4

Thermogravimetric Analysis of Polymers

Scott Kinzy and Robert Falcone

ICI Fluoropolymers, Bayonne, New Jersey, USA

PRINCIPLES OF OPERATION
Thermogravimetric analysis (TGA) is defined as the study of the change in
mass as a function of temperature, time, and/or atmosphere. TGA consists
of two essential components, mass and temperature detection.
The mass is measured using a balance. A balance uses the physical
principle of leverage: a sample is placed at the end of the arm while placing
a reference weight in the opposite end and the weight is recorded as the
change in force. In the TGA, the mass detection is based on the principle of
substitution weighing introduced by Mettler in 1945 (Fig. 1). In the TGA
shown in Fig. 1, the calibration weights and the sample are suspended from
a single arm. The calibration weight is substituted as the sample mass sub-
stitutes for it. The weighing principle is still leverage.
Most modern TGAs, however, in addition incorporate the principle of
electromagnetic balances that have relatively little dependence on vibration
(one of the common problems for weight measurements), have high sensi-
tivity, and display little thermal drift. The beam position is monitored by a
photodetection scheme. This concept was introduced by Cahn Instruments.
As shown in Fig. 2, after taring the sample, the balance is assumed to be in
equilibrium. Addition of the sample to the left side of the beam will cause
the right side of the beam to be displaced upward. Sufficient current is

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 Figure 1 The principle of substitute weighing.

Figure 2 The principle of electromagnetic balance.

Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.

 supplied to the electric torque motor to restore it to the original beam
position. The restoring force, and hence the current, is proportional to the
change in mass. Although manufacturers will claim a sensitivity of 0.1 mg,
due to the temperature changes experienced during the course of the testing,
1 mg is the more typical sensitivity. This is the equivalent of 0.1% error (1 mg
to a 1-mg sample).
Figures 3A and 3B show typical TGA assemblies. The heating is pri-
marily by convection and radiation. This is achieved by placing the sample
inside a miniature furnace capable of high heating and cooling. The heating
elements of the furnaces are based mostly on resistive heating. Table 1 lists
the most commonly used resistive elements. Nichrome and Kanthal are the
alloys of choice when operating in the range up to 1000–12008C. This is the
range for polymeric applications. There are actually four types of furnaces
used to cover the entire normal working range from 150 to 28008C. These
are 150 to 5008C, 25 to 10008C, 25 to 16008C, and 400 to 28008C. As to
be expected, the higher the temperature, the more complex is the design of
the furnace and controls, thus making them more expensive. In most con-
ventional TGA instruments, the temperature sensor is located in the vicinity
of the sample, thus avoiding disturbing the weigh signal. Usually, the
temperature sensor is very close to the furnace wall, or sometimes it can
be found outside to avoid accidental movement and exposure of the sensor
to corrosive gases.

CALIBRATION TECHNIQUES
All TGA instruments have the capability of being calibrated for mass and
temperature. The mass calibration usually consists of placing a standard
with a specific traceable NIST (National Institute of Standards, formerly
the NBS) weight, ranging between 50 and 100 mg. The scale then measures
the weight of the standard and by placing the expected weight it then adjusts
the tension in the weighing arm.
The recommended calibration procedure for a TGA is as follows:

Step 1: weight calibration

Step 2: temperature calibration
Step 3: furnace calibration

Step 1: Weight Calibration

Weight calibration is done by comparing the balance readout of a standard
weight. Most modern TGA instruments include this procedure in their soft-
ware.

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 Figure 3A Standard furnace and furnace tube in a typical TGA assembly.
(Courtesy of the Perkin Elmer Corporation.)

Figure 3B Cross section in a typical TGA assembly. (Courtesy of Mettler

Corporation.)

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 Table 1 Maximum Temperature Limits for Furnace Resistance
Elements (approximate values)
Approx.
temperature
Element (C8) Required atmosphere

Nichrome 1000 Oxygen/oxidizing

Chromel A 1100 Oxygen/oxidizing
Tantalum 1330 Nitrogen/inert/vacuum
Kanthal 1350 Oxygen/oxidizing
Platinum 1400 Nitrogen/inert/vacuum/oxygen/oxidizing
Globar 1500 Oxygen/oxidizing
Platinum–10% rhodium 1500 Nitrogen/inert/vacuum/oxygen/oxidizing
Platinum–20% rhodium 1500 Nitrogen/inert/vacuum/oxygen/oxidizing
Kanthal Super 1600 Oxygen/oxidizing
Rhodium 1800 Nitrogen/inert/vacuum/oxygen/oxidizing
Molybdenum 2200 Nitrogen/inert/vacuum/hydrogen
Tungsten 2800 Nitrogen/inert/vacuum/hydrogen

Step 2: Temperature Calibration

The temperature calibration can be done in two ways. One is by measuring
the melting points of materials, the other is by measuring the Curie tem-
perature, the temperature at which materials lose their ferromagnetism. This
is usually done by placing a sample of ferromagnetic material in the furnace
and letting it heat while a magnet is placed outside the furnace. The
temperature at which the loss in weight is noticed is the Curie temperature
(Fig. 4).
It is advisable to use several materials whose Curie temperatures will
encompass the temperature ranges of the intended plastics analysis. Table 2
shows materials and their Curie temperatures.

Step 3: Furnace Calibration

After completing the determination of the Curie temperatures, then proceed
with furnace calibration. All instrument manufacturers include this step in
their calibration protocols.

Measuring Weight Loss with Temperature Using Calcium

Oxalate Monohydrate
The measurement of weight loss with temperature using calcium oxalate
monohydrate is performed as follows:

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 Figure 4 Typical Curie temperature analysis.

CaC2 O4 H2 O!CaC2 O4 þ H2 O

Loss will occur between 113 and 2078C.

CaC2 O4 !CaCO3 þ CO

Loss will occur between 405 and 5238C.

CaCO3 !CaO þ CO2

Loss will occur between 626 and 7938C.

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 Table 2 Typical Curie
Temperatures
Metal Curie temperature (C8)

Alumel 154.2
Nickel 355.2
Perkalloy 596
Iron 780
Hisat-50 1000

The procedure is to place a sample of CaC2O4  H2O and set the instru-
ment to run between 50 and 850C at a rate of 158C/min (Table 3 and Fig. 5).

APPLICATIONS
Application 1: Determination of the Degradation Temperature
The degradation temperature is the temperature at which a plastic reverts to
its original component(s). This is also known as the ceiling temperature. The
importance of the degradation temperature is that it helps to determine the
maximum limits at which the plastic will no longer be a plastic.
There are two TGA techniques to determine the degradation tempera-
ture of a plastic. The first is called the isothermal method and is based on
setting the sample on a temperature that is between 50 and 150C above its
melting temperature and letting the instrument measure the weight loss with
time. This is one technique used to determine physical aging of a sample
under extreme conditions. A typical decomposition curve is shown in Fig. 6.
The second technique is based on running the sample under an increas-
ing temperature pattern while measuring the weight loss. This is known as a
nonisothermal degradation test. This technique is used when the decomposi-
tion temperature of the sample is not known. Figure 7 shows the use of this

Table 3 CaC2O4  H2O

Weight Percent Loss
Step number Weight loss (%)

1 12.33
2 21.88
3 44.00
Overall 61.64

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 Figure 5 Typical calcium oxalate monohydrate run. (Courtesy of TA
Instruments, TS 13.)

Figure 6 Isothermal decomposition method.

Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.

 Figure 7 Constant heat rate decomposition method. PVC = polyvi-
nylchloride; PMMA = poly(methyl methacrylate); HPPE; high-pressure
polyethylene; PTFE; PTFE = polytetrafluoroethylene; PI = polyimide.

technique for determining the degradation temperatures of some industrial

plastics.
The isothermal method should be used when the melting temperature of
the sample is known and a better understanding is needed of the degrada-
tion of the material. The nonisothermal method should be used when the
degradation temperature is not known.

Application 2: Physical Aging

It is often essential to know the lifetime performance of a plastic. The TGA
can provide an accelerated testing to predict lifetime performance. A typical
example is shown in Fig. 8.

Application 3: Moisture Determination

Some plastics are hygroscopic in nature. This means that they retain/get
water from the surroundings. Water, like any other chemical, can chemically
deteriorate the structure of the plastic, thus weakening some or all of its
mechanical properties. Therefore, in plastics such as nylon the determina-
tion of moisture content is very important. Although the water molecule is
smaller than all of the plastic molecules, it is very important to choose the
temperature(s) for moisture determination, because some plastics may
soften at 1008C (2128F), making it very difficult to determine the water
content in the plastic. Usually this is done by placing the sample at a tem-
perature below its melting point (40–608C below) and by using compressed/

Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.

 Figure 8 Physical aging method—wire insulation thermal stability.
(Courtesy of TA Instruments, TS-125.)

dry nitrogen atmosphere to run the test for a period between 1 and 2 h.
Ensure that the calibration procedure has been done before starting this
measurement. A typical example is shown in Fig. 9.

Application 4: Reverse Kinetics

Reverse kinetics involves a hyphenated technique. ‘‘Hyphenated techni-
ques’’ are procedures that require the use of more than one instrument or
techniques simultaneously. The reason for using these techniques is that the
measurement may be lost because of the limitations of one technique used.
Reverse kinetics is a procedure by which, using the degradation method
described in application 1 in combination with either a gas chromatograph
(GC) or a Fourier transform infrared spectrophotometer (FTIR), you can
find the following:
1. The original components of the plastic being degraded (FTIR
and TGA)
2. The amount of components of the plastic being degraded (GC
and TGA).
One of the limitations of the above techniques is that either the type of
components or the amount of each is known but not both. However, there is
a third hyphenated technique that combines all of the above. This technique
uses the method described in applications in combination with a gas chro-
matograph and a mass spectrometer (GC-MS) that is also coupled with an
infrared spectrometer (FTIR). Most GC-MS units are already equipped
with infrared capabilities. The advantage of this technique is that not only

Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.

 Figure 9 Moisture determination. (Courtesy of Mettler Instruments.)

the quantities of the original components are determined but also the types
of components. Figure 10 shows a typical instrument setup to run the TGA/
GC-MS technique, Fig. 11 shows the connection between the TGA and GC-
MS unit, and Fig. 12 shows typical GC-MS scans done on TGA polymer
samples.

Application 5: Determination of Filler/Additive Content

In most industrial applications, plastics do not possess the properties
needed, thus the use of additives and fillers. The procedure to determine
the content of additives/fillers is to run the sample to and above its decom-
position temperature. Most additives will decompose at temperatures below
the material’s decomposition temperature, while most fillers will still be
present after the sample has decomposed. The typical heating rate is
between 15 and 308C/min. See Figs. 13 and 14.

Application 6: Determination of Different Types of Plastics in

One Sample
Besides the use of additives and fillers to enhance the mechanical properties
of industrial plastics, it is also common to blend different plastics in order to

Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.

 Figure 10 Typical instrument setup to run the TGA/GC-MS technique.
(Courtesy of TA Instruments, H-16781.)

create a material whose properties are better than those of the individual
components.
The procedure is to run the sample under a heating rate of 20–308C
from around room temperature to 100C above the component having the
highest decomposition temperature. With the help of Table 4, the compo-
nents can be identified. This technique is approximate, and the best way to
determine the types of components present in a sample is by using DSC and
FTIR testing along with the TGA (Fig. 15).

Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.

 Figure 11 Connection between the TGA and GC-MS unit. (Courtesy of
TA Instruments, H-16781.)

Application 7: Modulated Thermal Gravimetric Analysis

Modulated thermal gravimetric analysis (MTGA) is a recently introduced
technique that provides the advantage of running a typical TGA while
modulating the temperature response (Fig. 16). Kinetic parameters can be
determined in a much faster mode. In some plastics, total decomposition
could be more than a single weight loss and typical weight loss procedure as
indicated in application 1 will not determine the multi-weight loss reactions.
Although there are ASTM procedures outlining such methods (E1641 and
E1877), these procedures can be time consuming when rates are below 2C8/
min. In such cases, the use of an MTGA technique will enable you to
determine the weight loss in less time.

ACKNOWLEDGMENTS
We are grateful to Mr. James Creedon and Dr. Roger Blaine, TA
Instruments; Mr. Jon Foreman, Mettler Corp.; Ms. Karen Gillette, Perkin
Elmer Instruments; and Mr. Tom Wampler, CDS Analytical.

Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.

 Figure 12 Typical GC-MS scans done on TGA polymer samples.
(Courtesy of TA Instruments, H-16781.)

Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.

 Figure 13 Typical curve showing the presence of additives in PTFE. In this
particular case, the additive is a surfactant. (Courtesy of ICI
Fluoropolymers.)

Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.

 Figure 14 Typical curve showing the presence of a filler in polyethylene. In
this particular case, the filler is carbon. (Courtesy of Perkin Elmer
Instruments.)

Table 4 TGA Decomposition Temperatures of Common Polymers

Acronym Polymer Decomposition temperature (C8)

ABS Acrylonitrile-butadiene-styrene 375

PMMA Poly methyl methacrylate 313
PTFE Polytetrafluoroethylene 525
PVDF Polyvinylidene fluoride 470
Nylon 6 Nylon 6 400
Nylon 6,6 Nylon 6,6 426
PC Polycarbonate 473
PBT Polybutylene terephthalate 386
PET Polyetheretherketone 575
LDPE Low-density polyethylene 459
HDPE High-density polyethylene 469
PPO Polyphenylene oxide 400
PPS Polyphenylene sulfide 508
PP Polypropylene 417
PS Polystyrene 351
PSO Polysulfone 510
PVC Polyvinyl chloride 265

Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.

 Figure 15 TGA analysis of ethylene vinyl acetate blend. (Courtesy of TA
Instruments, TA023.)

Figure 16 MTGA curve of PTFE. (Courtesy of TA Instruments.)

Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.

 BIBLIOGRAPHY
General
Bordoloi, B. K, Wright, C .E., and Pearce, E. M., Laboratory Experiments in
Polymer Synthesis and Characterization. EMMSE, 1982, p. 269.
Mathot, Vincent B. F., Calorimetry and Thermal Analysis of Polymers, Hanser, 1993.
Turi, Edith, Thermal Characterization of Polymeric Materials, Vols 1 and 2,
Academic Press, 1997.
Wendlandt, W. W. M., Thermal Analysis, 3rd ed., Wiley, New York, 1986.
Wunderlich, B., Thermal Analysis, Academic Press, 1990.

Standard Testing Methods

ASTM E473-85, Terminology Relating to Thermal Analysis.
ASTM E914-83, Evaluating Temperature Scale for Thermogravimetry.
ASTM E1131-93, Standard Test Method for Compositional Analysis by
Thermogravimetry.
ASTM E1582-93, Standard Practice for Calibration of Temperature Scale for
Thermogravimetry.
ASTM E1641-94, Decomposition Kinetics by Thermogravimetry.
ASTM E1868-97, Standard Test Method for Loss-on-Drying by Thermogravimetry.
ASTM 1877-97, Standard Practice for Calculating Thermal Endurance from
Thermogravimetric Decomposition Data.

Hyphenated Methods
Charsley, E. L., Warrington, S. B., Jones, G. K., and McGhie, A. R., TGA-MS
Using a Simple Capillary Interface. ‘‘Am. Lab., 1990.
Mettler Toledo Technical Notes.
Nicolet Instruments Technical Notes.
Perkin Elmer Technical Notes.
TA Instruments Technical Notes.

Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.