Fourier Transform Infrared
Spectroscopy
Shimadzu (Asia Pacific) Pte Ltd
Singapore
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Infrared Spectroscopy
UV VIS NIR IR Far IR Microwave
10-5 10-5 10-4 10-3 10-2 10-1
Wavelength (cm)
Energy
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Qualitative Analysis by IR
IR spectrum
What molecular motions ?
What functional group ?
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Symmetric In-plane bending
stretching
Antisymmetric Out-of-plane
stretching bending
When the molecule is irradiated with electromagnetic radiation, the
vibrating bond will absorb energy if the frequencies of the light and
the vibration are identical.
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Ethyl chloride
3000 1100 650
Overtone
Stretching Bending Bending Wagging C-C stretching Rocking
Fingerprint region
• The complex region of the infrared
spectrum below 1500 cm-1.
• Functional group region
- The characteristic absorption band of
functional groups are almost unchange from
one compound to another.
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Regions of the infrared spectrum
Wavenumber (cm-1)
4000 2500 2000 1500 625
100
Transmittance (%)
N-H C=N C=O
Fingerprint region
O-H C=C C=N
C-H C=C
0
2.5 4 5 7 16
Wavelength (10-6m)
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Functional groups Band position (cm-1) Intensity
C - H (alkyl group) 2850 - 2960 Medium to strong
= C - H (alkene) 3020 - 3100 Medium
C= C 1650 - 1670 Medium
C-H 3300 Strong
CC 2100 - 2260 Medium
C - Cl 600 - 800 Strong
C - Br 500 - 600 Strong
C-I 500 Strong
O-H 3400 - 3640 Strong, broad
C-O 1050 - 1150 Strong
Aromatic ring 1600, 1500 Strong
N-H 3310 - 3500 Medium
C-N 1030,1230 Medium
C=O 1670 - 1780 Strong
O - H (Carboxylic acid) 2500 - 3100 Strong, very broad
CN 2210 - 2260 Medium
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Optional Accessories of Fourier
Transform Infra-red (FTIR)
• Diffuse reflectance spectroscopy (DRS)
• Attenuated total reflectanc (ATR)
• Specular reflectance method (SRM)
• Reflectance absorption spectroscopy (RAS)
• FTIR-microscopy
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Applications
of
diffuse reflectance measurement
(DRS)
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Diffuse reflectance measurement
- In powder samples measurement, the KBr
pellet method is often used. However, not
all materials are blendable with KBr, i.e.,
polymer.
- The DRS method is easy to perform.
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Diffuse reflectane measurement
Incident light
Specular
Diffuse
reflectant
reflectant light
light
• Specular reflectant light
• Diffuse reflectant light
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Diffuse reflectance measurement
• Preparation
- The DRS is almost applicable to all samples
that can be pulverized. It also permits using
any diluting substances (sulphur, ..) which
are not applicable to the KBr pellet method.
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DRS
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Analysis of additives in polymers by
preparative LC-FTIR
• Infrared spectroscopy is an excellent
techniques for qualitative analysis of pure
sample. In the case of mixtures, FTIR can
be combined with a separative technique
such as LC.
• It is rather difficult to carry out on-line LC-
FTIR analysis due to the IR absorption of
mobile phase.
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Preparative LC-FTIR
UV (254nm)
C
10 15 20 25 30 35
A
RI
B
10 15 20 25 30 35
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Preparative LC-FTIR
Isolated compound KBr
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Compound B = Sebacic acid
dialkyl ester
100
80
60
40
20
0
3000 2000 1500 1000 400
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Compound C= Phthalic acid
dialkyl ester
100
80
60
40
20
0
3000 2000 1500 1000 400
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Analysis of degraded GC packing material
due to residual oxygen using DRS
100 P Q R
A-B
80
60
40 B
20 A
0
4000 2000 1000 400
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Diffuse reflectance measurement
with
the SiC sampler
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SiC sampler
Holder to be directly fitted to
the DRS
Sample
SiC sandpaper disk
SiC sampler is effective in sampling sample from large
formings and plastic pellets.
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DRS of a polyethylene tank surface
before and after use.
100 100
80 80
60 60
40 40
20 20
Oxidation due to UV
0 0
4000 2000 1000 400 4000 2000 1000 400
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Applications of
Attenuated total reflectance
(ATR)
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Type of samples can be measured
by ATR
• Paper, cloth and yarns
• Coating films on metals or resins (more than
1x10-6m)
- In general the sample must have smooth and
flat surface. The refractive index of sample is
smaller than that of prism.
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ATR
Measurement
- The sample is held in contact with a prism
made of highly refractive material which
transmits infrared rays.
- The incident angle of IR beam is larger than
the critical angle hence the IR beam is
totally reflected by reflected by the
interface between sample and the prism.
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prism
IR rays
sample
prism
dp
sample
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Horizontal-type ATR
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Material Wavelength range (cm-1) Refractive index Solubility in water Characteristics
KRS-5 20000 - 290 2.4 Insoluble Orange, poisonous
Ge 5000 - 700 4 Insoluble Black, opaque, fragile
ZnSe 20000 - 650 2.4 Insoluble Yellow, hard
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Depth-profile study
60o
55o
50o
45o
40o
3000 1500 1000 400
A two-layer film measured with continuously variable ATR angle
The first layer is polypropylene (PP)
The second layer is polyethylene terephthalate (PET)
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ATR Correction
ATR spectrum
(without correction)
ATR correction
(with correction)
Transmission mode
3000 1500 1000 400
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ATR spectrum of PP film
100
50 prism
0 Detector Source
4000 2000 1500 1000 700
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Acrylonitrile- Incident angle = 45o
butadiene rubber
containing carbon KRS-5
black as a
Ge
reinforcement
3000 1500 400
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Applications of
Specular Reflectance Method
(SRM)
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Specular Reflectance Method
• Suitable for coating films on resins/metals
which film thickness is more than 1x10 -6m
• The sample must have a smooth and flat
surface.
- i.e., drink can, plastic slab
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Type A of SRM
Metal substrate
Thin film
Detector IR rays
- Measurement of a thin film on a metal plate, generally the
obtained spectrum is similar to the transmittance spectrum.
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PVC film on metal
3000 1500 800
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Type B of SRM
Thin film
Detector IR rays
- The only reflectance light is obtained, therefore the spetrum
has to be corrected by Kramers-Kronig transform.
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IR reflectance spectrum
of PVC film on resin
IR transmission-like
spectrum after
the K-K transform
3000 1500 1000 800
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Type C of SRM
Metal substrate
Thin film
Detector IR rays
- The spectrum contains both transmission and reflectance results
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SRM
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Application on black
fuorinated rubber
Before correction
- K-K transformation
After correction
4000 1500 1000 400
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PMMA plastic slab of
1 cm thickness Before correction
- K-K transformation
After correction
4000 2000 1500 1000 400
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Reflectance absorption
spectroscopy
• Coating films on metals (the thickness of
the film is thinner than 1x10-6m)
- Use of a grid polarizer is required to
enhance the sensitivity about twice.
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Principle of RAS
Incident light Reflected light
Incident light Reflected light
When a polarizable light falls on a metal phase change will occur
between the incident and reflected light
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RAS
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A 100 nm lead sterate
LB film
- Strong absorption
band can be obtained
Incident angle =70o
by using a polarizer to with polarizer
make use of the
horizontally light.
Incident angle =70o
Incident angle = 10o
2000 1500 500
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Reflectance absorption spectrum
Coating on drink can
3000 1500 400
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Applications of FTIR-microscope
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FTIR microscope
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Analysis of thermally oxidized PE
using FTIR-microscope
Sample preparation
- A PE pellet heated for 10 minnutes at 200 oC
and cut into a thickness of 80x10-6m by
microtome.
- The masking area was set at 20 x 100 sq
micrometer.
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Oxidation study of PE
C=O
C=O
O
R
micrometer
0
500
1000
3000 1500 700
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Laminated plastic sheet
thickness = 10 micrometer
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PE First layer
EVA Second layer
PE Third layer
PP Forth layer
4000 3000 1500 1000
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PVC
EVA
Second layer
3000 1500 1000
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