Designation: D 3418 – 99

AMERICAN SOCIETY FOR TESTING AND MATERIALS

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Reprinted from the Annual Book of ASTM Standards. Copyright ASTM

Standard Test Method for

Transition Temperatures of Polymers By Differential
Scanning Calorimetry1
This standard is issued under the fixed designation D 3418; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.

This standard has been approved for use by agencies of the Department of Defense.

1. Scope * E 473 Terminology Relating to Thermal Analysis3

1.1 This test method covers determination of transition E 563 Practice for Preparation and Use of Freezing Point
temperatures of polymers (Note 1) by differential scanning Reference Baths4
calorimetry. E 793 Test Method for Heats of Fusion and Crystallization
by Differential Scanning Calorimetry3
NOTE 1—First-order transition temperatures or melting points of semi- E 794 Test Method for Melting and Crystallization Tem-
crystalline polymers may also be determined or approximated by the
perature by Thermal Analysis3
procedures found in Test Methods D 789.
NOTE 2—This test method may be used in conjunction with Test E 967 Practice for Temperature Calibration of Differential
Methods D 3417 or E 793 to simultaneously determine the enthalpies of Scanning Calorimeters and Differential Thermal Analyz-
melting and crystallization. ers3
1.2 This test method is applicable to polymers in granular E 1142 Terminology Relating to Thermophysical Proper-
form (below 60 mesh preferred, avoiding grinding if possible) ties3
or to any fabricated shape from which appropriate specimens E 1356 Test Method for Glass Transition Temperatures by
can be cut. Differential Scanning Calorimetry or Differential Thermal
1.3 The normal operating temperature range is from the Analysis3
cryogenic region to 600°C. With special equipment, the tem- E 1953 Practice for Description of Thermal Analysis Appa-
perature range can be extended. ratus3
1.4 The values stated in SI units are to be regarded as the 2.2 ISO Standards:5
standard. 11357-1 Plastics—Differential Scanning Calorimetry
1.5 This standard does not purport to address all of the (DSC)—Part 1: General Principles
safety concerns, if any, associated with its use. It is the 11357-2 Plastics—Differential Scanning Calorimetry
responsibility of the user of this standard to establish appro- (DSC)—Part 2: Determination of Glass Transition Tem-
priate safety and health practices and determine the applica- perature
bility of regulatory limitations prior to use. 3. Terminology
NOTE 3—This standard is similar but not equivalent to ISO 11357-1 and 3.1 Specialized terms used in this test method are defined in
ISO 11357-2. The ISO procedures provide additional information not Terminologies E 473 and E 1142.
supplied by this test method.
4. Summary of Test Method
2. Referenced Documents
4.1 This test method consists of heating or cooling the test
2.1 ASTM Standards:
material at a controlled rate in a specified purge gas at a
D 789 Test Methods for Determination of Relative Viscos-
controlled flow rate and continuously monitoring with a
ity, Melting Point, and Moisture Content of Polyamide
suitable sensing device the difference in temperature or the
(PA)2
difference in heat input between a reference material and a test
D 3417 Test Method for Enthalpies of Fusion and Crystal-
material due to energy changes in the material. A transition is
lization of Polymers by Differential Scanning Calorimetry
marked by absorption or release of energy by the specimen
resulting in a corresponding endothermic or exothermic peak
1
or baseline shift in the heating or cooling curve.
This test method is under the jurisdiction of ASTM Committee D-20 on Plastics
and is the direct responsibility of Subcommittee D20.30 on Thermal Properties
(Section D20.30.07).
3
Current edition approved April 10, 1999. Published July 1999. Originally Annual Book of ASTM Standards, Vol 14.02.
4
published as D 3418 – 75. Last previous edition D 3418 – 97. Annual Book of ASTM Standards, Vol 14.03.
2 5
Annual Book of ASTM Standards, Vol 08.01. Available from American National Standards Institute, 11 W. 42nd St., 13th
Floor, New York, NY 10036.

*A Summary of Changes section appears at the end of this standard.

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 D 3418
5. Significance and Use NOTE 4—Typically, 99+ % pure nitrogen, argon or helium are em-
ployed when oxidation in air is a concern. Unless effects of moisture are
5.1 Thermal analysis provides a rapid method for measuring to be studied, use of dry purge gas is recommended and is essential for
transitions due to morphological or chemical changes, or both, operation at subambient temperatures.
in a polymer as it is heated/cooled through a specified
7.1.2 Temperature Controller, capable of executing a spe-
temperature range. Change in specific heat capacity, heat flow
cific temperature program by operating the furnace(s) between
(in conjunction with Test Method D 3417), and temperature
selected temperature limits at a rate of temperature change of
values can be determined for these polymer transitions. Dif-
10 to 20°C/min constant to 60.1°C/min or at an isothermal
ferential scanning calorimetry can be used to assist in identi-
temperature constant to 60.1°C.
fying specific polymers, polymer alloys, and certain polymer
7.1.3 Recording Device, either digital or analog, capable of
additives, which exhibit thermal transitions. Chemical reac-
recording and displaying any fraction of the heat flow signal
tions that cause or affect certain transitions can be measured
(DSC curve) including the signal noise as a function of
with the aid of this technique; such reactions include oxidation,
temperature.
the curing of thermosetting resins, and thermal decomposition.
7.1.4 Containers (pans, crucibles, vials, and so forth) that
5.2 This test method is useful for both specification accep-
are inert to the specimen and reference materials and which are
tance, process control, and research.
of suitable structural shape and integrity to contain the speci-
6. Interferences men and reference in accordance with the specific requirements
6.1 An increase or decrease in heating rate from those of this test method.
specified can alter the results. The presence of impurities will 7.1.5 Cooling capability to hasten cool down from elevated
affect the calculated transition temperature, particularly if an temperatures, to provide constant cooling rates of up to
impurity tends to form solid solutions, or to be miscible in the 10°C/min, to achieve subambient operation, or to sustain an
melt phase. Since particle size has an effect upon detected isothermal subambient temperature, or combination thereof.
transition temperatures, the specimens to be compared should 7.2 Balance, with a capacity of 100 mg or greater to weigh
be approximately the same particle size (1-5).6 specimens or containers, or both, to 610 µg.
6.2 In some cases the specimens may react with air during
8. Sample
the temperature cycle, causing an incorrect transition tempera-
ture to be measured. Where it has been shown that this effect 8.1 Powdered or Granular Specimens—Avoid grinding if
is present, provision shall be made for running the test under the preliminary thermal cycle as outlined in 10.1.2 is not
vacuum or an inert gas blanket. Since some materials degrade performed. Grinding or similar techniques for size reduction
near the melting region, care must be used to distinguish often introduce thermal effects because of friction or orienta-
between degradation and transition. tion, or both, and thereby change the thermal history of the
6.3 Since milligram quantities of a specimen are used, it is specimen.
essential to ensure that specimens are homogeneous and 8.2 Molded or Pelleted Specimens—Cut the specimens with
representative. a microtome, razor blade, hypodermic punch, paper punch, or
6.4 Toxic or corrosive effluents, or both, can be released cork borer (Size No. 2 or 3) to appropriate size, in thickness or
when heating the material, and could be harmful to the diameter and length that will best fit the specimen capsule and
personnel or to the apparatus. will approximate the desired weight in the subsequent proce-
dure.
7. Apparatus 8.3 Film or Sheet Specimens—For films thicker than 40 µm,
7.1 Differential Scanning Calorimeter (DSC)—The essen- see 8.2. For thinner films, cut slivers to fit in the specimen
tial instrumentation required to provide the minimum differen- capsules or punch disks, if the circular specimen capsules are
tial scanning calorimetric capability for this test method used.
includes:
7.1.1 DSC Test Chamber—This chamber is composed of the 9. Calibration
following: 9.1 Calibrate the DSC temperature signal using Practice
7.1.1.1 Furnace(s), to provide uniform controlled heating E 967 and the same heating rates (that is, 10 or 20°C/min, or
(cooling) of a specimen and reference to a constant temperature both) to be used in this test method (see Note 5).
or at a constant rate within the applicable cryogenic to 600°C
temperature range of this test method. 10. Procedure
7.1.1.2 Temperature Sensor, to provide an indication of the 10.1 For First-Order Transition:
specimen temperature to 610 mK (0.01°C). 10.1.1 Use a specimen mass appropriate for the material to
7.1.1.3 Differential Sensor, to detect heat flow difference be tested. In most cases 5-mg specimen mass is satisfactory.
between the specimen and reference equivalent to 1 mW. Avoid overloading. Weigh the specimen to an accuracy of 10
7.1.1.4 Means of Sustaining a Test Chamber Environ- µg.
ment of inert purge gas at a purge flow rate of 10 to 50 6 5 10.1.1.1 Intimate thermal contact between the pan and
mL/min. specimen is essential for reproducible results. Crimp a metal
cover against the pan with the sample sandwiched in between
6
The boldface numbers in parentheses refer to the list of references at the end of to ensure good heat transfer. Take care to ensure flat pan
this test method. bottoms.

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 D 3418
10.1.2 Perform and record a preliminary thermal cycle by where:
heating the sample at a rate of 10°C/min under inert purge gas Teim 5 melting extrapolated onset temperature, °C,
atmosphere from 50°C below to 30°C above the melting point. Tefm 5 melting extrapolated end temperature, °C,
The selection of temperature and time are critical when effect Tpm 5 melting peak temperature,° C,
of annealing is studied. Minimize the time of exposure to high Teic 5 crystallization extrapolated onset temperature, °C,
temperature to avoid sublimation or decomposition. In some Tpc 5 crystallization peak temperature, °C, and
cases the preliminary thermal cycle may interfere with the Tefc 5 crystallization extrapolated end temperature, °C.
transition of interest, causing an incorrect transition or elimi- NOTE 7—The actual temperature displayed on the temperature axis
nating a transition. Where it has been shown that this effect is depends upon the instrument type (for example, specimen temperature,
present, omit the preliminary thermal cycle. program temperature, or specimen-program temperature average). Follow
any recommended procedures or guidelines of the instrument manufac-
NOTE 5—Other heating or cooling rates may be used but shall be
turer to obtain specimen temperature at the point of interest.
reported. It is the responsibility of the user of other rates to demonstrate
equivalency to this test method. 10.2 For Glass Transition:
NOTE 6—For some polymers, this high-temperature annealing may
result in degradation of the specimen. In such cases, shorter annealing
10.2.1 Use a specimen mass appropriate for the material to
times may be used but shall be reported. be tested. In most cases, a 10 to 20-mg specimen mass is
satisfactory. If both first- and second-order transitions are to be
10.1.3 Hold temperature for 10 min (10.1.2). determined, use a new specimen for each test. Weigh the
10.1.4 Cool to 50°C below the peak crystallization tempera- specimen to an accuracy of 10 µg.
ture at a rate of 10°C/min and record the cooling curve.
10.2.2 Perform and record a preliminary thermal cycle as in
10.1.5 Repeat heating (10.1.2) as soon as possible under
10.1.2 up to a temperature 30°C above the extrapolated end
inert purge gas at a rate of 10°C/min, and record the heating
temperature, Te, to erase previous thermal history, heating at a
curve.
rate of 20°C/min.
10.1.6 Measure the temperatures for the desired points on
the curves: Teim, Tpm, Tefm, Teic, Tpc, and Teic (see Fig. 1). NOTE 8—Stress relaxation peaks, caused by annealing, that appear in
Report two Tpm’s or Tpc’s if observed. some polymers above the glass transition are normally eliminated by the

FIG. 1 First-Order Transition of Nylon

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 D 3418
preliminary thermal cycle and a new baseline will be established after the 11.1.6 Results of the transition measurements using the
transition. temperature parameters cited in Fig. 1, or any combination of
10.2.3 Hold temperature for 10 min. parameters suitable for the purpose in hand. Tpm and Teic are
10.2.4 Quench cool to 50°C below the transition tempera- commonly used as single characteristic temperatures for the
ture of interest. first-order transition of semicrystalline polymers but must be
10.2.5 Hold temperature for 10 min. identified by including the subscript, and,
10.2.6 Repeat heating (10.2.2) at a rate of 20°C/min, and 11.1.7 Any side reaction (for example, crosslinking, thermal
record the heating curve until all desired transitions have been degradation, or oxidation) shall also be reported, and the
completed. (See Note 5.) reaction identified if possible.
10.2.7 Measure temperatures Teig, Tmg, and Tefg (see Fig. 2): 12. Precision and Bias
where: 12.1 No independent interlaboratory test was conducted.
Teig 5 extrapolated onset temperature, °C, However, the precision of this test method for measuring
Tmg 5 midpoint temperature, °C, and first-order melting and crystallization temperatures is essen-
Tefg 5 extrapolated end temperature, °C. tially equivalent to the that of Test Method E 793 (RR:E37-
A new baseline will likely be established after the transition, 1001).
rather than a peak (see Note 8). For most applications, the Tmg 12.1.1 An interlaboratory study was conducted in 1998 in
temperature is more meaningful and may be designated as the which the temperature of melting and crystallization of a
glass transition temperature (Tg) in place of the extrapolated polypropylene sample were determined in nine laboratories.
onset for the glass transition curve. 12.2 No independent interlaboratory test was conducted.
However, the precision of this test method for measuring the
11. Report glass transition temperature is essentially equivalent to that of
11.1 Report the following information: Test Method E 1356 (RR:E37-1013).
11.1.1 Complete identification and description of the mate- 12.2.1 An interlaboratory study was conducted in 1984 in
rial tested, including source, manufacturer’s code, which the midpoint temperature for three polymeric materials
11.1.2 Description of instrument used for the test, (polyurethane, polystyrene, and epoxy glass composite) were
11.1.3 Statement of the mass, dimensions, geometry, and determined in six laboratories.
materials of the specimen capsule; and the average rate of 12.3 Precision:
linear temperature change, 12.3.1 Within laboratory variability may be described using
11.1.4 Description of temperature calibration procedure, the repeatability value (r) obtained by multiplying the standard
11.1.5 Identification of the sample atmosphere by purge gas deviation by 2.8. The repeatability value estimates the 95 %
flow rate, purity, and composition, including humidity, if confidence limit.
applicable, 12.3.1.1 Repeatability values of r 5 2.3 and 1.0°C were

FIG. 2 Assignment of Glass Transition of Poly(Methyl Methacrylate) (PMMA)

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 D 3418
obtained for the melting and crystallization onset temperatures 12.4 Bias:
for polypropylene, respectively. 12.4.1 The bias of this test method for determining the
12.3.1.2 Repeatability values of r 5 2.2, 1.9, and 2.8°C first-order melting and crystallization temperature is essentially
were obtained for the glass transition midpoint temperature for the same as the bias for Test Method E 793 and is estimated to
a polyurethane, a polystyrene, and a epoxy glass composite, be 61.1°C (RR:E37-1001).
respectively.
12.4.2 The bias for this test method for determining the
12.3.2 Between-laboratory variability may be described us-
ing the reproducibility value (R) obtained by multiplying the glass transition temperature is undetermined as there are no
standard deviation by 2.8. The reproducibility value estimates reference values available for the materials tested.
the 95 % confidence limit.
12.3.2.1 Reproducibility values of R 5 2.7 and 4.2°C were 13. Keywords
obtained for melting and crystallization onset temperatures for 13.1 crystallization temperature; glass transition; differen-
polypropylene, respectively. tial scanning calorimetry (DSC); first-order transition; melting
12.3.2.2 Reproducibility values of R 5 4.2, 2.0, and 5.2°C temperature; polymer; transition temperature
were obtained for the glass transition midpoint temperature for
a polyurethane, a polystyrene, and a epoxy glass composite,
respectively.

REFERENCES

(1) Slade, P. E., and Jenkins, L. T., “Techniques and Methods of Polymer (4) Wunderlich, B., Differential Thermal Analysis in Physical Methods of
Evaluation,” Thermal Analysis, Vol 1, Marcel Dekker, ed., New York, Chemistry, Vol 1, Part V, A. Weissberger and B. W. Rossiter, eds., John
NY, 1966, p. 91. Wiley and Sons, Inc., New York, NY, 1971.
(2) Smothers, W. J., and Chiang, Yao, Handbook of Differential Thermal (5) Wunderlich, B., Macromolecular Physics, Academic Press, New York,
Analysis, Chemical Publishing Co., New York, NY, 1966, p. 143. NY, 1973.
(3) Garn, P. D., Thermoanalytical Methods of Investigation, Academic
Press, New York, NY, 1965, p. 95.

SUMMARY OF CHANGES

This section identifies the location of selected changes to this test method. For the convenience of the user,
Committee D-20 has highlighted those changes that may impact the use of this test method. This section may
also include descriptions of the changes or reasons for the changes, or both.

D 3418 – 99: and make it compatible with Practice E 1953. Upgrades have
(1) Revisions have been made to modernize this test method been made to the title and Sections 1, 2, 5, 7, 9, 10, 11, and 12.

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