A P P L I C AT I O N N O T E

Thermal Analysis

Importance of DSC Introduction

Differential scanning calorimetry (DSC) is widely used to
Rapid Cooling for the characterize the thermophysical properties of polymers. DSC
can measure important thermoplastic properties including:
Analysis of Plastic • Melting temperature

Microwave Food Trays • Heat of melting

• Percent crystallinity
• Tg or softening
• Crystallization
• Presence of recyclates/regrinds
• Nucleating agents
• Plasticizers
• Polymer blends (presence, composition and compatibility)

Most DSC experiments on polymers are conducted by heating

from ambient conditions to above the melting temperature. But,
for some thermoplastics, which do exhibit differences during
processing, standard heating DSC may not show any significant
DSC 8000 differences. A more sensitive test, for detecting subtle, but
important differences between different batches of a given
thermoplastic, is the DSC isothermal crystallization test.

During the manufacture of plastic products, such as bottles, fibers,

films, containers, housings, pipes and trays, the thermoplastic
is melted, cooled, thermoformed and crystallized. The complete
 study of the behavior of plastics, which are melt-processed, DSC cooling experiments are important for the assessment
requires having a DSC instrument that is capable of rapid of the effects of these nucleating agents on the crystallization
cooling to simulate and fully explore the properties of these properties of the PET resin. Standard DSC may not reveal
materials. obvious differences between two different nucleated resins,
whereas these differences will become evident during DSC
To study the melt-crystallization properties of polymers, cooling experiments. For the highly nucleated and fast crys-
several informative DSC tests can be conducted: tallizing PET microwave food trays, the Power Compensated
• Isothermal crystallization (at a single or multiple temperatures) DSC is necessary for the best in-depth study of the rapid
crystallization of the resin.
• Cooling (at different rates from very fast to normal)
• Reheating after cooling (at different rates)
Experimental
The successful measurement of these particular tests The heat flow properties of two different PET microwave
requires a DSC instrument with a very fast response time. food trays (Tray 1 and Tray 2) were studied, along with the
This is because many thermoplastics can crystallize rapidly non-nucleated PET precursor resin. The experiment conditions
when cooling from the melt. It is important that the DSC presented in the table were used to study the cooling
be able to cool and equilibrate as fast as possible in order properties of the PET resins.
to detect the complete crystallization exothermic peak.
The DSC with the fastest response time is the Pyris™ Power The outstanding rapid response of the Power Compensated
Compensated DSC from PerkinElmer. DSC may be seen in Figure 1. This plot shows the heating
and cooling performance of the Power Compensated DSC at
heating and cooling rates of 400 and 200 ˚C/min between
Power Compensated DSC
200 and 0 ˚C. The DSC was equipped with the refrigerated
The DSC 8000 from PerkinElmer uses the Power cooling system, Intracooler II and a helium purge was
Compensated approach. This DSC uses two independently applied. The actual sample temperature (red) and program
controlled, low mass (1 g) sample and reference furnaces. temperature (blue) are displayed as a function of time. The
The low mass of the Power Compensated furnaces yields a sample temperature tracks the program temperature very well
DSC with low thermal inertia and the fastest response time even at the ballistic cooling rate of 400 ˚C/min and the use
of any DSC instrument available. of a refrigerated cooling system, rather than liquid nitrogen.
No other DSC instrument can match this level of performance.
The Power Compensated DSC allows samples to be linearly
heated and/or cooled at rates as fast as 500 ˚C/min. This is
important when measuring isothermal crystallization times Experimental Conditions
and behaviors of polymers. Instrument DSC 8000
Cooling system Intracooler II
In contrast, heat flux DSC instruments employ a large mass
Sample pan Crimped aluminum standard pan
furnace. Some DSC devices use a silver block with a mass of
100 g or more. This provides a much higher thermal inertia Sample mass Approximately 10 mg
and a slower inherent DSC response time. The heat flux DSC Purge gas Helium
instruments cannot achieve the very fast cooling and heating Cooling rate (isothermal 500 ˚C/min from 300 ˚C
provided by the Power Compensated DSC. crystallization studies)
Cooling rates for cool-reheat 400, 300, 100 and 50 ˚C/min
Need for Fast Cooling for Microwave Food Trays experiments between 300 and 0 ˚C
The thermophysical properties of plastic microwave food Heating rate for heating 20 ˚C/min
trays were studied using Power Compensated DSC. The experiments
microwave food trays must be capable of withstanding large
and rapid extremes in temperatures. The trays are generally
thermoformed from polyethylene terephthalate (PET) since
this polymer is semicrystalline and exhibits the desired end-
use properties such as stability, ease of processing and
impact resistance. However, to further enhance the thermal
stability of the PET polymer for use as microwave food trays,
the crystallinity of the polymer is increased by adding nucleating
agents. These agents induce a higher level of crystallization
of the PET resin during cooling from the melt. Higher
concentrations of a given nucleating agent will result in a
higher level of crystallinity of the plastic during processing.

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 When the cooled food tray is reheated, the cold crystallization
exothermic peak occurs at a much lower temperature
(134 ˚C) and is much smaller than that of the PET chip.
These major differences are reflective of the changes
caused by the presence of the nucleating agents.

Figure 1. Fast heating and cooling performance of the Power Compensated

DSC.

Results
Displayed in Figure 2 are the DSC results obtained on the
PET precursor polymer before the nucleating agents are Figure 2. DSC results for PET chip (before additives) showing as received
added. The plot shows the first and second heating results. resin and resin after being melted and cooled at 200 ˚C/min.
The PET resin was rapidly cooled at a rate of 200 ˚C/min
between the first and second heats. During the first heating,
no crystallization exothermic peak is observed reflecting the
fact that the polymer has a high level of crystallinity in its as
received state. The resin undergoes melting at 261 ˚C with a
heat of melting of 66.7 J/g.

When the PET sample is rapidly cooled down to room

temperature and then reheated, a well-defined cold crystal-
lization peak is obtained at 173 ˚C, which is typical for this
polymer. The heat of crystallization is found to be 30.1 J/g.
During the second heating segment, the PET undergoes
melting at 257 ˚C with a heat of melting of 33.0 J/g. The net
heat of crystallization (melting – cold crystallization) is 2.9 J/g,
which is reflective of a nearly amorphous polymer. This
demonstrates the ability of the Power Compensated DSC
to yield an amorphous polymer directly in the DSC with the
Figure 3. DSC heating results for PET microwave tray resin after cooling from
application of a fast cooling rate. In comparison, many heat
the melt at 200 ˚C/min.
flux DSC instruments require that the sample be physically
removed from the hot cell in order to generate an amor-
For quality assurance purposes, the manufacturers of the
phous state by manual quench cooling.
plastic microwave food trays like to induce a more well-
To make the PET resin suitable for the manufacture of the defined cold crystallization peak for the nucleating resin.
microwave food trays, nucleating agents are added to the This provides a sensitive indicator as to the effectiveness of
polymer. The presence of these nucleating additives drasti- the nucleating agents based on the peak shape, magnitude
cally changes the morphology of the polymer allowing it to and temperature. However, this requires ballistically cooling
crystallize much more rapidly. Displayed in Figure 3 are the the PET resin from the melt to develop an amorphous material.
DSC results obtained from the PET sample extracted from Displayed in Figure 4 are the DSC results obtained on the
a microwave food tray (Tray 1). The sample was heated food tray PET resin when cooled at the very fast rate of 400
through its melt temperature and then cooled at a rate of ˚C/min. It may be seen that a well-defined cold crystallization
200 ˚C/min back to room temperature. peak is observed at 131 ˚C. This is possible only with the
cooling capability provided by the Power Compensated DSC
for such heavily nucleated polymers.

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 In contrast, most heat flux DSC units can heat at a maximum
rate of only 100 ˚C/min. This is not fast enough to avoid
crystallization for fast crystallizing polymers such as nylon
or nucleated PET. Shown in Figure 5 are the DSC results
generated for the PET tray resin when cooled from the
melt at a rate of 100 ˚C/min. The cold crystallization peak
is just barely observed, as these results demonstrate. Much
valuable characterization information on the effects of the
nucleating agents is lost when required to use the slower
heating rates necessitated with heat flux DSC. The Pyris
Power Compensated DSC provides the ability to cool over
an extremely wide range of rates for the most comprehensive
characterization information.

Figure 6. Overlay of DSC results on PET tray after cooling at rates of 400,
200, 100 and 50 ˚C/min.

This demonstrates the great importance of the need for the

very fast cooling to get a complete picture of the crystallizable
nature of this PET resin material.

Additional supplementary characterization information can

be obtained by performing isothermal crystallization measure-
ments on the nucleated PET resins. With this test, a sample
of polymer is heated up through its melt and held under
isothermal conditions for several minutes to destroy the
existing crystalline structure. The sample is then ballistically
cooled to a temperature below the melting temperature to
allow the polymer to crystallize under tightly controlled condi-
Figure 4. DSC results for PET tray resin after cooling at 400 ˚C/min. tions. DSC monitors the resulting crystallization exothermic
peak as a function of time.

The isothermal crystallization test provides valuable information

on polymers including:
• Average molecular weight
• Molecular weight distribution
• Presence of recyclates/regrinds
• Plasticizers
• Nucleating agents, pigments or other additives
• Copolymers
• Injection molding lubricants or flow enhancers

Because of its very fast response time and ability to cool

quickly, the Power Compensated is ideally suited for the
measurement of the isothermal crystallization of polymers.
Figure 5. DSC results for PET tray resin after cooling at 100 ˚C/min.
Displayed in Figure 7 are the isothermal crystallization results
generated for Tray 1. The sample was cooled from 300 ˚C
The effects of the applied cooling rate for the PET tray resins to the target isothermal temperatures at a cooling rate of
may be seen in Figure 6. This shows a direct overlay of the 500 ˚C/min. The crystallization behavior was monitored at
heating curves obtained after cooling from the melt at 400, temperatures of 230, 225, 220, 215 and 210 ˚C. At the
200, 100 and 50 ˚C/min. Due to the heavy nucleation of the temperature of 210 ˚C, the resin reached its maximum rate
PET resin, there is a major change in the results when the of crystallization in about 30 seconds. This demonstrates the
cooling is slowed from the very fast 400 ˚C/min to 200 ˚C/min. ultra fast responsiveness of the Power Compensated DSC.

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Figure 7. Isothermal crystallization results for PET Tray 1. Figure 9. Overlay of DSC isothermal crystallization results at 220 ˚C for PET
microwave trays 1 and 2.

Another PET microwave tray (Tray 2) was analyzed using These differences would not be apparent with standard
the DSC isothermal crystallization test and these results are heating DSC, but are very noticeable with the DSC isothermal
displayed in Figure 8. This resin was clearly different in its crystallization measurements. The measurement of the
resulting crystallization behavior as compared to the Tray 1 very fast crystallization responses of these nucleated resins
sample in that it took longer for it to crystallize under identical requires a DSC with an ultra-fast response time, and this is
conditions. This indicates that the Tray 1 resin was more the Power Compensated DSC.
heavily loaded with nucleating agents as compared to Tray 2.
Summary
The differences between the crystallization behaviors of the
Tray 1 and Tray 2 PET resins is more evident in an overlay Most plastic processes require that the polymer be melted
(Figure 9) of the isothermal crystallization behaviors at 220 ˚C. and cooled during the thermoforming stage. The most
Tray 1 clearly crystallizes more rapidly as compared to Tray 2. comprehensive characterization of plastics undergoing melt
processing necessitates that the material be studied under
both heating and cooling conditions. The cooling analysis
allows the effects of nucleating and plasticizing agents to
be more fully quantified. Oftentimes thermoplastics may not
exhibit any significant differences by standard heating DSC.
However, when cooling studies are performed, significant
differences, due to the presence of nucleating agents or
flow enhancers, may become apparent. Such DSC data is
extremely valuable for quality assurance or for process con-
trol purposes. The successful performance of cooling studies
requires a DSC with a fast response time so that the sample
can be analyzed at ballistic cooling rates. The DSC instru-
ment with the fastest response time and the ability to heat
and cool ballistically (up to 500 ˚C/min) is the power
compensated DSC 8000 from PerkinElmer.
Figure 8. Isothermal crystallization results for PET Tray 2.

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