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PIKE Technologies · 6125 Cottonwood Drive · Madison, WI 53719
Phone: (608) 274-2721 · info@piketech.com · www.piketech.com
Analysis of Polymers by ATR/FT-IR
Spectroscopy
Polymer materials have become widely utilized for many
different applications ranging from food packaging and
consumer products to use in medical devices and in aerospace
technologies. The composition of polymer materials may be
readily determined by measuring their infrared spectra using
a Fourier transform infrared (FT-IR) spectrometer and then
comparing the results with a commercially available or
specifically prepared spectral database.1 This application note
describes the benefits of using attenuated total reflectance
(ATR) in combination with FT-IR for the analysis of polymeric
materials.
Experimental
A PIKE MIRacle™ ATR accessory equipped with a single
reflection Zinc Selenide (ZnSe) or diamond ATR crystal was
used for all of the analysis shown in this work.2 The MIRacle
accessory was fitted with a High-Pressure Clamp, providing
intimate contact between the sample and the ATR crystal. The
MIRacle ATR (shown in Figure 1) has a unique optical design
offering high throughput of the IR beam and thereby provides
the ability to collect high quality spectral data within a
minute or less.3 The MIRacle ATR accessory utilizes a pre-
aligned, pinned-in-place crystal plate design enabling easy
exchange of the ATR crystal for sampling optimization.
The FT-IR spectrometer was equipped with a KBr beamsplitter
and a DLaTGS detector. The instrument was sealed and
desiccated to minimize purge effects. Polymer samples were
placed over the ATR crystal and maximum pressure was
applied using the slip-clutch mechanism of the clamp. All
spectra were collected at 4 cm-1 spectral resolution using 1
minute sample and background collection times. Resulting
spectra were searched using the PIKE Technologies ATR
Spectral Database.4
Figure 1. PIKE MIRacle ATR accessory with High-Pressure Clamp.
Benefits of ATR vs. Transmission for FT-IR Analysis
of Polymers
Polymer samples presented for analysis are often too thick for
measurement by transmission sampling techniques since the
ideal IR beam pathlength for sample identification is typically
less than 20 microns. However, the relatively thin depth of
penetration of the evanescent wave (typically 0.5 to 2.0
microns) in ATR generally eliminates the need to do sample
preparation. This benefit is shown in Figure 2 for the FT-IR
analysis of a 150 micron thick polymer film.
Figure 2. FT-IR spectra of thick polymer film by ATR (upper blue) and
Transmission (lower red).
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PIKE Technologies · 6125 Cottonwood Drive · Madison, WI 53719
Phone: (608) 274-2721 · info@piketech.com · www.piketech.com
In Figure 2, the transmission spectrum of the thick polymer
film shows numerous totally absorbing IR bands preventing a
high quality comparison with the spectral database. However,
the thick polymer film measured using the MIRacle ATR shows
an excellent result and is identified as a polyvinyl chloride
based polymer.
Choice of ATR Crystal for Polymer Analysis
The two most popular ATR crystal materials used for polymer
analysis are ZnSe and diamond. Both of these crystals have a
refractive index of 2.4 and with a typical polymer refractive
index of 1.5 at a 45° angle of incidence and at 1000 cm-1 the
ATR depth of penetration is about 2 microns. The most likely
differentiation for use of ZnSe or diamond is the form and
hardness of the polymer sample. The Knoop hardness
(kg/mm2) of diamond is 5700 whereas that of ZnSe is 120.5 In
practical terms this means that for softer or for flat polymer
samples we can routinely use ZnSe as an ATR crystal material.
In Figure 3, results for the ATR analysis of inner and outer
layers of a polymer electronic storage bag using the MIRacle
ATR fitted with a ZnSe crystal.
Figure 3. ATR/FT-IR spectra of inner (upper blue) and outer (lower red)
sides of an electronics storage bag.
The upper blue spectrum is identified as polyethylene and the
lower red spectrum is identified as a polyethylene
terephthalate. For relatively hard polymer samples where the
material is irregular such that application of pressure may
cause deformation of the ZnSe crystal surface, the use of
diamond as an ATR crystal material is recommended. The
hardness of diamond is such that it will not scratch and it will
not deform with application of high pressure onto the
polymer sample.
Examples of the ATR analysis of rigid and irregular shaped
polymer materials are shown in Figure 4. The upper blue
spectrum is generated from a single polymer pellet about 3
mm in diameter and is identified as Nylon 6/6. The lower red
spectrum is collected from a screwdriver handle placed
directly upon the diamond crystal of the MIRacle ATR and is
identified as a cellulose acetate.
Figure 4. ATR/FT-IR analysis of a hard polymer pellet (upper, blue) and
a screw driver handle (lower, red).
Summary
The MIRacle ATR accessory with an FT-IR spectrometer is a
powerful sampling tool for the analysis of polymers. ATR
eliminates sample preparation generally required for FT-IR
analysis by transmission sampling techniques and thereby
greatly speeds the measurement. Analysis and identification
of unknown polymer samples can be routinely done within 1
minute using the MIRacle ATR. A ZnSe crystal works very well
for the routine analysis of relatively soft polymer materials
and also is compatible with flat polymer samples. The
diamond crystal is compatible with all polymer samples
including irregular shaped, rigid polymers because it cannot
be scratched or deformed by application of high pressure
onto the polymer sample.
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PIKE Technologies · 6125 Cottonwood Drive · Madison, WI 53719
Phone: (608) 274-2721 · info@piketech.com · www.piketech.com
References
1 B. H. Stuart, Polymer Analysis (John Wiley & Sons, UK, 2002).
2 MIRacle ATR, Product Data Sheet, PIKE Technologies, 2013.
3 United States Patents 5,965,889 and 6,128,075, Philip R.
Brierley, PIKE Technologies, 1999, 2000.
4 ATR Spectral Databases, Product Data Sheet, PIKE
Technologies, 2013.
5 Transmission Sampling Techniques – Theory and
Applications, Application Note, PIKE Technologies, 2013.