You are on page 1of 7

Designation: E537 − 12

Standard Test Method for
The Thermal Stability of Chemicals by Differential Scanning
Calorimetry1
This standard is issued under the fixed designation E537; 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.
This standard has been approved for use by agencies of the U.S. Department of Defense.

INTRODUCTION

Committee E27 is currently engaged in developing methods to determine the hazard potential of
chemicals. An estimate of this potential may usually be obtained by the use of program CHETAH 7.0
to compute the maximum energy of reaction of the chemical or mixture of chemicals.2
The expression “hazard potential” as used by this committee is defined as the degree of
susceptibility of material to ignition or release of energy under varying environmental conditions.
The primary purpose of this test method is to detect enthalpic changes and to approximate the
temperature of initiation and enthalpies (heats) of these events. Differential scanning calorimetry offers
the advantage of using very small specimens on the order of a few milligrams.

1. Scope the responsibility of the user of this standard to establish
1.1 This test method describes the ascertainment of the appropriate safety and health practices and determine the
presence of enthalpic changes in a test specimen, using applicability of regulatory limitations prior to use. Specific
minimum quantities of material, approximates the temperature safety precautions are given in Section 8.
at which these enthalpic changes occur and determines their
2. Referenced Documents
enthalpies (heats) using differential scanning calorimetry or
pressure differential scanning calorimetry. 2.1 ASTM Standards:3
E473 Terminology Relating to Thermal Analysis and Rhe-
1.2 This test method may be performed on solids, liquids, or
ology
slurries.
E691 Practice for Conducting an Interlaboratory Study to
1.3 This test method may be performed in an inert or a Determine the Precision of a Test Method
reactive atmosphere with an absolute pressure range from 100 E967 Test Method for Temperature Calibration of Differen-
Pa through 7 MPa and over a temperature range from 300 to tial Scanning Calorimeters and Differential Thermal Ana-
800 K (27 to 527°C). lyzers
1.4 The values stated in SI units are to be regarded as E968 Practice for Heat Flow Calibration of Differential
standard. No other units of measurement are included in this Scanning Calorimeters
standard. E1445 Terminology Relating to Hazard Potential of Chemi-
cals
1.5 There is no ISO standard equivalent to this test method.
E1860 Test Method for Elapsed Time Calibration of Ther-
1.6 This standard may involve hazardous materials, mal Analyzers
operations, and equipment. This standard does not purport to
address all of the safety concerns associated with its use. It is 3. Terminology
3.1 Definitions:
1
This test method is under the jurisdiction of ASTM Committee E27 on Hazard 3.1.1 Specific technical terms used in this standard are
Potential of Chemicals and is the direct responsibility of Subcommittee E27.02 on defined in Terminologies E473 and E1445, and include
Thermal Stability and Condensed Phases.
Current edition approved Dec. 1, 2012. Published December 2012. Originally
approved in 1976. Last previous edition approved in 2007 as E537 – 07. DOI:
3
10.1520/E0537-12. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
2
A complete assessment of the hazard potential of chemicals must take into contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
account a number of realistic factors not considered in this test method or the Standards volume information, refer to the standard’s Document Summary page on
CHETAH program. the ASTM website.

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

1

5.1 A host of environmental factors affect the existence. air) gas at a purge rate of 50 6 5 mL/min.2 Definitions of Terms Specific to This Standard: 5.5 The four significant criteria of this test method are: the 3. that change is indicated by a departure (T). necessarily denote the relative hazard in a particular applica. 7.2. 7. occur and their enthalpies (heats).2. use of dry purge gas is recommended and is essential for exotherm and its approximate temperature are the most signifi. at least 99 % pure nitrogen. observed. 7.1 DSC curve—a record of a differential scanning calo. change of enthalpy. the approximate temperature deviation-from-baseline. Unless effects of moisture are to be studied. NOTE 1—The choice of pressure may sometimes be estimated by the 3.4 Means of sustaining a test chamber environment of tion.2 A sample of the material to be examined and of a confinement.1 K/min. As an example. elevate the boiling point of a volatile organic substance 100°C. certain exothermic reactions are often inert (for example. to provide uniform controlled heating of 5. Alternatively.1. detection of a change of enthalpy. 1 and 2 and Terminology E473).1.2 Temperature sensor. Thus. scanning calorimetric capability for this test method include: 7. an exothermic reaction may be small at normal atmospheric rimeter where the change in heat flow (∆q) is plotted on the pressure. A record of ∆q on the ordinate is 7. and Under these conditions exothermic decomposition is often thermal stability. the estimation of its enthalpy and the observance of effects due to the cell atmosphere and pressure.2. hazard. nitrogen.1 The equipment used in this test method shall be capable 4. NOTE 3—Other purge gas rates may be used but shall be reported. or reference or the average temperature of both. cant criteria in this test method (see Section 3 and Fig. to detect a temperature or heat flow difference between the specimen and reference equivalent 5.1 K. 5.2.1 Furnace(s). reaction.1 Discussion—This is also known as the first. making an assessment of the temperature of instabil- ordinate and temperature or time is plotted on the abscissa (see ity difficult. 4. including heating rate.3 When volatile substances are being studied.1. instrument sensitivity. extrapolated on. instrumentation required to provide the minimum differential mined and reported. it is impor. 1). extrapolated onset tempera. a measurement is made of the heat flow (∆q) 6. differential scanning calorimetry. Apparatus made as a function of temperature (T) on the abscissa. uncharacterized chemical substance or mixture (see Section 8). 4. Limitations associated with the observed change of enthalpy. a rate of temperature change of from 2 to 20 K/min constant to an absolute pressure of 1. operation at subambient temperatures.2 Differential Scanning Calorimeter (DSC)—the essential ture (Te).3 Differential sensor. capable of executing a spe- tant to perform this test with a confining pressurized atmo. 7. 7.1 mW.2.1. degree of 4. 7.2 The magnitude of the change of enthalpy may not to 0. and atmosphere reactivity.1 In DSC. For example.3. to different atmospheres of equilibrated pressures. set value. 3. at which the event occurs. first-deviation-from baseline. will affect the detect- thermally inert reference material are placed in separate ability of an exothermic reaction using this procedure. and the integrated peak area (enthalpy) are deter. ing to the maximum deflection of the DSC curve. to provide an indication of the mended as an early test for detecting the thermal hazards of an specimen/furnace temperature to 60. peak. E537 − 12 calorimeter.4 For some substances the rate of enthalpy change during 3.2. Therefore. are made to measure the absolute temperature (T) of the sample magnitude.5 The onset temperature (To). Significance and Use 7. pressure will improve the assessment by increasing the rate of 3. helium or argon) or reactive (for accompanied by gas evolution that increases the potential example.2.2.3 onset temperature (To)—the temperature at which a pressure of the application to which the material is exposed.2. Provisions 6. and temperature of an exothermic reaction.1 A test chamber composed of: 5.14 MPa (150 psig) will generally 60. and 2 .2 peak temperature (Tp)—the temperature correspond. it is imperative that the qualitative results obtained from the application of this test method be viewed only as an 4.1 This test method is useful in detecting potentially a specimen and reference to a constant temperature or at a hazardous reactions including those from volatile chemicals constant rate within the applicable temperature range of this and in estimating the temperatures at which these reactions method. the presence of an employed when oxidation in air is a concern. holders. the extent of energy release for certain exothermic reactions may differ widely with the extent of NOTE 2—Typically.1.5 Temperature controller. heated at a controlled rate of 2 to 20 K/min under an equilibrated atmosphere. and shall have the capability of subjecting the sample cell from the initially established baseline of the heat flow record. Generally a repeated analysis at an elevated Figs.3 The sample and reference materials are simultaneously indication of the thermal stability of a chemical. cific temperature program by operating the furnace(s) between sphere so that changes of enthalpy that can occur above normal selected temperature limits (ambient temperature to 800 K) at boiling or sublimation points may be detected. Some. This test method is recom. Summary of Test Method 4.2. argon or helium is confinement of volatile products.4 When the sample undergoes a transition involving a of displaying changes of enthalpy as a function of temperature change of enthalpy. deflection from the established baseline is first observed.

1 Typical DSC Curve with Exotherm .3 E537 − 12 FIG.

4 E537 − 12 FIG. 2 DSC Curve Illustrating a Melting Process Immediately Followed by an Exothermic Decomposition .

27 MPa (0 to Method E1860. with a capacity of 100 mg or greater to weigh to start with a specimen size of no more than 1 mg. Accordingly.6 A data collection device. conditions: 7. 9. 170 psig) pressure limits required by this test method. NOTE 6—The onset temperature. therefore.3 10.3 If subambient temperatures are desired: transformation over the temperature range under study. the applied pressure shall exceed the vapor with such temperatures and pressures should be observed. signals.1 The selection of an adequate sample size will depend MPa (0 and 170 psig).2. or similar device to adjust the energy release.4 Pressure Range— An equilibrated absolute pressure of The Material Safety Data Sheet shall be acquired and studied 1. Practice E967. to hasten cool down from elevated reference materials include calcined aluminum oxide. (pans.3 The use of this test method may require operation at characteristics of the material. In some cases.3 Temperature Range—The temperature typically ranges appropriate test shall be conducted on those materials prior to from 300 to 800 K (27 to 527°C).2. may be released which the applied pressure shall exceed the vapor pressure of the material depends upon the test apparatus. The amount by 8. crucibles. and time .2.2). or both. 50 mg.2 Samples should be representative of the material being 7.2. sample temperature dependence of the transducer. To elevated temperatures and pressures.2 Where particle size reduction by grinding is necessary. conditions.2. Only results obtained at the the user of the test method should presume that the material is same heating rate shall be compared. or both. The minimum output signals required for 9. it may be desirable to set the applied personnel or the apparatus.2. extrapolated onset temperature.4 Calibrate the time signal within 60. it may evaporate before the end temperature is reached.1 The use of this test method as an initial test for material an exotherm (see and Fig. it is safest 7. this method. or similar means to maintain the applied pressure in the test chamber constant to 65 %.3 Pressure transducer.10 and 1. If the material to be tested has a high vapor pressure. capable of sustaining a 10. 11. Typical 7. Recommended Conditions of Tests to the specimen and reference materials and which are of 11.3 Calibrate the heat flow signal within 61 % using Test 7.2. grinding. temperature. All precautions associated minimize evaporation. Additionally.3 The reference material must not undergo any thermal 7.2 Calibrate the temperature signal within 62 K using differential scanning calorimetry are.2.2. 11. size of the pinhole (12. 7. sensitive to friction and electrostatic discharge. 7. to a sensitivity of 610 µg.2. the degree of dilution 7. If an endothermic response is immediately followed by 8.2 MPa (150 psig) is adequate for most elevated pressure tests. heating rate when heating the material and could be harmful to the and other factors.2. be carried applied pressure in the test chamber to 65 % of the desired out on as small a quantity of material as possible. or both.3 Containers. 2). peak temperature are affected by heating rate. upon the availability of the material.4 Pressure regulator. etc.2 Heating Rate— A rate of 10 to 20 K/min is considered 8. size must be compatible with the potential for a sudden large 7. and displaying measured or calculated manual. to control pressurizing gas in the test cham. Use of an exhaust system to remove pressure to be the maximum pressure anticipated under production such effluents is recommended. studied including particle size and purity. or similar device to measure required. ber or to isolate components of the pressure system. or an empty container. beads.2. or both. 7. to provide a means of the apparatus manufacturer as described in the operator’s acquiring. vials. 9.1 Perform any calibration procedures recommended by 7. E537 − 12 NOTE 4—The temperature range of the apparatus and the experiment 9. then lower heating rates of 2 to whose potential hazards are unknown requires that precautions 6°C/min are recommended.2.2. pressure of the material at the maximum test temperature. glass temperatures and to sustain an isothermal subambient tempera.) which are inert 11.1 Cooling system. silicone oil. Safety Precautions normal.1 Specimen Size—A 1 to 5-mg specimen is generally suitable structural shape and integrity to contain the specimen considered adequate. size if the exothermic response is insufficiently large.5 Ballast. Calibration may be extended to 120 K with the use of appropriate cooling or to 1273 K or greater with suitable apparatus. 5 . 11.2. be taken during the sample preparation and testing.1. 10. heat flow.2 If experiments are to be carried out under pressure Method E968. storing.5 % using Test chamber at any applied pressure within 0. Sample and Reference Materials regulated gas pressure in the test chamber between 0. This test method should.3. prior to handling unknown materials.4 Toxic or corrosive effluents.1 Pressure vessel.10 to 1. NOTE 7—The applied pressure should be selected based upon the 8. and the heating rate. the sensitivity of the instrument.2 Pressurized gas source. Decrease the specimen size if the re- and reference in accordance with the specific requirements of sponse is greater than 8 mW. or similar means of sealing the test 9. Use of suitable protective equipment is always recommended when preparing materials of unknown hazard.4 Balance. typically 1 to value. ture. and 8. 10.6 Valves. the magnitude of the the pressure inside the test chamber to 65 % including any change of enthalpy. NOTE 5—For materials whose characteristics are unknown. and then increase the specimens or containers.2.

and more importantly. response for the ordinate but will also increase the measured onset 14.1. seal and adjust the measuring cell atmosphere to the desired equilibrium pressure. place the sample and reference 13. point on the baseline aster the reaction (see Fig. and K/min and record the DSC curve. NOTE 10—Hermetically sealed containers will self-pressurize with the enthalpy of the reaction. specimen to within 6 10 µg and record this weight as n in mg. 14. or both. For most organic 14.3 Composition and pressure of the sample atmosphere. Calculations permit the loss of material.5 Record the onset temperature (To). Compare the con- tainer weight with n determined in 12.2 Integrate the area under the reaction exotherm as a materials in hermetically sealed containers with an appropriate function of time. A vent hole may also 13. 2).1 Sample and reference by name. For most specimens. extrapolated onset 12.3 Calculate.1. E537 − 12 12. Enthalpies measured with sealed containers may be different from those with vented containers due to differences in where: the heat of vaporization. NOTE 9—When sealed containers are used. NOTE 12—Any increase in heating rate may accentuate the recorder pretreatment. FIG. 3).2 Apparatus and sample containers. 13. 3 Integration of Exotherm 6 . Procedure 12. combi- nation thereof. measuring temperature due to increased partial pressures and gas evolu- tion. or any sample preparation or NOTE 11—Other heating rates may be used but shall be reported. 12. ∆H = enthalpy of reaction. they should be provided with a 50 to 100 µm diameter vent (pinhole) to ensure that the internal pressure is in equilibrium with the applied pressure.7 Reweigh the specimen container. sure within its measuring cell. highest temperature of interest is recorded or until the sample is destroyed or is lost by volatilization.1 Report the following information: (20 to 500°C).3 For equipment that cannot maintain an elevated pres. cell. composition. In either situation a encountered (see Fig. 12. samples suspected of being potentially energetic may exhibit heating rate (2 to 10 K/min) when a complex change of enthalpy is nondescript exothermic activity at ambient pressure. weigh the test observed (see Fig.6 Restore the measuring cell to ambient temperature and NOTE 8—For volatile materials it is often of interest to examine thermal pressure upon completion of the analysis.8 Calculate the enthalpy of the exothermic reaction by the procedures described in 14. Report compounds the normal temperature range is from 290 to 770 K 14.1.4 Heat the measuring cell at a controlled rate of 2 to 20 m = mass of the text specimen. the loss of heat that will 13. J g-1. Continue heating until the A = area of the reaction exotherm.1.2 For equipment that includes a pressurizable measuring container weight observed. stability at temperatures beyond the normal boiling or sublimation point. NOTE 13—It may be informative to repeat the analysis at a slower Additionally. Into this tared specimen container. J/g. or formula. atmosphere. this internal pressure will not be known but is ∆H 5 A/m typically less than 300 kPa. retaining all the meaningful decimal places. repeat analysis in an atmosphere of elevated pressure using either sealed sample containers or a pressurized measuring cell is recommended. 12. from a point on the baseline before the reaction exotherm to a 12. temperature of an exothermic reaction.1 Weigh and record the mass of the empty specimen temperature (Tc) and peak temperature (Tp) for any reaction(s) container. 14.1 Construct a baseline on the differential heat flow curve nullify the determination of enthalpy. 12. Report any change in 12. 1). mg.

1 The reproducibility relative standard deviation for 14. thermal stability 4 5 Supporting data have been filed at ASTM International Headquarters and may Villenave. This standard is copyrighted by ASTM International. 1980.2. or extrapolated 15. 610-832-9555 (fax).1 The mean values for the reaction enthalpy.3. B. butylperoxybenzoate) in a single laboratory provides the fol- scribed using the repeatability value (r) obtained by multiply. 15.4 Heating rate and temperature range.2. PO Box C700. and the risk of infringement of such rights.4 (158.1 The mean value for the extrapolated onset tempera- ity value estimates the 95 % confidence limit. lowing information: ing the repeatability standard deviation by 2.7°C).2. Precision and Bias value for reaction enthalpy. Your comments will receive careful consideration at a meeting of the responsible technical committee.org (e-mail).2 The mean value for the enthalpy of reaction by action is enthalpy is 3.2 Precision—Within laboratory variability may be de.4.2 When a thermal analysis is repeated using a different reaction enthalpy is 4.3 The repeatability standard deviation for the onset temperature is 3. This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and if not revised. Te= 469. 15.2. two ture is 391.1 differential scanning calorimetry. Users of this standard are expressly advised that determination of the validity of any such patent rights. Thermochimica Acta. Mallard.2 Intralaboratory testing on one material (t- 15. Danvers.4.J.1 An interlaboratory study (ILS) was conducted in 2000 onset temperature for trityl azide. and specimen percent weight loss.2 The reproducibility standard deviation for extrapo- note any significant changes in the DSC curves resulting from lated onset temperature is 3. either reapproved or withdrawn.8.2 The repeatability standard deviation for extrapolated literature of 709 6 23 J g -1 for thermal decomposition in onset temperature is 0.3.3 K (118. West Conshohocken. PA 19428-2959. atmospheric composition or pressure or a different heating rate. The study is on file at ASTM Headquarters.1 The repeatability relative standard deviation for re. which you may attend. two between temperatures of all reactions recorded from the DSC curve.org). That is. onset temperature. MA 01923. with the determination of one or more of these parameters. Tel: (978) 646-2600. at the address shown below.8. 15. Each labo.9 K Practice E691. The reproducibility 14. the reproducibility value (R) obtained by multiplying the thermal analysis. hazard potential. 15. 14. or through the ASTM website (www.9 to 395. 15.5 Determine the onset. Permission rights to photocopy the standard may also be secured from the Copyright Clearance Center.3 Between laboratory variability may be estimated using 16. the different experimental conditions. To= 431.3 The specific dated version of this test method used. 16. are entirely their own responsibility.5 %. It ranges within laboratory results should be considered suspect if they from 382. There is no accepted reference 15.2 K (109. E537 − 12 14. or service@astm. This values compare with values in the 15.0°C) for heating rates differ by more than the repeatability value (r).com/ 7 . and peak value estimates the 95 % confidence limit. laboratory results should be considered suspect if they differ by Report any processes (such as melting) which may interfere more than the reproducibility value (R). 15. DSC is 987 6 83 J g -1. The results were evaluated using were observed to be: ∆H = 722. Therefore.. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above address or at 610-832-9585 (phone). J. ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned in this standard. If you feel that your comments have not received a fair hearing you should make your views known to the ASTM Committee on Standards.astm. onset ratory characterized trityl azide (also known as azidotriphenyl. Report the enthalpy of 15. Keywords 15.8 kJ g-1.7 to 122.1. 100 Barr Harbor Drive. The repeatabil. pp.7 %.copyright. be obtained by requesting Research Report RR:E27-1003. organic solvents measured by microcalorimetry5.4 K. Vol 39. and reproducibility standard deviation by 2.52 K.5°C). http://www. Your comments are invited either for revision of this standard or for additional standards and should be addressed to ASTM International Headquarters. no bias informa- involving participation by six laboratories using apparatus tion can be provided.4. That is. Filliatre.3 The reproducibility standard deviation for the onset reaction.1°C) at 10 K min-1 heating rate. 222 Rosewood Drive. thermal hazard.2.4 K. temperature is 10 K. between 4 and 14 K min-1. C.4 Bias—Bias is the difference between a test result and an accepted reference value. 15.3. United States.4. from three manufacturers five instrument models. 15..9 K (196. temperature and extrapolated onset temperature of trityl azide methane) in quintuplicate. 15. 215–226.1.. extrapolated onset.