Using FT-IR Spectroscopy to
Characterize Plastics and Other Materials
I
nfrared spectroscopy historically has been a
Stephen Lowry method of choice for characterizing a broad
Mike Bradley range of materials such as plastics, catalysts,
Thermo Fisher ceramics, coatings, and chemicals. Fourier
Scientific transform infrared (FT-IR) spectrometers are
Madison, Wisc. found in many material science groups as well
as quality control departments and testing lab-
oratories. Acquiring an infrared spectrum is
Acquiring an frequently the first step in identifying or char-
infrared acterizing a sample of unknown material, as
spectrum is well as analyzing for contaminants or chemical
differences in a sample of a rejected product.
frequently the
The infrared spectrum of a material can be
first step in considered a molecular fingerprint, which can
identifying or be used to identify the specific chemical com-
characterizing ponents. Large databases of infrared spectra
a sample of from many chemicals and materials make it
possible to rapidly compare the fingerprint
unknown from a sample to thousands of reference spec-
material. tra and determine the most similar com-
pounds. Reference spectra are available for
solids, liquids, and gases in items such as poly-
mers, additives, coatings, ceramics, minerals,
and many other commercial materials. Sophis-
ticated computer algorithms were developed to
perform complex matches for multiple compo-
nents in seconds, providing valuable informa-
tion about the chemical composition of
unknown materials, degradation, contami-
nants, or treatments.
Preparing a sample for infrared analysis tra-
ditionally involves grinding or dissolving a sam-
ple, mixing it with a dispersant, applying it to a
sample holder or liquid cell, and then directing
Fig. 1 — To check whether a plastic toy contains phthalate plasticizers, the toy
is placed on the ATR accessory and pressed down on the optical crystal using
the pressure controller to obtain a spectrum for analysis.
22 ADVANCED MATERIALS & PROCESSES • APRIL 2011
infrared light through it to obtain a spectrum.
Today, the combination of modern high sensi-
tivity FT-IR spectrometers with rugged ATR
(attenuated total reflectance) accessories pro-
vide a fast, reliable, nondestructive technique
to characterize a broad range of materials. A
high quality spectrum from many materials can
be acquired in less than a minute by simply
pressing the sample against the optical crystal
of the ATR accessory and starting the scan.
ATR spectroscopy is the most popular FT-
IR sampling technique for material characteri-
zation. Hyphenated methods such as TGA-IR
(thermal gravimetric analysis-infrared) provide
additional valuable information about the
makeup of a material through decomposition.
This article provides some examples of using FT-
IR to characterize multicomponent materials.
Plastics characterization
FT-IR spectroscopy is used extensively for
material characterization in the plastics indus-
try. While FT-IR provides valuable information
about the base polymer and its morphology,
one of its most important applications may be
analyzing the complex additive packages found
in many plastics formulations. This has become
more important with many global regulatory
agencies requiring documentation that con-
firms the chemical composition of many con-
sumer products.
A good example of this is confirming that
children’s toys do not contain phthalates plas-
ticizers. Recent evidence that the phthalate
plasticizers may cause health problems, par-
ticularly in children, resulted in many coun-
tries prohibiting the use of phthalates in toys.
In this example, a toy is simply placed on the
ATR accessory and pressed down on the opti-
cal crystal using the pressure controller. The
spectrum is acquired in less than 10 seconds
using a Thermo Scientific Nicolet iS10 FT-IR
spectrometer equipped with the Smart iTR
accessory as shown in Fig. 1. The resulting
spectrum is automatically analyzed using sev-
eral of the multivariate statistical techniques
provided with the OMNIC software.
An automatic two-step process is used to
screen the material. The sample is confirmed
first as a PVC (polyvinyl chloride) plastic by
comparing the peaks in a specific region of the
spectrum to those in a reference spectrum. The
 *Yellow Handle
PVC Match value 1000 0.008 *Yellow Handle

Absorbance
0.006
Phthalates are
present! 0.004

0.002

0.000
0.008 Phthalate reference 33
Match 99.72

Absorbance
0.006
peaks are then examined in a region specific to
0.004
phthalates (1620-1560 cm-1), and if the match is
good, a report similar to the one shown in Fig. 2 0.002

is produced. If the match is poor, the ATR analy- 0.000

1600 1550
sis is reported as inconclusive, and further work Wavenumbers, cm -1

may be necessary to check for phthalates at The best match is excellent

lower levels. The sensitivity of the ATR tech- Spectrum: *Yellow handle
nique is limited by the depth of penetration of Region: 2600.00-450.00
Search type: Correlation
the infrared light into the sample. One way to Hit list:
improve the detection limits of the analysis is to Index Match Compound name Library
increase the optical path-length by pressing a 1 99.72 Phthalate reference 33 Confirm_Phthalate2
piece of the material into a film using a hot press Fig. 2 — The peaks of a specific region of a spectrum obtained from a sample are
and acquiring an infrared transmission spec- compared to those in a reference spectrum to verify the presence of phthalates.
trum through the film.
This is an example of a dedicated
0.060 A – Stamped “Knauf”: XRF Sr/Ca = 2.6, 2190 ppm
application for a very specific material
B – 2009 USG from a FL: XRF Sr/Ca = 0.9, 530 ppm
screening requirement. Similar tech- C - Gridmarx from a south: XRF Sr/Ca = 0.4, 110 ppm
niques can be developed to check for 0.050 D – Stamped “Made in China”: XRF Sr/Ca = 2.6, 1260 ppm
E – Stamped “Knauf”: XRF Sr/Ca = 2.5, 1750 ppm
contamination or material degradation,
F – Unknown but high Sr: XRF Sr/Ca = 2.5, 2350 ppm
as well as verifying that materials are
meeting specifications or that all steps 0.040
Absorbance

in a process have been completed. A

0.030
Analysis of minerals D
and inorganic materials by ATR
Diamond ATR crystals provide a 0.020
very hard surface that can withstand E
F
heavy use. The availability of diamond
ATR makes analyzing minerals and in- 0.010
B
organic compounds fast and easy. Sev- C
eral years ago, a large number of 0.000
homeowners in the state of Florida and 1700 1600 1500 1400 1300
other communities in the southeast Wavenumbers, cm-1
United States reported severe corrosion
Fig. 3 — Analysis of spectra from drywall samples reveal clear differences in the spectra from
of the copper electrical and plumbing samples of imported drywall. The major spectral differences are attributed to the presence of
hardware in their houses. This corro- small amounts of carbonate in the samples.
sion was attributed to the presence of
imported drywall. Several samples of (x-ray fluorescence) to determine if the compo-
drywall were analyzed, some of them manufac- nent was strontium carbonate. While it is un-
tured in China, to try to understand the possi- likely that the presence of carbonate
ble cause of the corrosion. Small pieces of contributed to corrosion, it does indicate that
drywall less than 2 mm in diameter were the gypsum used in this drywall was less pure
pressed onto the Diamond ATR crystal of a and might contain other naturally occurring
Nicolet iS10 FT-IR spectrometer, and spectra minerals that could lead to corrosion. This is a
were acquired. These low-noise spectra were good example of using FT-IR spectroscopy to
obtained in less than a minute, and they reveal identify small differences in composition of in-
clear differences in the spectra from samples of organic materials.
the imported drywall as shown in Fig. 3. Epoxy characterization using TGA-IR
The major spectral differences are attrib- Thermal gravimetric analysis (TGA) is a
uted to the presence of small amounts of car- powerful deformulation tool commonly used in
bonate in the samples. These were compared to materials analysis. Basically, a small amount of
the strontium concentrations measured by XRF sample placed on a pan is inserted into a fur-

ADVANCED MATERIALS & PROCESSES • APRIL 2011 23

 nace, with the pan hanging on a sensitive microbalance. A
slow temperature ramp is applied with the sample bathed
in an inert purge gas. The increasing temperature forces
various components of the material into the vapor phase,
resulting in weight loss. TGA provides excellent quantita-
tive information about weight losses as a function of tem-
perature, but does not identify the vapors being driven off.
Coupling the TGA to an FT-IR spectrometer provides
a powerful technique that can identify the volatile compo-
nents evolved from the sample during the heating cycle.
The vapors released from the material pass through a gas
cell inserted in the FT-IR, where the spectrum is obtained.
Spectral searching provides the last link – identification of
the vapors. The weight-loss data from the TGA, the rapid
response and high sensitivity of the spectrometer, and
spectral searching combine to provide potent analytical in-
sights into the chemistry of the sample. Figure 4 shows one
configuration consisting of a Thermo Scientific Nicolet
6700 FT-IR spectrometer with an in-sample compartment
TGA accessory equipped with a double-pass gas cell
heated to 220°C, which is coupled to a TA Instruments
Fig. 4 —Thermo Scientific Nicolet 6700 FT-IR spectrometer with an
in-sample compartment TGA accessory equipped with a double-pass gas
cell coupled to a TA Instruments Q5000 TGA with a heated transfer line
used to identify the volatile components evolved from the sample during the
heating cycle.
0.08
Gram-Schmidt
Time point
0.06
Intensity
0.04
0.02
Carbon dioxide
0.00
5 10 15
Time, min
0.06 Linked spectrum at 16.975 minutes
Spectrum from
Absorbance
0.04
time point
0.02
0.00
3500 3000 2500 2000 1500
Wavenumbers, cm -1
Fig. 5 — Results of analysis of heated two-part epoxy placed in a TGA sample pan. The upper trace
reveals the total response of the IR signal in time (the GS plot), while the lower trace is the IR spectrum
present at the time point indicated by the scroll bar in the upper window.
24 ADVANCED MATERIALS & PROCESSES • APRIL 2011
(New Castle, Del.) Q5000 TGA with a heated transfer line.
A single drop of a freshly mixed two-part epoxy (nor-
mal 12 hour cure time) was placed in a TGA sample pan.
The temperature was increased from ambient to 500°C at
the rate of 15°C/min.
Figure 5 shows the results of measuring a series of spec-
tra over time as the evolved gas from the TGA flows through
the gas cell in the FT-IR. The upper trace reveals the total re-
sponse of the IR signal at each time (the GS plot), while the
lower trace is the IR spectrum present at the time point in-
dicated by the scroll bar in the upper window. The small sig-
nals in the GS plot around 11-12 minutes (190-210°C) result
from CO2 and water bubbles evolving from the sample. The
larger peak rising after 15 minutes (about 250°C) is associ-
ated with many features in the infrared, and the leading edge
of the peak contains different components than those ob-
served later in the weight loss.
Traditionally, the one difficulty with identifying the var-
ious components is the simultaneous evolution of gases. The
TGA does not discriminate between simple and complex
gas evolutions, but the instantaneous IR spectra are sum-
mations of all the gases being driven off at that time. This
complexity normally requires some skill to untangle. The
need to use multiple search regions to selectively extract in-
dividual components and the generally unfamiliar look of
gas phase spectra to many investigators contribute to the
potential for missed critical answers. Thermo Scientific cre-
ated a software package for material identification and
characterization called OMNIC Specta. One useful feature
of this package is the multicomponent search option,
which compares the spectrum from a sample to a linear
combination of spectra from the reference library spectra
that provide the best fit to the sample spectrum.
The first gases to emerge are from the unreacted base ma-
terials of the epoxy and hardener, including the common
epoxy ingredient bisphenol-A. As the temperature rises, ester
peaks appear, indicative of accelerated curing. After a period
of time, methane evolution
along with low levels of bisphe-
nol-A are evident as the epoxy
breaks down. The results of a
multicomponent search from
one of the spectra acquired dur-
ing the run reveal that several
major components are present.
The results are summarized in
20 25
the MCS search screen shown
in Fig. 6. The upper trace is the
sample spectrum, and the spec-
trum below it is a weighted sum
of the four spectra that provided
the best fit to the sample. The
individual spectra are shown in
1000 500
the lower portion of the figure.
The reference spectrum con-
tributing the most to the sample
spectrum is Bisphenol A, a com-
mon epoxy ingredient.
 Linked spectrum at 17.746 min.

This TGA-IR example demonstrates

how the OMNIC Specta multicomponent
Multicomponent search
search can be applied to the gases that composite for 4
evolve when a sample is heated. This tech- componenets in match

nique can be used to characterize both the

components in material and the thermal
3500 3000 2500 2000 1500 1000
degradation components evolving at high Wavenumbers, cm-1
x = 3159.50 y = 0.0682
temperatures. It can also be used to identify
4,4’-Isopropylidenediphenol; Bisphenol A
residual solvents or other volatiles that
might be trapped in a material.
3-methyl-2-butanone;
Methyl isopropyl ketone
Conclusion
Three applications were briefly described 4,9-Dioxa-1,12-dodecanediamine

where FT-IR provided valuable information

related to the characterization of different
materials. Because of its broad acceptance as
a prime technique for material identification,
large libraries of high quality reference spec-
tra are available for almost any application
and can be used with a multitude of sophisti-
cated matching algorithms.
Methane
Fig. 6 — Results of analysis of heated two-part epoxy. Results of a multicomponent search
from one of the spectra acquired during the run reveal that several major components are
present. The upper trace is the sample spectrum, and the spectrum below it is a weighted
sum of the four spectra that provided the best fit to the sample. The individual spectra are
shown in the lower portion of the figure.

Nicolet, iS, OMNIC, and Specta are trademarks of Thermo Fisher Scientific.

For more information contact: Stephen Lowry, Ph.D., Application Scientist, Molecular Spectroscopy, Thermo Fisher Scientific,
5225 Verona Rd., Madison, WI 53711; tel: 608/276-5675; e-mail: steve.lowry@thermofisher.com; www.thermofisher.com.

ADVANCED MATERIALS & PROCESSES • APRIL 2011 25