This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles

for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

Designation: E1356 − 23

Standard Test Method for Assignment of the

Glass Transition Temperatures by Differential Scanning
Calorimetry1
This standard is issued under the fixed designation E1356; 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 (´) indicates an editorial change since the last revision or reapproval.

1. Scope ASTM Test Methods

1.1 This test method covers the assignment of the glass E473 Terminology Relating to Thermal Analysis and Rhe-
transition temperatures of materials using differential scanning ology
calorimetry or differential thermal analysis. E691 Practice for Conducting an Interlaboratory Study to
Determine the Precision of a Test Method
1.2 This test method is applicable to amorphous materials or E967 Test Method for Temperature Calibration of Differen-
to partially crystalline materials containing amorphous regions, tial Scanning Calorimeters and Differential Thermal Ana-
that are stable and do not undergo decomposition or sublima- lyzers
tion in the glass transition region. E1142 Terminology Relating to Thermophysical Properties
1.3 The normal operating temperature range is from 2.2 ISO Standards:3
−120 °C to 500 °C. The temperature range may be extended, 11357–2 Differential Scanning Calorimetry (DSC)-Part 2
depending upon the instrumentation used. Determination of Glass Transition Temperature
1.4 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this 3. Terminology
standard. 3.1 Definitions:
1.5 ISO standards 11357–2 is equivalent to this standard. 3.1.1 Definitions—The following terms are applicable to
this test method and can be found in Terminologies E473 and
1.6 This standard does not purport to address all of the E1142: differential scanning calorimetry (DSC); differential
safety concerns, if any, associated with its use. It is the thermal analysis (DTA); glass transition; glass transition
responsibility of the user of this standard to establish appro- temperature (T g); and specific heat capacity.
priate safety, health, and environmental practices and deter- 3.2 Definitions of Terms Specific to This Standard:
mine the applicability of regulatory limitations prior to use. 3.2.1 There are commonly used transition points associated
1.7 This international standard was developed in accor- with the glass transition region—(see Fig. 1).
dance with internationally recognized principles on standard-
ization established in the Decision on Principles for the 3.2.1.1 extrapolated end temperature, (Te), °C—the point of
Development of International Standards, Guides and Recom- intersection of the tangent drawn at the point of greatest slope
mendations issued by the World Trade Organization Technical on the transition curve with the extrapolated baseline following
Barriers to Trade (TBT) Committee. the transition.
3.2.1.2 extrapolated onset temperature, (Tf), °C—the point
2. Referenced Documents of intersection of the tangent drawn at the point of greatest
2.1 ASTM Standards:2 slope on the transition curve with the extrapolated baseline
E177 Practice for Use of the Terms Precision and Bias in prior to the transition.
3.2.1.3 inflection temperature, (Ti), °C—the point on the
thermal curve corresponding to the peak of the first derivative
1
This test method is under the jurisdiction of ASTM Committee E37 on Thermal (with respect to time) of the parent thermal curve. This point
Measurements and is the direct responsibility of Subcommittee E37.01 on Calo- corresponds to the inflection point of the parent thermal curve.
rimetry and Mass Loss.
Current edition approved Aug. 1, 2023. Published August 2023. Originally 3.2.1.4 midpoint temperature, (Tm), °C—the point on the
approved in 1991. Last previous edition approved in 2014 as E1356 – 08 (2014) thermal curve corresponding to 1⁄2 the heat flow difference
which was withdrawn March 2023 and reinstated in August 2023. DOI: 10.1520/
between the extrapolated onset and extrapolated end.
E1356-23.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
3
Standards volume information, refer to the standard’s Document Summary page on Available from American National Standards Institute (ANSI), 25 W. 43rd St.,
the ASTM website. 4th Floor, New York, NY 10036, http://www.ansi.org.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States

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 E1356 − 23

FIG. 1 Glass Transition Region Measured Temperatures

3.2.1.5 Discussion—Midpoint temperature is most com- 6. Interferences

monly used as the glass transition temperature (see Fig. 1). 6.1 A change in heating rates and cooling rates can affect the
3.2.2 Two additional transition points are sometimes iden- results. The presence of impurities will affect the transition,
tified and are defined: particularly if an impurity tends to plasticize or form solid
3.2.2.1 temperature of first deviation, (To), °C—the point of solutions, or is miscible in the post-transition phase. If particle
first detectable deviation from the extrapolated baseline prior to size has an effect upon the detected transition temperature, the
the transition. specimens to be compared should be of the same particle size.
3.2.2.2 temperature of return to baseline, (Tr), °C—the point 6.2 In some cases the specimen may react with air during
of last deviation from the extrapolated baseline beyond the the temperature program causing an incorrect transition to be
transition. measured. Whenever this effect may be present, the test shall
be run under either vacuum or an inert gas atmosphere. Since
4. Summary of Test Method some materials degrade near the glass transition region, care
4.1 This test method involves continuously monitoring the must be taken to distinguish between degradation and glass
difference in heat flow into, or temperature between a reference transition.
material and a test material when they are heated or cooled at 6.3 Since milligram quantities of sample are used, it is
a controlled rate through the glass transition region of the test essential to ensure that specimens are homogeneous and
material and analyzing the resultant thermal curve to provide representative, so that appropriate sampling techniques are
the glass transition temperature. used.
5. Significance and Use 7. Apparatus
5.1 Differential scanning calorimetry provides a rapid test 7.1 Differential Scanning Calorimeter—The essential in-
method for determining changes in specific heat capacity in a strumentation required to provide the minimum differential
homogeneous material. The glass transition is manifested as a scanning calorimetric capability for this method includes a Test
step change in specific heat capacity. For amorphous and Chamber composed of a furnace(s) to provide uniform con-
semicrystalline materials the determination of the glass transi- trolled heating (cooling) of a specimen and reference to a
tion temperature may lead to important information about their constant temperature or at a constant rate over the temperature
thermal history, processing conditions, stability, progress of range from –120 °C to 500 °C, a temperature sensor to provide
chemical reactions, and mechanical and electrical behavior. an indication of the specimen temperature to 60.1 °C, differ-
5.2 This test method is useful for research, quality control, ential sensors to detect heat flow difference between the
and specification acceptance. specimen and reference with a sensitivity of 6µW, a means of

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 E1356 − 23
sustaining a test chamber environment of a purge gas of NOTE 1—Other, preferably inert, gases may be used, and other heating
10 mL ⁄min to 100 mL/min within 4 mL/min, a Temperature and cooling rates may be used, but must be reported.
Controller, capable of executing a specific temperature pro- 10.3 Hold temperature until an equilibrium as indicated by
gram by operating the furnace(s) between selected temperature the instrument response is achieved.
limits at a rate of temperature change of up to 20 °C ⁄min 10.4 Program cool at a rate of 20 °C ⁄min to 50 °C below the
constant to 60.5 °C ⁄min. transition temperature of interest.
7.2 A Data Collection Device, to provide a means of 10.5 Hold temperature until an equilibrium as indicated by
acquiring, storing, and displaying measured or calculated the instrument response is achieved.
signals, or both. The minimum output signals required for DSC
are heat flow, temperature and time. 10.6 Repeat heating at same rate as in 10.2, and record the
heating curve until all desired transitions have been completed.
7.3 Containers, (pans, crucibles, vials, etc.) that are inert to Other heating rates may be used but must be reported.
the specimen and reference materials and that are of suitable
structural shape and integrity to contain the specimen and 10.7 Determine temperatures Tm (preferred) Tf, or Ti. (See
references. Fig. 1.)
7.4 For ease of interpretation, an inert reference material where:
with an heat capacity approximately equivalent to that of the Tig = inflection temperature, °C
specimen may be used. The inert reference material may often Tf = extrapolated onset temperature, °C, and
be an empty specimen capsule or tube. Tm = midpoint temperature, °C.
7.5 Nitrogen, or other inert purge gas supply, of purity equal
to or greater than 99.9 %.
Increasing the heating rate produces greater baseline shifts
7.6 Analytical Balance, with a capacity greater than 100 mg,
thereby improving detectability. In the case of DSC the signal
capable of weighing to the nearest 0.01 mg.
is directly proportional to the heating rate in heat capacity
8. Specimen Preparation measurements.
8.1 Powders or Granules—Avoid grinding if a preliminary NOTE 2—The glass transition takes place over a temperature range and
is known to be affected by time dependent phenomena, such as the rate of
thermal cycle as outlined in 10.2 is not performed. Grinding or heating (cooling). For these reasons, the establishment of a single number
similar techniques for size reduction often introduce thermal for the glass transition needs some explanation. Either Tf or Tm or Ti may
effects because of friction or orientation, or both, and thereby be selected to represent the temperature range over which the glass
change the thermal history of the specimen. transition takes place. The particular temperature chosen must be agreed
on by all parties concerned. In selecting which value should be taken as
8.2 Molded Parts or Pellets—Cut the samples with a Tg, the reader may wish to consider the following:
microtome, razor blade, paper punch, or cork borer (size No. 2 (1) Tm was found to have higher precision than Tf (see 12.3).
or 3) to appropriate size in thickness or diameter, and length (2) The measurement of Tf is often easier for those who construct the
respective tangents by hand.
that will approximate the desired mass in the subsequent
(3) Tm (preferred) or Ti is more likely to agree with the measurement of
procedure. Tg by other techniques since it is constructed closer to the middle of the
8.3 Films or Sheets—For films thicker than 40 µm, see 8.2. temperature range over which the glass transition occurs.
(4) Tf may be taken to more closely represent the onset of the
For thinner films, cut slivers to fit in the specimen tubes or temperature range over which the glass transition occurs. Any comparison
punch disks, if circular specimen pans are used. of glass transition temperatures should contain a statement of how the test
8.4 Report any mechanical or thermal pretreatment. was run and how the value was obtained.
10.8 Recheck the specimen mass to ensure that no loss or
9. Calibration decomposition has occurred during the measurement.
9.1 Using the same heating rate, purge gas, and flow rate as 11. Report
that to be used for analyzing the specimen, calibrate the
temperature axis of the instrument following the procedure 11.1 Report the following information:
given in Test Method E967. 11.1.1 A complete identification and description of the
material tested.
10. Procedure 11.1.2 Description of instrument used for the test.
11.1.3 Statement of the dimensions, geometry, and material
10.1 Use a specimen mass appropriate for the material to be of the specimen holder.
tested. In most cases a 5 mg to 20 mg mass is satisfactory. An 11.1.4 The scan rate in °C/min.
amount of reference material with a heat capacity closely 11.1.5 Description of temperature calibration procedure.
matched to that of the specimen may be used. An empty 11.1.6 Identification of the specimen environment by
specimen pan may also be adequate. pressure, gas flow rate, purity and composition, including
10.2 If appropriate, perform and record an initial thermal humidity, if applicable.
program in flowing nitrogen or air environment using a heating 11.1.7 Results of the transition measurements using tem-
rate of 10 °C ⁄min to a temperature at least 20 °C above Te to perature parameters (Tg, etc.) cited in Fig. 1, or any combina-
remove any previous thermal history. (See Fig. 1.) tion of parameters that were chosen.

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 E1356 − 23
11.1.8 Tg (half extrapolated heat capacity temperature) is 12.3 Precision:
preferred. DSC Determination of Tg: Tf Data
11.1.9 Any side reactions (for example, crosslinking, ther- 95 % Limit, °C
Material Tf, °C Repeatability Reproducibility
mal degradation, oxidation) shall also be reported and the Polyurethane 4.5 4.59 6.53
reaction identified, if possible. Polystyrene 103.6 2.05 3.18
Epoxy Glass 118.4 3.90 6.88
12. Precision and Bias4 DSC Determination of Tg:Tm Data
95 % Limit, °C
12.1 Interlaboratory Test Program—An interlaboratory Material Tm, °C Repeatability Reproducibility
study for the determination of glass transition temperature as Polyurethane 12.2 2.24 4.15
indicated by both the midpoint and the extrapolated onset was Polystyrene 106.3 1.85 2.02
Epoxy Glass 123.0 2.77 5.17
conducted in 1984. Three polymeric materials were tested;
polyurethane, polystyrene, and epoxy glass. Each of six par- The above terms repeatability and reproducibility limit are
ticipants tested four specimens of each material. (One did not used as specified in Practice E177. The respective standard
report test data on polyurethane.) Practice E691 was followed deviations among test results may be obtained by dividing the
for the design and the analysis of the data. numbers in the third and fourth columns by 2.8.
12.2 Test Result—The precision information given below in 12.4 The bias for these measurements is undetermined
Celsius degrees is for the comparison of two test results, each because there are no reference values available for the mate-
of which is a single determination. rials used.

13. Keywords
4
Supporting data have been filed at ASTM International Headquarters and may
be obtained by requesting Research Report RR:E37-1012. Contact ASTM Customer 13.1 differential scanning calorimetry (DSC); differential
Service at [email protected]. thermal analysis (DTA); glass transition; specific heat capacity

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