732 Principles of Polymer Systems

reaction is important to the second criterion. Some subtle changes in structure can
be observed when the polymer sample is compared to another material undergoing a
similar heating process but not undergoing any transitions or reactions.
Differential scanning calorimetry (DSC) uses a servo system to supply energy
to a sample and a reference material in such a way that both undergo a linearly
rising temperature. The difference in energy supplied between the sample and the
reference is a measure of various thermal events, the most common of which are
glass transition, crystallization, and melting. Other processes can take place such as
evaporation and chemical reactions. Although the most common test uses an increas-
ing temperature, some processes such as crystallization and chemical reactions can
be characterized by the energy supplied under isothermal conditions.
In one commercial instrument, the polymer sample is held in an aluminum pan
with a crimped-on lid (Figure 18.4). The reference most often is simply an empty
pan. Both the sample and the reference are heated to give a constant rate of tempera-
ture change by separate platinum resistance heaters, which are controlled by the sig-
nals from platinum resistance thermometers. The difference in power needed to keep
both at the same temperature is amplified and provides the information on thermal
events. For a properly calibrated DSC, the level of the power flux is a direct measure
of the specific heat of the sample. Since the specific heat of a polymer melt is greater
than that of the corresponding glass, a discontinuity is expected at Tg. When crystal-
lization or melting occurs, the area under a peak represents the enthalpy change.
A sample mass of 5–15 mg and a heating rate of 10°C–40°C/min are typical condi-
tions. As indicated in Section 3.8, DSC has become accepted as a standard measure
of Tg (ASTM D3418). In an illustrative example (Figure 18.5), mixtures of poly(vinyl
chloride) (PVC) with a plasticizer, di-2-ethylhexylphthalate, are sealed in aluminum
pans. At the rapid rate of temperature increase used, each test requires only 5 or 10 min.

Sample Platinum alloy Reference

PRT sensor

Platinum resistance heaters

Heat sink

FIGURE 18.4 Differential scanning calorimeter (power compensation type). The platinum
resistance thermometer (PRT) sensor detects a small error signal between the programmed
temperature and the sample temperature and calls for more or less power to each heater to
keep both holders on program. The difference in power required between the sample and the
reference is amplified and recorded. (Courtesy of PerkinElmer Corporation, Norwalk, CT.)
Analysis and Identification of Polymers 733

100
Unplasticized PVC

20% DOP

Heat flow (mW) 30%

50
40%
50%

100%

0
−50 0 50 100
Temperature (°C)

FIGURE 18.5 The glass transition for plasticized PVC as determined by DSC. The heating
rate was 40°C/min. (Reprinted from Brennan, W. P. et al., Amer. Lab., 20, 36, 1988; copyright
by International Scientific Communications, Inc.)

The transitions seen for mixtures like these are not as clear-cut as those for the pure
components. As indicated in Section 3.6, it is not unusual for the transition zone for
mixtures to be broader than it is for individual components. The Tg measured by
DSC at a fast heating rate (Figure 18.5) is substantially higher than the flex tempera-
ture of Figure 3.10, which corresponds to a much longer timescale of testing. Some
other typical effects can be seen when a partly crystalline polymer is examined
(Figure 18.6). A thermoplastic polyester exhibits a melting transition at about 250°C.
The sample cooled at 20°C/min shows very little change at the expected glass transi-
tion point (77°C). The sample quenched from the melt, having a greater amorphous
fraction, shows a substantial shift in heat flow at 77°C and crystallization at 135°C
followed by melting at 250°C (refer also to Figures 3.23 and 3.24).
Some workers have superimposed a sinusoidal pattern on the heating rate in order
to derive a more detailed information from the heat flow pattern [7]. Many other
applications have been found for DSC, including the study of kinetics of polymeriza-
tion or cross-linking, absorption, adsorption and desorption, and almost every other
possible thermal event.
In conventional differential thermal analysis (DTA), the temperature at the cen-
ter of the sample is compared with a reference material (often powdered alumina)
as both are heated at a uniform rate. Any change in the sample’s specific heat as at
Tg, any structural change that is endothermic or exothermic as at Tm, or chemical
reactions will show as changes in the temperature difference between sample Ts and
reference Tr. A primitive instrument consists of thermocouples inserted in the sample
and the reference. The sample and the reference material are held in a heated metal
block at a controlled temperature T0. As T0 is raised (a rate of 10°C/min is common),
Ts and Tr follow perhaps by as little as 0.1°C. If an endothermic reaction takes place,
Ts will lag behind Tr temporarily. If an exothermic reaction takes place, Ts will exceed
Tr temporarily. Superficially, DTA resembles DSC in that temperatures of a sample
and a reference material are increased at almost the same rate. However, in DTA the
difference in temperature, ΔT, is the measured quantity rather than the difference in
734 Principles of Polymer Systems

Cooled at 20°C/min
Heat flow (mW)

Quench cooled

Tg = 77°C Melting

Endothermic

Cold crystallization
Exothermic

50 100 150 200 250

Temperature (°C)

FIGURE 18.6 Samples of a thermoplastic polyester show different DSC traces depending
on preparation kinetics. (Data from Brennan, W. P., Characterization and Quality Control
of Engineering Thermoplastics by Thermal Analysis, Instrument Division, PerkinElmer
Corporation, Norwalk, CT, 1977.) Rapid quenching yields a sample that, on heating, shows a
distinct glass transition as well as crystallization and melting. The heating rate was 20°C/min.
(Courtesy of PerkinElmer Corporation, Norwalk, CT.)

energy being supplied. If an endothermic event such as crystallization takes place,

the sample temperature will lag slightly behind the reference temperature, giving a
peak in the ΔT versus T (average) plot similar in appearance to that in Figure 18.6.
The method is a sensitive one for detecting Tm, but the area under the peak is not eas-
ily related quantitatively to the enthalpy change.

18.4 OTHER METHODS OF THERMAL ANALYSIS

In thermogravimetric analysis (TGA), a sample is weighed continuously as the
temperature is raised. Volatilization, chemical reaction, and dehydration are some
of the processes that affect the sample weight. When many compounds have to be
screened for their applicability in a high-temperature environment, TGA may be
the only test needed. For example, if a rubbery gasket material is needed for short-
term service at 300°C, the limitation on most materials will not involve Tg or Tm .
Moreover, the chemical stability may be affected by fillers, cross-linking agents,
antioxidants, plasticizers, and lubricants. Whether the test is run in a vacuum or an
atmosphere of air or oxygen will be important. When TGA is combined with DTA