Designation: E968 02 (Reapproved 2014)

Standard Practice for

Heat Flow Calibration of Differential Scanning Calorimeters1

This standard is issued under the fixed designation E968; 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
1.1 This practice covers the heat flow calibration of differential scanning calorimeters over the temperature range
from 130C to +800C.
1.2 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this
standard.
1.3 Computer or electronic based instruments, techniques or
data manipulation equivalent to this practice may also be used.
1.4 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
responsibility of whoever uses this standard to consult and
establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.
See also Section 7.
2. Referenced Documents
2.1 ASTM Standards:2
E473 Terminology Relating to Thermal Analysis and Rheology
E793 Test Method for Enthalpies of Fusion and Crystallization by Differential Scanning Calorimetry
E967 Test Method for Temperature Calibration of Differential Scanning Calorimeters and Differential Thermal Analyzers
E1142 Terminology Relating to Thermophysical Properties
3. Terminology
3.1 DefinitionsSpecific technical terms used in this practice are in accordance with Terminologies E473 and E1142.
3.2 Definitions of Terms Specific to This Standard:
3.2.1 coeffcient of variation, na measure of relative precision calculated as the standard deviation of a series of values
1
This practice is under the jurisdiction of ASTM Committee E37 on Thermal
Measurements and is the direct responsibility of Subcommittee E37.01 on Calorimetry and Mass Loss.
Current edition approved March 15, 2014. Published April 2014. Originally
approved in 1983. Last previous edition approved in 2008 as E968 02 (2008).
DOI: 10.1520/E0968-02R14.
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
Standards volume information, refer to the standards Document Summary page on
the ASTM website.

divided by their average. It is usually multiplied by 100 and

expressed as a percentage.
NOTE 1The term quantitative differential thermal analysis refers to
differential thermal analyzers that are designed to obtain quantitative or
semiquantitative heat flow results. This procedure may also be used to
calibrate such apparatus.

4. Summary of Practice
4.1 Differential scanning calorimeters measure heat flow
(power) into or out of a test specimen and provide a signal
output proportional to this measurement. This signal often is
recorded as a function of a second signal proportional to
temperature or time. If this heat flow signal is integrated over
time, the resultant value is proportional to energy (or enthalpy
or heat). To obtain the desired energy information, the observed
instrument response (such as the area under the curve scribed)
must be multiplied by a proportionality constant that converts
the units of instrument output into the desired energy units.
This proportionality constant is called the instrument calibration coefficient (E). The value and dimensions (units) of E
depend upon the particular differential scanning calorimeter
and recording system being used and, moreover, may vary with
temperature.
4.2 This practice consists of calibrating the heat flow
response of a differential scanning calorimeter (that is, determining the calibration coefficient) by recording the melting
endotherm of a high-purity standard material (where the heat of
fusion is known to better than 61.5 % (rel)) as a function of
time. The peak is then integrated (over time) to yield an area
measurement proportional to the enthalpy of melting of the
standard material.
4.3 Calibration of the instrument is extended to temperatures other than that of the melting point of the standard
material through the recording of the specific heat capacity of
a (second) standard material over the temperature range of
interest. The ratio of the measured specific heat capacity at the
temperature of interest to that of the temperature of calibration
provides an instrument calibration coefficient at the new
temperature.
4.4 Once the calibration coefficient at a given temperature is
determined, it may be used to determine the desired energy
value associated with an enthalpic transition in an unknown
specimen at that temperature (see Test Method E793).

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E968 02 (2014)
5. Significance and Use

6.2 A balance, with capacity of 100 mg to weight

specimens, or containers, or both, to 61 g,

5.1 Differential scanning calorimetry is used to determine

the heat or enthalpy of transition. For this information to be
meaningful in an absolute sense, heat flow calibration of the
apparatus or comparison of the resulting data to that of a
known standard is required.

7. Precautions

5.2 This practice is useful in calibrating the heat flow axis of

differential scanning calorimeters or quantitative differential
thermal analyzers for subsequent use in the measurement of
transition energies and specific heat capacities of unknowns.

8. Reagents and Materials

6. Apparatus
6.1 Differential Scanning Calorimeter (DSC)The essential
instrumentation required to provide the minimum differential
scanning calorimetric capability for this method includes:
6.1.1 A DSC test chamber, composed of the following:
6.1.1.1 A furnace(s) to provide uniform controlled heating
(cooling) of a specimen and reference to a constant temperature
or at a constant rate with the temperature range of 100 to
600C.
NOTE 2This temperature range may be extended to higher and lower
temperatures depending upon the capabilities of the apparatus.

6.1.1.2 A temperature sensor, to provide an indication of the

specimen/furnace temperature to 60.01 K.
6.1.1.3 A differential sensor, to detect a heat flow (power)
difference between the specimen and reference equivalent to 1
W.
6.1.1.4 A means of sustaining a test chamber environment,
of an inert purge gas at a purge gas rate of 10 to 100 mL/min
6 5 mL/min.
NOTE 3Typically, 99.9+ % pure nitrogen, argon or helium are
employed when oxidation in air is a concern. Unless effects of moisture
are to be studied, use of dry purge gas is recommended and is essential for
operation at subambient temperatures.

6.1.2 A temperature controller, capable of executing a

specific temperature program by operating the furnace(s)
between selected temperature limits at a rate of temperature
change of between 1 and 35 K/min constant to 61 % and at an
isothermal temperature constant to 60.1 K.
6.1.3 A recording device, either digital or analog, capable of
recording and displaying the heat flow (DSC curve) signal
versus temperature, displaying any fraction including the
signal noise.
6.1.4 Containers, (pans, crucibles, vials, etc. and associated
lids), that are inert to the specimen and reference materials and
that are of suitable structural shape and integrity to contain the
specimen and reference.
NOTE 4Most containers require special tool(s) for opening, closing or
sealing. The specific tool(s) necessary to perform this action also are
required.

6.1.5 Cooling capability, to achieve and sustain cryogenic

temperatures, to hasten cool down from elevated temperatures,
or to provide constant cooling rates, or a combination thereof.
6.1.6 Computer and software capability to perform the
mathematical treatments of this method including peak integration.

7.1 Toxic or corrosive effluents, or both, may be released

when heating some material and could be harmful to personnel
and apparatus.

8.1 For the temperature range covered by many

applications, the melting transitions of the following greaterthan-99.9 % pure material may be used for calibration.

Indium
A
B

Melting
Temperature,
KA
429.75

Heat of Fusion,
J/gB
28.58 0.07

PrestonThomas, H., Metrologia, Vol 27, 1990, p. 3.

Stolen, S., Gronvold, F., Thermochimica Acta, Vol 327, 1999, p.1.

8.2 Sapphire, ( Al2O3), 20 to 80 mg, solid disk.

9. Calibration
9.1 Perform any calibration procedures described by the
manufacturer in the operations manual.
9.2 Perform a temperature signal calibration according to
Practice E967.
10. Procedure
10.1 Calibration at a Specific TemperatureThe following
procedure is used to calibrate the heat flow response of the
instrument with the same type specimen holder, heating rate,
purge gas, and purge gas flow rate as will be used for specimen
measurement. A dry nitrogen purge gas with a flow rate of 10
to 50 6 5 mL/min is recommended. Other purge gases and
rates may be used but shall be reported.
10.1.1 Place a 5 to 10 6 0.001-mg weighed amount of melt
transition calibration material into a clean specimen holder.
10.1.2 Seal the specimen holder with a lid, minimizing the
free space between the specimen and the lid. Load the
specimen into the instrument.
10.1.3 Allow the specimen to equilibrate at a temperature
30C below the melting temperature.
10.1.4 Heat the specimen at 10C/min through the endotherm until the baseline is reestablished above the melting
endotherm. Record the accompanying thermal curve of heat
flow versus time.
NOTE 5Other heating rates may be used but shall be reported.

10.1.5 Cool and reweigh the specimen. Reject the data if

mass losses exceed 1 % of the original mass or if there is
evidence of reaction with the specimen holder.
10.1.6 Calculate the calibration coefficient at the temperature of measurement using the procedure described in Section
11. Duplicate determinations shall be made on different specimens and the mean value determined and reported.
10.2 Calibration at Other TemperaturesOnce a calibration coefficient at a specific temperature has been obtained by
the procedure in 10.1, extension of the calibration coefficient to

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E968 02 (2014)
other temperatures may be accomplished using the interpolative technique described below.
10.2.1 Select a temperature range for calibration of the
instrument. The range should be at least 30C below the lowest
temperature of interest (to permit attainment of dynamic
equilibrium) to 10C above the highest temperature of interest
and include the temperature of calibration established in 10.1.
10.2.2 Condition the sapphire calibration material and
specimen holder by heating to the maximum temperature
determined in 10.2.1 and holding for 2 min. Cool to room
temperature and store in a desiccator until needed.
NOTE 6Any volatilization (such as from absorbed moisture) from the
calibration material during the experiment will invalidate the test.

10.2.3 Establish a baseline as follows:

10.2.3.1 Load the instrument with the specimen pan and lid
(from 10.2.2) to be used in 10.2.5.
10.2.3.2 Establish the initial temperature conditions of the
experiment (determined in 10.2.1) and equilibrate for 5 min.
10.2.3.3 Heat the specimen holder and lid at 10C/min
throughout the temperature range established in 10.2.1. Record
the accompanying thermogram of heat flow versus temperature.
NOTE 7Other heating rates may be used but shall be reported.

10.2.4 After cooling the specimen holder and lid to room

temperature, introduce and weigh 20 to 70 mg of the sapphire
heat capacity reference material from 10.2.2 to an accuracy of
0.01 mg.
10.2.5 Cover the specimen holder with the same lid minimizing the free space between the specimen and the lid. Load
the specimen into the instrument.
10.2.6 Take the specimen to the initial temperature determined in 10.2.1 and allow to equilibrate for 5 min.
10.2.7 Heat the specimen at 10C/min through the temperature range of test recording the accompanying thermal curve.
10.2.8 Calculate the calibration coefficient at any temperature of interest within the temperature range described in
Section 11. Duplicate determination shall be made on the same
specimen and the mean value determined and reported.
11. Calculation
11.1 Calculate the calibration coefficient at a specific temperature as follows:
11.1.1 Using the thermal curve obtained in 10.1, construct a
baseline on the differential heat flow curve by connecting the
two points at which the melting endotherm deviates from the
baseline before and after the melt (see Fig. 1). Integrate this
area as a function of time to achieve the melting endothermic
peak area in mJ.
11.1.2 Calculate the experimental calibration coefficient at
the melting temperature of the standard reference material as
follows:
E 5 ~H m!/~A!

FIG. 1 Melting Endotherm

where:
E = calibration coefficient at the temperature of the melting
endotherm,
H = enthalpy of fusion of the standard material, in J/g
(mJ/g),
m = mass of the standard, in g, and
A = melting endotherm peak area, in mJ.
11.2 Calculate the calibration coefficient at other temperatures.
11.2.1 Measure the heat flow difference between the sapphire and baseline trace on the heat flow recorder axis in the
thermal curve obtained in 10.2 at the temperature of interest T
and the melting temperature T s of the reference material. These
values are D and D used in (Eq 2) (see Table 1 and Fig. 2).
11.2.2 Obtain specific heat capacity values of the sapphire at
the temperature of interest (T) and at the melting temperature
of the reference material (Ts) from Table 2. Interpolate between
those values given in the table to obtain the specific heat
capacity at the desired temperature. These values are C and C
used in (Eq 2).
11.2.3 Calculate the calibration coefficient at temperature T
as follows:
E 5 E ~ C D ! / ~ C D !

(2)

where:
E = calibration coefficient at temperature T,
E = calibration coefficient at the melting temperature of the
standard reference material (Ts), as calculated in
11.1.2,
C = specific heat capacity of sapphire reference material at
temperature of interest T, in J/(g K),
C = specific heat capacity of the sapphire reference material at the melting temperature of the reference material
(Ts), in J/(g K),
D = difference in recorder heat flow deflection between
blank and calibration runs at the melting temperature
of the reference material (Ts), in mW, and
D = difference in recorder heat flow deflection between
blank and calibration runs at the temperature of interest
T, in mW.
NOTE 8In cases where different specimen holders are used for the
baseline and calibration runs, the difference in recorder heat flow
deflections D and D may be corrected for small differences in specimen
holder weight by adding the following value of D to D and D:

(1)

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E968 02 (2014)
TABLE 1 Sapphire ( Al2O3) Specific Heat CapacityA
Temperature,
K

Specific Heat
Capacity, J/gK

140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
610
620

0.2739
0.3133
0.3525
0.3912
0.4290
0.4659
0.5014
0.5356
0.5684
0.5996
0.6294
0.6577
0.6846
0.7102
0.7344
0.7574
0.7792
0.7999
0.8194
0.8380
0.8555
0.8721
0.8878
0.9027
0.9168
0.9302
0.9429
0.9550
0.9665
0.9775
0.9879
0.9978
1.0073
1.0164
1.0250
1.0332
1.0411
1.0486
1.0559
1.0628
1.0694
1.0758
1.0819
1.0877
1.0934
1.0988
1.1039
1.1090
1.1138

Temperature, K

Specific Heat
Capacity, J/gK

630
640
650
660
670
680
690
700
710
720
730
740
750
760
770
780
790
800
810
820
830
840
850
860
870
880
890
900
910
920
930
940
950
960
970
980
990
1000
1010
1020
1030
1040
1050
1060
1070
1080
1090
1100

1.1184
1.1228
1.1272
1.1313
1.1353
1.1393
1.1431
1.1467
1.1503
1.1538
1.1572
1.1604
1.1637
1.1667
1.1698
1.1727
1.1756
1.1784
1.1811
1.1839
1.1864
1.1890
1.1914
1.1939
1.1962
1.1986
1.2008
1.2031
1.2053
1.2074
1.2095
1.2115
1.2135
1.2155
1.2174
1.2194
1.2212
1.2230
1.2249
1.2266
1.2284
1.2301
1.2318
1.2335
1.2351
1.2367
1.2383
1.2400

FIG. 2 Reference MaterialSpecific Heat Capacity

12.1.1 Complete identification and description of the reference materials used for the calibration, including source and
manufacturers code.
12.1.2 Description of the instrument used in the calibration.
12.1.3 Statement of the mass, dimensions, geometry, and
material of the specimen holder, and the heating rate used.
12.1.4 Identification of the instrument purge by gas flow
rate, purity and composition.
12.1.5 Calibration coefficient at the melting temperature of
the standard and selected temperatures of interest.
12.1.6 The dated version of this standard used.
13. Precision and Bias

Archer, D. G., Journal of Physical and Chemical Reference Data, Vol 22, No. 8,
1993, pp. 14411453.

D 5

c p
W 2W
1000 E ~ c

(3)

where:
cp
= specific heat of aluminum (or other specimen holder
material of construction), in J/(g K) for aluminum),
Wc
Wb

= mass of the specimen holder for the calibration run, in

g,
= mass of the specimen holder for the blank run, in g,
and
= heating rate, in K/s (C/s).

12. Report
12.1 The report shall contain the following:

13.1 The precision of this practice was determined in an

interlaboratory test in which thirteen laboratories participated
using four instrument models. Based upon this test, the
following conclusions are made:
13.1.1 Repeatability (Single Analysis)The coefficient of
variation of results (each the average of duplicate) for calibration coefficient derived from the melting endotherm of the
indium, obtained by the same analyst on different days, has
been estimated to be 0.94 % with 11 df.
13.2 The following criteria should be used for judging the
acceptability of calibration coefficient values extended to
temperatures other than that of the melting temperature of
Indium (that is, 430 K):
13.2.1 Repeatability (Single Analyst)The coefficient of
variation of results (each the average of duplicates), obtained
by the same analyst on different days, has been estimated to be
1.4 % with 18 df at temperatures within 265 K of the primary
calibration temperature. Two such averages should be considered suspect (95 % confidence level) if they differ by more than
4.2 %.
13.2.2 Reproducibility (Multilaboratory)The coefficient
of variation of results (each the average of duplicates) obtained
by analysts in different laboratories, has been estimated to be
2.7 % with 16 df at temperatures within 265 K of the primary
calibration temperature. Two such averages should be considered suspect (95 % confidence level) if they differ by more than
8.2 %.

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E968 02 (2014)
13.2.3 Repeatability and reproducibility appear to become
poorer as the difference between the desired and primary
calibration temperature increases. Beyond those limits stated
previously, repeatability is anticipated to decrease by 0.7 % per
each additional 100 K and reproducibility by 2.0 % per each
additional 100 K.

two high-purity metal samples using this calibration practice

with values reported in the literature:
Material
Lead
Zinc5

Testing
22.27 0.68
103.7 2.9

Heat of Fusion (J/g)

Literature4
23.08 0.11
108.09 0.43

13.3 An estimation of the accuracy of this procedure was

obtained by comparing the heat of fusion values obtained for
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