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: E793 − 06 (Reapproved 2018)

Standard Test Method for

Enthalpies of Fusion and Crystallization by Differential
Scanning Calorimetry1
This standard is issued under the fixed designation E793; 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 mendations issued by the World Trade Organization Technical

1.1 This test method describes the determination of the Barriers to Trade (TBT) Committee.
enthalpy (heat) of fusion (melting) and crystallization by 2. Referenced Documents
differential scanning calorimetry (DSC).
2.1 ASTM Standards:2
1.2 This test method is applicable to solid samples in E473 Terminology Relating to Thermal Analysis and Rhe-
granular form or in any fabricated shape from which an ology
appropriate specimen can be cut, or to liquid samples that E794 Test Method for Melting And Crystallization Tempera-
crystallize within the range of the instrument. Note, however, tures By Thermal Analysis
that the results may be affected by the form and mass of the E968 Practice for Heat Flow Calibration of Differential
specimen, as well as by other experimental conditions. Scanning Calorimeters
1.3 The normal operating temperature range is from −120 to E1142 Terminology Relating to Thermophysical Properties
600°C. The temperature range can be extended depending E1860 Test Method for Elapsed Time Calibration of Ther-
upon the instrumentation used. mal Analyzers
1.4 This test method is generally applicable to thermally 2.2 ISO Standard:3
stable materials with well defined endothermic or exothermic ISO 11357–3 Plastics – Differential Scanning Calorimetry
behavior. (DSC) – Part 3: Temperature and Enthalpy of Melting and
Crystallization
1.5 Computer or electronic based instruments, techniques,
or data treatment equivalent to those in this test method may 3. Terminology
also be used.
3.1 Definitions—Specialized terms used in this test method
1.6 The values stated in SI units are to be regarded as are defined in Terminologies E473 and E1142.
standard. No other units of measurement are included in this
standard. 4. Summary of Test Method
1.7 The enthalpy of melting and crystallization portion of 4.1 This test method involves heating (or cooling) a test
ISO 11357-3 is equivalent to this standard. specimen at a controlled rate in a controlled environment
1.8 This standard does not purport to address all of the through the temperature region of fusion or crystallization. The
safety concerns, if any, associated with its use. It is the heat flow associated with fusion, an endothermic process (and
responsibility of the user of this standard to establish appro- crystallization, an exothermic process), is recorded and inte-
priate safety, health, and environmental practices and deter- grated over time. Absolute values for the enthalpy of fusion
mine the applicability of regulatory limitations prior to use. (and enthalpy of crystallization) or relative values for compara-
1.9 This international standard was developed in accor- tive purposes can thus be obtained.
dance with internationally recognized principles on standard- NOTE 1—Melting (or crystallization) temperatures are sometimes de-
ization established in the Decision on Principles for the termined in conjunction with measurements of the enthalpy of fusion or
Development of International Standards, Guides and Recom- crystallization. These temperature values may be obtained by Test Method
E794.

1 2
This test method is under the jurisdiction of ASTM Committee E37 on Thermal For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Measurements and is the direct responsibility of Subcommittee E37.01 on Calo- contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
rimetry and Mass Loss. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved April 1, 2018. Published May 2018. Originally the ASTM website.
3
approved in 1981. Last previous edition approved in 2012 as E793 – 12. DOI: Available from American National Standards Institute (ANSI), 25 W. 43rd St.,
10.1520/E0793-06R18. 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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 E793 − 06 (2018)
5. Significance and Use 6.5.3 A cooling capability to hasten cool down from el-
evated temperatures, to provide constant cooling rates, or to
5.1 Differential scanning calorimetry provides a rapid
sustain an isothermal subambient temperature.
method for the determination of enthalpic changes accompa-
nying first-order transitions of materials. 7. Hazards and Interferences
5.2 This test method is useful for quality control, specifica- 7.1 Since milligram quantities of specimens are used, it is
tion acceptance, and research. essential that samples are homogeneous.

6. Apparatus 7.2 Toxic or corrosive effluents, or both, may be released

when heating the material and could be harmful to the
6.1 DSC, The essential instrumentation required to provide personnel or the apparatus.
the minimum differential scanning calorimetric capability for
7.3 Samples that release volatiles upon heating will change
this method includes:
mass and invalidate the test.
6.1.1 DSC Test Chamber composed of:
7.4 In the use of commercial instrumentation, the operator
6.1.1.1 a furnace(s), to provide uniform controlled heating
should read the manufacturer’s operations manual to be aware
and cooling of a specimen and reference to a constant
of potential hazards of operation, such as burn hazards from
temperature or at a constant rate from –120 to 600°C.
hot surfaces.
6.1.1.2 A temperature sensor, to provide an indication of the
specimen temperature to 60.1°C. 8. Sampling
6.1.1.3 Differential sensors, to detect a heat flow difference
8.1 Powdered or granular materials should be mixed thor-
between specimen and reference with a range of at least 6100
oughly prior to sampling and should be sampled by removing
mW and a sensitivity of 65 mW.
portions from various parts of the container. These portions, in
6.1.1.4 A means of sustaining a test chamber environment turn, should be combined and mixed well to ensure a repre-
of an inert purge gas as at rate of 10 to 50 6 5 mL/min. sentative specimen for the determination. Liquid samples may
NOTE 2—Typically, 99.99+ % pure nitrogen, argon or helium is used be sampled directly after mixing.
when oxidation in air is a concern. Unless effects of moisture are to be 8.2 In the absence of other information, samples are as-
studied, use of dry purge gas is recommended and is essential for
operation at subambient temperatures. sumed to be analyzed as received. If some heat or mechanical
treatment is applied to the sample prior to analysis, this
6.1.2 A temperature controller, capable of executing a treatment, and any mass loss resulting from this treatment,
specific temperature program by operating the furnaces(s) should be noted in the report.
between selected temperature limits at a rate of temperature
change of up to at least 20°C/min constant to 60.1°C/min. or 9. Calibration
at an isothermal temperature constant to 60.1°C.
9.1 Using the same heating rate, purge gas, and flow rate to
6.1.3 A recording device, capable of recording and display- be used for specimens, calibrate the heat flow axis of the
ing on the Y-axis any portion of the heat flow signal (DSC instrument, using the procedure in Practice E968.
curve) including the signal noise as a function of any portion of
the temperature or time signal on the X-axis including the 9.2 Calibrate the elapsed time signal of the differential
signal noise. scanning calorimeter using Test Method E1860.
6.2 Specimen Containers, (pans, crucibles, vials, lids, 10. Procedure
closures, seals, etc.) that are inert to the specimen and reference
10.1 Weigh 1 to 15 mg of specimen to an accuracy of 60.1
materials and that are of suitable structural shape and integrity
% into a clean, dry specimen capsule.
to contain the specimen and reference.
NOTE 4—The specimen mass to be used depends on the magnitude of
6.3 Nitrogen, or other inert gas supply for purging purposes. the transition enthalpy and the volume of the capsule. For comparing
6.4 Balance, with capacity greater than 100 mg, capable of multiple results, use similar mass (65 %) and encapsulation. Weighing to
less accuracy than one part per thousand may limit the accuracy of the
weighing to the nearest 0.01 mg, or better. enthalpy determination.
NOTE 3—Balances readable to 0.01 mg are suitable for use with test 10.2 Seal or crimp the specimen capsule with a lid under
specimens on the order of 10 mg in mass. A balance readable to 0.001 mg ambient conditions. Minimize the free space between the
is required for test specimens on the order of 1 mg in mass. to achieve the
specimen and the lid. For specimens sensitive to oxidation,
precision described in this standard.
hermetic sealing under an inert atmosphere may be desirable.
6.5 Auxiliary instrumentation considered useful or neces-
10.3 Load the specimen into the instrument chamber. Purge
sary for conducting this method includes:
the chamber with dry nitrogen (or other inert gas) at a flow rate
6.5.1 Data Analysis capability of integrating the heat flow of 10 to 50 mL/min throughout the experiment.
signal as a function of time to produce enthalpy information in
units of mJ to a precision of 61 %. 10.4 The specimen may be heated rapidly to 50°C below the
6.5.2 A means, tool or device to close, encapsulate, or seal expected melting temperature and allowed to equilibrate.
the container of choice. NOTE 5—For some materials, it may be necessary to start the scan

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 E793 − 06 (2018)
substantially lower in temperature, for example, below the glass transition,
in order to establish a baseline where there is no evidence of melting or
crystallization.
10.5 Heat the specimen at 10°C/min through the melting
range until baseline is reestablished above the melting endo-
therm.
NOTE 6—Other heating rates may be used but shall be noted in the
report. Results may depend on heating rate and equilibration times.
NOTE 7—To allow the system to achieve steady state, provide at least
3 min of scanning time both before and after the peak.
10.6 Hold the specimen at this temperature for 2 min.
NOTE 8—Other periods may be used, but shall be noted in the report
10.7 Cool the specimen at 10°C/min through the exotherm FIG. 2 Crystallization Exotherm (DSC)

NOTE 9—Other cooling rates may be used but must be noted in the
report.
NOTE 10—To allow the system to achieve steady state, provide at least
3 min of scanning time both before and after the peak.
12. Report
NOTE 11—For some materials, it may be necessary to scan several tens 12.1 Report the following information:
of degrees below the peak maximum in order to attain a constant baseline. 12.1.1 Complete identification and description of the mate-
Record the accompanying thermal curve.
rial tested including source and manufacturer code.
10.8 Reweigh the specimen after completion of scanning 12.1.2 Description of the instrument used for test.
and discard. Discard the data if mass losses exceed 1 % of the 12.1.3 Statement of the mass, dimensions, geometry, and
original mass or if there is evidence of reaction with the material of the specimen capsule, and the heating (cooling) rate
specimen capsule. used.
11. Calculation 12.1.4 Description of the calibration procedure.
12.1.5 Identification of the specimen environment by gas
11.1 Construct a baseline on the differential heat flow flow rate, purity, and composition.
thermal curve by connecting the two points at which the 12.1.6 Enthalpy of fusion (or crystallization) in J/g.
melting endotherm (or freezing exotherm) deviates from the 12.1.7 The specific dated edition of the method used.
relatively straight baseline (see Fig. 1 and Fig. 2).
11.2 Integrate the area under the fusion endotherm (or 13. Precision and Bias4
crystallization exotherm) as a function of time. 13.1 The precision of this test method was determined in an
11.3 Calculate, retaining all meaningful decimal places, the interlaboratory investigation in which 18 laboratories partici-
enthalpy of fusion (or enthalpy of crystallization) (Ho) using pated using six instrument models. Polymeric, organic, and
Eq 1. inorganic materials were included for measuring both enthalpy
H 5 E H o /W (1) of fusion and crystallization.
13.2 The following criteria should be used for judging the
where:
acceptability of enthalpy of fusion or crystallization results:
H = enthalpy of fusion (or crystallization) of the sample in 13.2.1 Repeatability (Single Analyst)—The coefficient of
J/g, variation of results (each the average of duplicates), for
W = mass of the specimen, mg, enthalpy of fusion or crystallization, obtained by the same
E = Calibration constant from Practice E968,
analyst or instrument on different days, is estimated to be 2.8 %
Ho = observed enthalpy of fusion (or crystallization), mJ
with 88 degrees of freedom. Two such averages should be
considered suspect (95 % confidence level) if they differ by
more than 7.8 %.
13.2.2 Reproducibility of Polymers (Multilaboratory)—The
coefficient of variation of results (each the average of dupli-
cates) for enthalpy of fusion or crystallization for polymers
(that is, materials melting or crystallizing over a broad tem-
perature range), obtained by analysts in different laboratories,
is estimated to be 8.0 % at 30 degrees of freedom. Two such
results should be considered suspect (95 % confidence level) if
they differ by more than 23 %.

4
Supporting data have been filed at ASTM International Headquarters and may
be obtained by requesting Research Report RR:E37-1001. Contact ASTM Customer
FIG. 1 Melting Endotherm (DSC) Service at [email protected].

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 E793 − 06 (2018)
13.2.3 Reproducibility of Pure Materials 13.5.1 Within laboratory variability may be described using
(Multilaboratory)—The coefficient of variation of results (each the repeatability value (r) obtained by multiplying the standard
the average of duplicates) for enthalpy of fusion or crystalli- deviation by 2.8. The repeatability value estimates the 95 %
zation for organic and inorganic materials (that is, materials confidence limit.
melting or crystallizing over a narrow temperature range), 13.5.2 Repeatability, r, for ∆H, the melting enthalpy of tin
obtained by analysts in different laboratories, is estimated to be was 0.92 J/g (1.5 %).
3.0 % at 58 degrees of freedom. Two such results should be 13.5.3 Repeatability, r, for ∆H, the melting (peak) enthalpy
considered suspect (95 % confidence level) if they differ by of polypropylene was 9.3 J/g (10.3 %).
more than 8.6 %.
13.5.4 Repeatability, r, for ∆H, the crystallization enthalpy
13.3 An estimation of the accuracy of the enthalpy of fusion of polypropylene was 3.1 J/g (3.4 %).
measurement was obtained by comparing the overall mean 13.5.5 Between laboratory variability may be described
value obtained during the interlaboratory testing with values using the reproducibility value (R) obtained by multiplying the
reported in the literature. standard deviation by 2.8. The reproducibility value estimates
Material Heat of Fusion (J/g) the 95 % confidence limit.
Interlaboratory Test Literature
LeadA 22.2 ± 0.8 23.16 ± 0.30 13.5.5.1 Reproducibility, R, for ∆H, the melting enthalpy of
Adipic acidB 252 ± 9 238.5 ± 2.4 tin was 1.22 J/g (2.0 %).
A
13.5.5.2 Reproducibility, R, for ∆H, the melting (peak)
Hultgren, R. R., et al., Selected Values of Thermodynamic Properties of the
Elements, John Wiley & Sons, Inc., New York, NY, 1973.
enthalpy of polypropylene was 20.1 J/g (22.5 %).
B
Cingolani, A., et al., Journal of Thermal Analysis, Vol 6, 1974, p. 87. 13.5.5.3 Reproducibility, R, for ∆H, the crystallization en-
Based on this comparison, the accuracy of the enthalpy of thalpy of polypropylene was 6.7 J/g (7.3 %).
fusion measurement is estimated to be 65.5 %. 13.6 Bias:
13.4 A second interlaboratory test (ILT) was carried out in 13.6.1 An estimate bias is obtained by comparing the mean
1997 to determine the extent to which more modern instru- melting value of tin compared to the known melting point
mentation and computer calculations have improved the pre- using literature values. That is, bias = (mean value) – (known
cision and bias over the original ILT. The tests were carried out value). The average from this ILT was found to be 60.27 J/g.
on two materials, one pure material which melts completely at The literature value (NIST certified value) for 99.9995 % pure
a single temperature, and one polymer which melts over a tin is 60.22 J/g. This ILT average and the literature value are
temperature range. A total of 10 laboratories using 6 different the same within the ILT precision; hence, the bias is not
DSC models from 4 manufacturers participated. significant.
13.5 Precision results for melting tin, and for melting and
crystallization of polypropylene. For the melting of 14. Keywords
polypropylene, an uncertainty in how to define the peak start 14.1 crystallization; differential scanning calorimeter; DSC;
resulted in a large apparent imprecision. energy; enthalpy; fusion; heat; melting

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