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
CC 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
CN 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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