application note

Characterization of Polymers Using TGA

W.J. Sichina, Marketing Manager

• Compositional analysis of The extended capabilities of the

Introduction multi-component materials or PerkinElmer TGA, as a valuable tool
blends for polymeric characterization and
• Thermal stabilities quality assurance are demonstrated by
Thermogravimetric analysis (TGA) these applications.
• Oxidative stabilities
is one of the members of the family
of thermal analysis techniques used • Estimation of product lifetimes
• Decomposition kinetics Thermal Stabilities and Moisture
to characterize a wide variety of Content
materials. TGA provides compli- • Effects of reactive atmospheres
mentary and supplementary on materials
• Filler content of materials Figure 1 shows the TGA results
characterization information to the generated on nylon 6,6 toothbrush
most commonly used thermal • Moisture and volatiles content
bristles. The plot shows the percent
technique, DSC. mass as a function of sample
PerkinElmer offers a variety of high temperature for the nylon 6,6 bristles
TGA measures the amount and rate under a nitrogen purge.
(velocity) of change in the mass of a performance TGA instruments
encompassing a wide range of Approximately 10 mg of sample was
sample as a function of temperature heated at a rate of 20 C/min with the
or time in a controlled atmosphere. application needs and operational
requirements. All of the TGA PerkinElmer TGA.
The measurements are used
primarily to determine the thermal instruments feature an optional,
and/or oxidative stabilities of state-of-the-art autosampler for
materials as well as their reliable, unattended operation.
compositional properties. The
technique can analyze materials that
exhibit either mass loss or gain due
to decomposition, oxidation or loss
of volatiles (such as moisture). It is
especially useful for the study of
polymeric materials, including
thermoplastics, thermosets, elasto-
mers, composites, films, fibers,
coatings and paints.

TGA measurements provide

valuable information that can be
used to select materials for certain
end-use applications, predict product
performance and improve product
quality. The technique is
particularly useful for the following Figure 1. TGA results obtained for nylon 6,6 bristles
types of measurements: showing thermal degradation
The TGA results show that the nylon The epoxy resin undergoes thermal option of an automated gas flow and
6,6 polymer undergoes thermal degradation beginning at 440 C gas switching accessory for ease of
degradation beginning at 482 C and with a mass loss of 57.4%. At 650 conducting TGA thermo-oxidative
with a total mass loss of 99.0%. C, the purge gas flowing over the experiments]. The material remaining
There is a small amount of inert sample was automatically switched behind after exposing the sample to
residue remaining (0.15%). to oxygen and the carbon residue oxygen is the inert glass filler, which
was burned off at 655 C with a mass the TGA shows comprises 31.8% of
Nylon polymers absorb a small loss of 10.5%. [The PerkinElmer the mass of the epoxy resin.
amount of ambient moisture and TGA instruments all feature the
TGA can be used to determine this
level of water. This may be seen in
Figure 2 for the nylon 6,6 sample,
which is an enlarged view of the
TGA results in the temperature
region below the onset of
degradation. At about 56 C, the
nylon polymer starts to evolve the
small amount of moisture, which is
found to be 0.86% by TGA. A high
performance TGA instrument is
required to detect this small level of
moisture content. Knowing this
moisture content is important as it
has a major bearing on the end use
properties and processing
performance of nylon.

Filler Content in Polymers

Figure 2. TGA results showing water wright loss for nylon 6,6
One major application of TGA is the
assessment of the filler content in
polymers and composites. The level
of fillers can have a significant
impact on the end use properties
(thermal expansion, stiffness,
damping) of the final product. This
is particularly important for
electronics applications where the
level of filler affects the coefficient
of thermal expansion (CTE) as
measured using the PerkinElmer
TMA. It is important for the
components in a printed circuit
board to have very similar expan-
sivities or else built-in stresses over
time can occur. Displayed in Figure
3 are the TGA results generated on a
glass filled epoxy resin used for
electronic applications. Figure 3. TGA results for epoxy-glass powder

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Characterization of the toughness properties to the ABS However, Auto Stepwise TGA does
Differences in Polymers blend. ABS is typically used for provide the ability to resolve the two
housings for personal computers weight loss events and makes the
A high performance TGA, such as and other electronic equipment and quantitative compositional analysis of
the ones available from Perkin- the material’s impact resistance is the ABS possible. This may be seen
Elmer, allow for the detection of important for its long term in the Auto Stepwise TGA results
subtle, but potentially important, durability. The weight loss obtained on ABS displayed in Figure
differences between polymers. transition of the butadiene rubber 5. The butadiene, rubber component
Shown in Figure 4 are the TGA component occurs extremely close is nicely separated from the SAN
results obtained on two different to the decomposition of the SAN decomposition and this provides
high density polyethylene (HDPE) copolymer. Standard TGA cannot excellent characterization information.
containers. One is an opaque soap separate out the two events.
container while the other is a semi-
transparent water bottle. The soap
bottle HDPE resin has a slightly, but
significantly, higher level of filler
(2.1% versus 0.65%). This
information is important for the
production of the containers.

Compositional Analysis of
Multi-component Polymers

One of the most important

applications of TGA is the
assessment of the compositional
analysis of polymeric blends. The
compositional characterization
information can be enhanced
through the use of Auto Stepwise Figure 4. TGA degradation for two different HDPE bottles
TGA, where the TGA instrument
automatically heats the sample and
then holds it under isothermal
conditions when the instrument
detects a significant weight loss.
This provides the highest possible
separation of overlapping
decomposition events and provides
for the most accurate compositional
analysis of polymers.

An example of the ability of the

Auto Stepwise approach to provide
useful compositional information is
in the characterization of ABS. This
is a polymer alloy comprised of a
SAN matrix (styrene acrylonitrile
copolymer) with butadiene. The
butadiene is a rubbery component Figure 5. Auto Stepwise TGA results for ABS showing
and provides the desired impact and separation of SAN and butadiene components
3
Another example of the ability of the
Auto Stepwise approach to provide
outstanding separation of over-
lapping weight loss events is for tire
elastomers. These elastomers
consist of a blend of polymer, oil
extender, carbon black and fillers.
It is difficult to separate out the oil
from the polymer using standard
TGA since the two events severely
overlap. However, with the Auto
Stepwise approach, all of the
components in a tire elastomer can
be clearly identified as is shown in
Figure 6. This information is
valuable for the production of an
automotive tire with the desired end
use and long term properties.

Measurement of Low Level of

Volatiles
Figure 6. Auto Stepwise TGA compositional results for tire elastomer
Many polymer applications are showing separation of oil, polymer, carbon black and filler
sensitive to occurrence of low level
volatilization. On a large production
basis, even a small level of volatiles
(e.g., less than 1%) can have a major
impact on the processing of the Low Level of Volatiles
polymer. It is known that low levels
of volatiles can affect the injection from PET Resin at 130 C
molding or blow molding processing Single Pellet
of polymers. Shown in Figure 7 is
the low level of volatilization
obtained for a single pellet of PET
resin. This measurement was
performed holding the sample under
gentle isothermal conditions at 130
C. The mass loss observed at 10
hours was 0.219% for the PET
pellet. This is an important aspect
for PET resins used to make
beverage containers as low levels of
soluble volatile components can
affect the taste of the beverage. The
high performance TGA instruments Figure 7. Low level emission of volatiles from single PET chip under
from PerkinElmer provide the high
gentle isothermal conditions at 130 C
degree of sensitivity and stability to
make these long term measurements
possible.
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TGA Decomposition Kinetics
for Lifetime Predictions

TGA decomposition information can

be used to predict the useful product
lifetimes of some polymeric
materials, such as the coatings for
electrical or telecommunication
cables. The sample is heated at
three or more different heating rates.
The use of the different heating
changes the time scale of the
decomposition event. The faster the
applied heating rate, the higher the
given decomposition temperature
becomes. This approach establishes
a link between time and temperature
for the polymer decomposition and
this information can be used to
model the decomposition kinetics. Figure 8. Effect of heating heat on thermal decomposition of
polyethylene
Shown in Figure 8 are the TGA
results generated on a sample of
polyethylene at heating rates ranging
from 1 to 40 C/min. As the heating
rate is increased, the onset of
decomposition is moved to higher
temperatures. This data can then be
analyzed using the PerkinElmer
TGA Decomposition Kinetics
Software. The kinetics analysis
provided by the software provides
valuable predictive information on
polymeric materials, including
lifetime estimations. Displayed in
Figure 9 are the isoconversion
curves, which presents the time to
achieve a particular level of
conversion as a function of
temperature. These are particularly
useful for product lifetime Figure 9. Isoconversion curves for polyethylene thermal
assessments. If the desired level of degradation based on kinetics modeling
critical conversion is known, then
the time to achieve this critical level
at a particular operating or end use
temperature can be predicted.

PETech-78