IR-Spectroscopy in Polymer Science

IR-spectroscopy is probably the oldest of the spectroscopic methods

used in polymer science. It is basing of the analysis of molecular
vibrations. It can be subdivided into near-infrared (NIR), medium-infrared
(MIR), and Raman-spectroscopy.
Raman

4000 cm-150 cm-1

fundamental vibrations

NIR

MIR

4000 cm-1400 cm-1

fundamental vibrations

scattering

absorption

monochromatic excitation source

12500 cm-14000 cm-1

overtones & combinations
absorption

dispersed polychromatic radiation

information from scattered radiation

information from absorbed radiation

homonuclear functionalities
changes inpolarizability

polar functionalities
changes in dipol moment

CH/OH/NH
functionalities

high structural selectivity

high structural selectivity

low structural selectivity

I raman~ c
no sample preparation
required
sample volume L
sample thickness m
light-fiber optics
>100 m

Lambert-Beer-Law
sample preparation
required (except ATIR)
sample volume L
sample thickness m
limited

Lambert-Beer-Law
no sample preparation
required
sample thickness up to cm-range
light-fibre optics
>100 m

A multitude of techniques are available such as microscopic

techniques, measurements in reflection, at high temperatures and low
temperatures, solid, liquid (and gaseous) samples, on large and on microsamples. Even only a few scattered photons can be determined with highend CCD-detectors.

In particular in polymer science it is the translational periodicy of the

macromolecules which creates collective motions and phonons which are
detectable by Raman spectroscopy. The stereochemical, conformational
structure, and symmetry properties give rise for characteristic and specific
bands. Starting from only a few basic concepts a real treasure of chemical
and physical information can be drawn from IR-spectroscopy, see for
example Lin and Brown1, who have demonstrated the determination of
fifteen properties of water by NIR.
The simplest application is just the identification of a material, in
particular under the scope of this short course, the identification of
polymer classes. There is a simple flow chart that can give a crude
overview:
1790-1720

very strong

no

yes
1610-1590,
1600-1580 and
1510-1490

All numbers have the meaning of wave numbers

and are given in cm-1

1610 1590,
1600 1580 and
1510 - 1490

3500 - 3200

840 - 820

strong

1450 - 1410

sharp

3500 - 3200

Alkyd-,
Polyesters,
Cellulose=
ether,
PVC
(plasticized)

Polyvinyl=
acetate,
PVC-copo=
lymers

Cellulose=
ester
Polyure=
thane

Acrylics,
Polyester

strong

1450 -1410

sharp

1550 - 1530

1100 - 1000

Modif.
Epoxies
Polycarbo=
nates

1680 - 1630

Phenol
derivatives,
Epoxies

Polystyrenes,
Arylsilicones,
Aryl-alkyl=
Silicone Co=
polymers

Polyamides, Nitrocellulose
amines
cellophan

Cellophan,
Alkylcellulose,
PVA, PEO

PAN, PVC,
Polyvinyliden
chlorid,
POM

Alkylsilicone,
aliphatic hy=
drocarbons,
Polytetra=
Fluorethylene,
Thiokol

In the following there are some examples:

1790-1720 cm-1
3500-3200 cm-1
1680-1630 cm-1
1550-1530 cm-1
epoxies, polycarbonate, alkyd resins, polyesters,
1610-1590
cellulose-ether, PVC
poly(vinyl acetate), PVC-copoly., cellulose ester, PU
1600-1580 cm-1
acryl polymers
1510-1490
Phenol resins, epoxies, aryl polymers

Polyamid

1610-1590
1600-1580 cm-1
1510-1490

820-840 cm-1

1790-1720 cm-1
modified epoxides, polycarbonate, Alkyd resins, polyester, cellulose ester, cellulose ether, PVC (plast),
PVAc, PVC-copolym., PU, acrylics
modified epoxides, polycarbonate, Alkyd resins, polyester, cellulose ester, cellulose ether, PVC (plast)
Modified epoxies, polycarbonate

polycarbonate

?
typical pattern of PU

polycarbonate

typical pattern of normal PC

? cellulose ester or polyurethane ? 1610-1590

1600-1580 cm-1
1510-1490

C-O-C-ether region
1100-1000 cm-1
1450-1410 cm-1

Poly (ether urethane)

A large amount of spectra of common polymers, special polymers,

additives etc. can be found in literature, see bibliography.
If the thickness of a film or the distance of the windows in a cuvette
is in the appropriate range it can be measured by the interference pattern
that occurs if the surfaces are parallel and smooth. The light reflected
between the parallel surfaces of a film causes "fringes" in the spectrum
which are frequently undesired. They can be removed by roughening the
surface.

Intensity, arbitrary units

wave length
1/d= 2/n (1/

n = number of minima between two maxima and

Polarization Fourier transform spectroscopy 2 and 2D-spectroscopy3

have opened the field of determination of
segmental motions and
orientation under the influence of external force fields.

Samples are exposed to external pertubations such as:

temperature
pressure
stress
Resolution (the large number of) overlapping NIR bands can be enhanced
and MIR and NIR correlation spectra are very useful for peak assignement

general pertubation
mechanical, electric, electro-magnetic, chemical,

Electro-magnetic probe
IR
X-ray, UV-vis, NMR,

NIR-spectroscopy has recently become an important application of

IR-spectroscopy because it can be used in combination with light-fibre
optics in on-line probe accessories and high-temperature applications.
Besides other applications NIR has been successfully applied to the
diffusion of small molecules in a polymeric matrix and rheo-optical
vibrational spectroscopy to determine transient structural changes during
deformation, information which can hardly be obtained from other
techniques4.

Bibliography

Hummel D, Scholl (1968...) Atlas of Polymer Spectroscopy, Wiley-VCh

Kamowo S, Siesler H W, Ozaki Y, Kawata S (2001) NIR-Spectroscopy:
Principles, Instrumentation, Application Wiley-VCh, Weinheim
Zerbi G (ed) (1999) Modern Polymer Spectroscopy, Wiley-VCh,
Weinheim

References

Lin J, Brown C W (1993) Appl Spectrosc 47, 1720

Siesler H W, Zebger I, Kulinna C, Okretic S, Shilov S, Hoffmann U (1998) in
Zerbi G (ed) Modern Polymer Spectroscopy, Wiley-VCh, Weinheim
3
Noda I, Downrey A E, Marcott C (1998) in Zerbi G (ed) Modern Polymer
Spectroscopy, Wiley-VCh, Weinheim
4
Siesler H W (1998) in Zerbi G (ed) Modern Polymer Spectroscopy, Wiley-VCh,
Weinheim
2