the
Wien displacement law:
λmax =3000 /T (K)
• W filament lamp for Near-IR
• Nernst glower about 1500 C is fused mixture of Zr, Y, and
Th oxides. Good for Mid-IR.
• Globar is rod of SiC about 1300 C. Also good for Mid-IR.
• High pressure Hg arc lamp for Far-IR.
• Tuneable dye lasers can be used for non-dispersive work
where an intense source is needed to monitor one
wavelength.
 More instrumentation
• Dispersing element:
– Prism, filter, or monochromator (dispersive)
• Detectors
– Photoconductive cells
– Thermister, pyroelectric, semiconductor (Ge
and InGaAs), Golay, DTGS (deuteriated
triglycine sulphate)

➔Photoconductive detectors have higher sensitivity and are based

on the photoconductive properties of mercury cadmium telluride
(MCT). Operate at liquid nitrogen temperatures. Increases the
signal/noise.
Light Sources
Detectors
 Instrumentation Dispersive
Detector
Sample

Source Dispersing

Computer
Instrumentation FT-IR (non-dispersive)

Detector
Sample

Interferometer
Source

Computer
 Infrared
detector

Sliding
Beamsplitter mirror

Source

Fixed mirror

Michelson interferometer. A beamsplitter transmits half of the source radiation to the fixed mirror
and the other half to the sliding mirror. A phase difference between the beams can be induced by
sliding the mirror causing detection of the two beams at different times. The detector provides the
interferogram, a plot of energy as a function of differences in optical paths. Beams have been
slightly shifted in the drawing to allow easy following of their path.
 Advantages of FT-IR
• 1. Speed of analysis
• 2. Small samples can be analyzed i.e. use
a microscope
• 3. Signal to noise is 100,000 : 1.
• 4. Data manipulation
• 5. Fewer Optical Element: No Slit/
attenuator–- More power, greater signal to
noise ratio
 Infrared Spectroscopy
Incoming IR signal Measured reflection (or
(reference) transmission)
Focussed onto
sample

Resultant absorbance
spectra (or
transmission)
 S/N is very important

0.955

0.9
0.95

0.8
0.945

0.7 0.94
Transmittance

Transmittance
0.6 0.935

0.93
0.5

0.925
0.4

0.92

0.3
0.915

0.2
0.91

TUMIX.SPC TUMIX.SPC
0.1 0.905

4000 3750 3500 3250 3000 2750 2500 2250 2000 1750 1500 1250 1000 750 500 4000 3950 3900 3850 3800 3750 3700 3650 3600 3550 3500 3450 3400 3350 3300 3250
Wavenumbers Wavenumbers

Resolution ?
Baseline and baseline shift ? Curve Fitting
 Various modes / sample preparation
1. Transmission – form of thin film For
liquid
2. Reflectance – reflective surface
3. Scattering – diffuse reflectance infrared
spectroscopy (DRIFT) by Fourier transform
4. Attenuated total reflectance (ATR)

For gas

ATR
DRIFT using ellipsoid or paraboloid mirror
On-line control – with liquid samples

To FTIR Detector
 Advantages of IR
• A universal technique i.e., solids, liquids, gases,
semi-solids, powders, and polymers can be
routinely analyzed.
• IR spectra are information rich; peak positions,
intensities, widths, and shapes in a spectrum all
give useful information about the analyte.
• IR is relatively fast and easy technique. Most
samples can be prepared and scanned in less
than five minutes.
• IR is very sensitive. Micro to nano gram
quantities can routinely be detected.
 Disadvantages of IR
• Homonuclear compounds don’t absorb.
• Aqueous solutions difficult to analyze because the strong
absorbance of water.
• Some compounds give broad bands that interfere with
other compounds.
• Complex mixtures difficult to separate
• Dark (black) compounds often absorb the IR beam
completely, i.e., 0% transmittance.
• Homologous series cannot be separated – no information
about the molecular size
 Instrument Vendors
• SensIR (microscope, ATR)
• Bruker
• Schmazhu
• Agilent
• Perkin Elmer
• Digilab
• Nicolet
• BioRad
• Buck Scientific (inexpensive)
Machine, make of, model no., mode and resolution
Interpretation
Interpretation
Interpretation
Interpretation
Interpretation
Interpretation
1019 – Si-O
1234 Si-CH3
800 Si-C
865 –
CH=CH2
 Polymer blends
Maleated EPDM – compatibility is improved with polychloroprene -1738
cm-1 is used
>C=O…..Cl-C
Vinyl trimethoxy silane - peak at 1090 cm-1 Si-O-Si

Self-crosslinking blends

ENR and X-NBR, ENR – chlorinated polymers, CSM-X-NBR

Rubber-filler interaction
C-black shows bands at 3200-3400, 1740, 1600, 1275-1195
corresponding to hydroxyl, carboxyl, lactone, quinone, ether phenol etc
CSM-C-black 1161 and 1366 of –SO2Cl diminished
Silica –NBR with ppt. silica. Even with silica-NR peak broadening and
shifting is observed – coupling agent
Surface oxidation