Designation: C1702 − 15a

Standard Test Method for

Measurement of Heat of Hydration of Hydraulic
Cementitious Materials Using Isothermal Conduction
Calorimetry1
This standard is issued under the fixed designation C1702; 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* the same mass and thermal properties as a cement sample, but
1.1 This test method specifies the apparatus and procedure which is not generating or consuming heat.
for determining total heat of hydration of hydraulic cementi- 3.1.2 heat, n—the time integral of thermal power measured
tious materials at test ages up to 7 days by isothermal in joules (J).
conduction calorimetry. 3.1.3 isothermal conduction calorimeter, n—a calorimeter
1.2 This test method also outputs data on rate of heat of that measures heat flow from a sample maintained at a constant
hydration versus time that is useful for other analytical temperature by intimate thermal contact with a constant
purposes, as covered in Practice C1679. temperature heat sink.
1.3 The values stated in SI units are to be regarded as 3.1.4 reference cell, n—a heat-flow measuring cell that is
standard. No other units of measurement are included in this dedicated to measuring power from a sample that is generating
standard. no heat.
1.4 This standard does not purport to address all of the 3.1.4.1 Discussion—The purpose of the reference cell is to
safety concerns, if any, associated with its use. It is the correct for baseline drift and other systematic errors that can
responsibility of the user of this standard to establish appro- occur in heat-flow measuring equipment.
priate safety and health practices and determine the applica- 3.1.5 sensitivity, n—the minimum change in thermal power
bility of regulatory limitations prior to use. reliably detectable by an isothermal calorimeter.
3.1.5.1 Discussion—For this application, sensitivity is taken
2. Referenced Documents
as ten times the random noise (standard deviation) in the
2.1 ASTM Standards:2 baseline signal.
C186 Test Method for Heat of Hydration of Hydraulic
3.1.6 thermal mass, n—the amount of thermal energy that
Cement
can be stored by a material (J/K).
C1679 Practice for Measuring Hydration Kinetics of Hy-
3.1.6.1 Discussion—The thermal mass of a given material is
draulic Cementitious Mixtures Using Isothermal Calorim-
calculated by multiplying the mass by the specific heat capacity
etry
of the material. For the purpose of calculating the thermal mass
E691 Practice for Conducting an Interlaboratory Study to
used in this standard, the following specific heat capacities can
Determine the Precision of a Test Method
be used: The specific heat capacity of a typical unhydrated
3. Terminology portland cement and water is 0.75 and 4.18 J/(g·K), respec-
tively. Thus a mixture of A g of cement and B g of water has
3.1 Definitions of Terms Specific to This Standard: a thermal mass of (0.75 × A + 4.18 × B) J/K. The specific heat
3.1.1 baseline, n—the time-series signal from the calorim- capacity of typical quartz and limestone is 0.75 and
eter when measuring output from a sample of approximately 0.84 J ⁄(g·K), respectively. The specific heat capacity of most
amorphous supplementary cementitious material, such as fly
1
This test method is under the jurisdiction of ASTM Committee C01 on Cement ash or slag, is approximately 0.8 J/(g·K).
and is the direct responsibility of Subcommittee C01.26 on Heat of Hydration.
Current edition approved Aug. 1, 2015. Published August 2015. Originally
3.1.7 thermal power, n—the heat production rate measured
approved in 2009. Last previous edition approved in 2015 as C1702 – 15. DOI: in joules per second (J/s).
10.1520/C1702-15A.
2
3.1.7.1 Discussion—This is the property measured by the
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
calorimeter. The thermal power unit of measure is J/s, which is
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on equivalent to the watt. The watt is also a common unit of
the ASTM website. measure used to represent thermal power.

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

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

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 C1702 − 15a
4. Summary of Test Method 6.1.2 Volumetric Dispenser—A device for measuring vol-
4.1 Principle—An isothermal heat conduction calorimeter ume or mass of water, accurate to 0.1 mL. This could be a
consists of a constant-temperature heat sink to which two syringe, pipette, or weighing device.
heat-flow sensors and sample holders are attached in a manner 6.1.3 Sample Holder—A device that holds the cement paste
resulting in good thermal conductivity. One heat-flow sensor and provides intimate contact with the calorimeter heat sensing
and sample holder contains the sample of interest. The other device and prevents evaporation of mixing water. If using
heat-flow sensor is a reference cell containing a blank sample commercially manufactured equipment, consult the recom-
that evolves no heat. The heat of hydration released by the mendations of the manufacturer in choosing sample holders.
reacting cementitious sample flows across the sensor and into 6.1.4 Resistance Heater—An electrical device fabricated
the heat sink. The output from the calorimeter is the difference from material with similar heat capacity and shape as the test
in heat flow (thermal power) between the sample cell and the sample, but containing a resistor connected to a constant-
reference cell. The heat-flow sensor actually senses a small voltage power supply such that a stable output of 0.010 6
temperature gradient that develops across the device, however 0.0002 J/s can be generated (see Note 1).
the heat is removed from the hydrating sample fast enough NOTE 1—A simple procedure for fabricating heaters and blanks having
that, for practical purposes, the sample remains at a constant the same approximate shape and heat capacity as a sample is to make
temperature (isothermal). specimen similar to one used in a determination out of plaster of Paris
embedded with a small resistor. Plaster of Paris has only a transient heat
4.2 The output from the heat-flow sensor is an electrical of hydration and is not aggressive to electronic components. A resistance
voltage signal that is proportional to the thermal power from of 100 to 300 Ω is a convenient value when using voltages of 0.1 to 10 V
the sample. This output must be calibrated to a known thermal to drive heat production.
power. In this method this is accomplished by measurements 6.1.5 Reference Specimen—A sample fabricated from an
on a heat source that emits a constant and known thermal inert material with similar heat capacity and shape as the test
power. The integral of the thermal power over the time of the sample. This is used in the reference cell.
test is the heat of hydration. Alternatively, a cementitious
6.1.6 Multimeter—An instrument for measuring DC voltage
material with a known heat of hydration can be used for
and resistance values for the resistance heater described in
calibration as described in Appendix X1.
6.1.4 to an accuracy of 1 %. This instrument is only required if
4.3 Two methods are described. In Method A the sample and the calorimeter does not contain built-in calibration capability.
water are both temperature equilibrated and mixed inside the 6.1.7 Power Supply—A constant voltage DC power supply
calorimeter. This method is the most direct way to determine with a power output range sufficient to simulate the maximum
heat of hydration. In Method B the sample is mixed in the output of a hydrating cement sample (see Note 2). This
sample vial outside of the calorimeter using temperature equipment is only required if an instrument does not contain
equilibrated materials then put into the calorimeter. This built-in calibration capability.
method offers certain practicality, but depending on the mate-
rials being analyzed and procedures used for mixing and NOTE 2—A power output of at least 0.33 J/s is needed for most
applications.
handling, this method may suffer from small errors due to
periods of hydration being missed or spurious heat being 6.2 Calorimeter—The schematic design of a calorimeter is
introduced or taken away from the calorimeter during setup or given in Fig. 1. It shall consist of a sample holder for the test
combinations thereof. and reference specimens, each thermally connected to heat-
flow sensors, which are thermally connected to a constant-
5. Significance and Use temperature heat sink. The actual design of an individual
5.1 This method is suitable for determining the total heat of instrument, whether commercial or homemade, may vary, but
hydration of hydraulic cement at constant temperature at ages it should follow the criteria given below. Any other suitable
up to 7 days to confirm specification compliance. It gives test arrangement that satisfies sections 6.2.1 – 6.2.3 is acceptable.
results equivalent to Test Method C186 up to 7 days of age 6.2.1 Instrument Stability—The baseline shall exhibit a low
(1).3 random noise level and be stable against drift. This property
5.2 This method compliments Practice C1679 by providing shall be verified on a new instrument and whenever there are
details of calorimeter equipment, calibration, and operation. questions about performance. The rate of change of the
Practice C1679 emphasizes interpretation significant events in baseline measured during a time period of 3 days shall be
cement hydration by analysis of time dependent patterns of ≤20 µJ ⁄s per gram sample per hour of the test and a baseline
heat flow, but does not provide the level of detail necessary to random noise level of ≤10 µJ/s per gram sample (see Note 3).
give precision test results at specific test ages required for In practice the baseline is measured for 3 days and a straight
specification compliance. line is fitted to the power (J/(g·s)) versus time (h) data using a
linear regression procedure. The long term drift is then the
6. Apparatus slope in the line (J/(g·s·h)) and the baseline noise level is the
6.1 Miscellaneous Equipment: standard deviation (J/(g·s)) around this regression line.
6.1.1 Balance—Accurate to 0.01 g. NOTE 3—The rationale for these limits is found in Poole (2007) (1).
3
The boldface numbers in parentheses refer to the list of references at the end of 6.2.2 Instrument Sensitivity—The minimum sensitivity for
this standard. measuring power output shall be 100 µJ/s.

2
 C1702 − 15a

FIG. 1 Schematic Drawing of Heat Conduction Calorimeter

6.2.3 Isothermal Conditions—The instrument shall maintain cementitious materials may have instrument specific calibra-
the temperature of the sample to within 1 K of the thermostated tion procedures. Conform to these procedures if they exist. In
temperature. addition, the instrument shall be capable of providing data
6.3 Data Acquisition Equipment—Data acquisition equip- described in 7.1.1.1, 7.1.2.1, and 7.1.2.2, and calculations in
ment may be built into the calorimeter instrument package, or 7.1.4. If there are no instrument calibration procedures, cali-
it may be an off-the-shelf, stand-alone, item. The data acqui- brate the instrument according to the following procedure.
sition equipment shall be capable of performing continuous Calibration shall be at least a two-point process. This is
logging of the calorimeter output measurement at a minimum illustrated schematically in Fig. 2 Alternatively use a generic
time interval of 10 s. It is useful, for purposes of reducing calibration procedure for a cementitious material with known
amount of data, to have the flexibility to adjust the reading heat of hydration as described in Appendix X1. Alternatively,
interval to longer times when power output from the sample is use a generic calibration procedure for a cementitious material
low. Some data acquisition equipment is designed to automati- with known heat of hydration as described in Appendix X1.
cally adjust reading intervals in response to power output. The 7.1.1 Mount the resistance heater and the blank specimen in
equipment shall have at least 4.5-digit-measuring capability, their respective measuring cells and start data collection. This
with an accuracy of 1 %, or comparable capabilities to condi- step measures the baseline calorimeter output (in units of V or
tion the power output into the same quality as integrated signal mV) when no heat is being generated.
amplifiers. 7.1.1.1 Measure this baseline when it reaches a constant
value (drift ≤ 20 µJ/s per gram sample per hour).
7. Instrument Calibration 7.1.1.2 Record this output as V0 for P0 = 0 (see Note 4).
7.1 Instrument Calibration—Commercially manufactured NOTE 4—V0 may not be zero voltage, but may be a positive or negative
instruments designed for measuring heat of hydration of number. The practice of using a test cell and a reference cell usually results

FIG. 2 (A) Schematic Steady-State Calibration Using 2-Point Calibration Process, and (B) Multi-Point Calibration Process

3
 C1702 − 15a
in the V0 being a relatively small number but, depending on the variability stable over a period of 30 min or longer. The temperature of the
in properties of some hardware, it may not be zero. heat sink during the test shall be 23.0 6 1.0°C, unless a
7.1.2 Power in the heater circuit is related to voltage and different temperature is required by the analysis.
resistance by the following equation: NOTE 7—The time required to reach thermal equilibrium depends on
P 5 I 2R (1) the instrument. Generally, it is recommended to set the temperature
control unit of the calorimeter at target temperature at least 18 h before
where: testing.
P = power, J/s, 8.1.1 Baseline Verification Test—This test is recommended
I = applied current, amperes, and prior to testing and required whenever there is a change in the
R = resistance, ohms. operating temperature of the calorimeter or in ambient operat-
Apply sufficient voltage to the heater circuit to generate a ing conditions. For each active calorimeter cell, prepare a
heat output of approximately 0.1 J/s, measured to an accuracy sample of water without any cement and without any mixing,
of 5 %. but with the same thermal mass as the inert reference speci-
7.1.2.1 Allow the output to stabilize signal at a drift of men. Alternatively, use another inert material with equal
≤0.1 % over 60 min or ≤0.05 % over 30 min. thermal mass as the inert reference specimen. Seal each vial
7.1.2.2 Record this output as V1 for a power P1 (see Note 5). with a vapor-tight lid (see Note 8). For each active calorimeter
This is the minimum requirement for a calibration sequence. At cell, load the sample container with water or other inert
the users discretion any number of voltage levels may be used material of equal thermal mass into the calorimeter and start
to characterize the operating range of the calorimeter. logging. Log the signal for a minimum of 24 h. Calculate the
NOTE 5—The early C3A reaction of a typical portland cement evolves
heat as a function of time per gram cement normally used in the
a maximum power of about 0.02 J/(g·s). The alite phase typically evolves calculation section, although no cement is used for this
heat at a maximum power of about 0.002 J/(g·s) during the first 24 h of baseline verification test. A re-calibration is required if the
hydration. A 5-g sample then generates power peaks in the range of absolute value of the calculated heat per hour obtained 6 h from
0.10 J ⁄ s in the first few minutes after adding water, and in the range of start of logging to the end of the test is higher than 0.10 J/(gh),
0.010 J ⁄ s in the first 24 h.
where the mass (g) refers to the mass of cement intended to be
7.1.3 Calibration Coeffıcients—Calculate calibration coeffi- used.
cients by fitting the power versus voltage output data to a to a
mathematical relationship using standard curve fitting tech- NOTE 8—The effectiveness of this sealing in preventing any evapora-
tion (and its accompanying evaporative cooling) is variable depending on
niques. Power (P), in units of J/s (or watts), is the dependent the materials and techniques employed. Determining the mass of the
variable (y) in the calibration equation, and output voltage (V), sealed vial to the nearest 0.001 g for a small (up to 10.000 g) sample or
in units of mV, is the independent variable (x). This equation is 0.01 g for a larger sample at the beginning and end of the test is a
then used to translate mV output to power units meaningful for convenient method to assess the adequacy of the sealing operation for a
sample with hydrating cementitious material. As a rule of thumb, for a w/c
calculating heat flow (see Note 6). = 0.5 cement paste, 0.3 % loss of water due to evaporation over 7 days,
NOTE 6—A linear calibration equation is found to be suitable in many may, if not corrected for, result in a heat loss of approximately 3.7 J/g
instruments over the operating range necessary to analyze portland cement. If the measured mass loss is assumed to be due to water
cements, as in the following equation: P = A + BV. In this case, the fitted evaporation, it can be converted to an equivalent heat release (loss) using
coefficients A (y-axis intercept) and B (slope) are in units of J/s and the known heat of vaporization of water of 43.99 kJ/mol or 2440 J/g at
J/(mV·s), respectively. 25°C. A convenient method to approximate and compensate for the heat
loss due to evaporation during calibration is to measure the voltage signal
7.1.4 In a multi-channel instrument containing several and mass loss with water in the sample vials as part of the baseline
calorimeters, all channels shall be calibrated individually. calibration.
However, it is possible to calibrate all calorimeters simultane- NOTE 9—The results from the baseline verification test can be used to
ously using multiple resistance heaters and having the same recalculate the baseline value P0 in 7.1.
NOTE 10—When performing the baseline verification test, use the same
current passing through the heaters in all calorimeter cells. thermal mass of water as in target cement paste.
7.1.5 Calibration shall be executed at regular intervals to NOTE 11—Calculation of thermal mass. The heat capacity of a typical
determine the calibration coefficient. The length of the time portland cement and water is 0.75 and 4.18 J/g/K, respectively. If, for
intervals between calibrations is dependent on the instrument example, a cement paste is prepared using 3.00 g cement and 1.5 g water,
and the personnel, and must be determined empirically. If the the resulting cement paste has an approximate thermal mass of (3.00 ×
0.75 + 1.5 × 4.18) = 8.52 J/K, which is also the target thermal mass of the
calibration coefficient differs more than 2 % from one calibra- inert reference specimen. If using water for the baseline verification test,
tion to the next, then calibrations intervals must be reduced the corresponding mass of water used is (8.52 4.18) = 2.04 g. After
until this stability limit is reached. completion of the baseline verification test, a fraction of this water (1.5 g
in this example) can be used for the heat of hydration tests in the
8. Procedure procedure section.
8.1 The thermal mass of the inert reference specimen should 8.2 Method A—This method is used when an instrument is
always be similar to the thermal mass of the target cement configured so that cementitious materials and water can be
paste. Verify that the calorimeter equipment temperature is temperature equilibrated and mixed while in place in the
within 0.2°C of target temperature with the proper mass of calorimeter cell.
inert material charged in the reference cells no later than one 8.2.1 Weigh at least 3 g of cementitious material (see Note
day before performing a test. Determine that the calorimeter is 12), the mass recorded to the nearest 0.01 g, and place in the
at temperature equilibrium by verifying that the baseline is calorimeter cell. Weigh or determine volumetrically sufficient

4
 C1702 − 15a
water to give a paste water-cementitious materials ratio of at way that the time between the addition of water and the time
least 0.40, but in any case sufficient water to completely wet when the sample is put into the calorimeter is less than 2 min.
the sample, and place the water holder in the cell. Higher Determine the mass of the cement sample to the nearest 0.01 g
water-cementitious materials ratios may be required to get and the mass of mixing water to the nearest 0.1 g. Mix
thorough mixing of cement and water (see Note 13). Allow any sufficient cement paste at a water-cementitious materials ratio
change in the calorimeter output caused by this process to of 0.40 or higher to give a sample containing a mass of dry
return to the baseline level. cement in the range described in Method A or as recommended
NOTE 12—Amount of sample required varies among calorimeter by the instrument manufacturer.
designs. Since the exothermic reaction tends to slow down after the first NOTE 16—Use of a vortex-type mixing device (as commonly used for
24 h, a sample that is too small will generate a signal late in the test period mixing materials in test tubes) has been found to generate adequate mixing
that is too weak to detect reliably. If inconsistent results are obtained, then of cement paste typically in less than 60 s, for samples vials smaller than
a larger sample size may be required. Sample sizes between about 3 and 50 mL. Hand mixing using disposable spatulas left inside the vial after
15 g have been reported to be useful for maintaining a strong signal late mixing has been found to generate adequate mixing of cement paste
in the test for portland-cement based cements. Normally a signal of at least typically in less than 60 s, for samples vials larger than 50 mL. If needed,
10 µJ/(g·s) at the end of the test is sufficient to give good results. Tests after mixing tap the sample vial ten times against a flat surface to
designed to run for 1 to 3 days can use a sample mass at the smaller end consolidate the paste sample against the bottom of the sample vial.
of this range, while longer tests, such as 7 days, require a sample mass at
the larger end of this range. 8.3.2.2 Care should be taken that the incidental warming or
NOTE 13—The w/c required for good mixing will probably have to be cooling of the sample and the sample holder due to handling
determined empirically by examining specimens after completion of are minimal.
testing for evidence of poor mixing.
8.2.2 Start data collection, then mix the water with the NOTE 17—Use of insulating cotton gloves may be helpful in minimiz-
ing heating of the sample from handling.
cementitious materials to form a uniform paste. Some com-
mercial calorimeters and data acquisition equipment are pro- 8.3.3 Load the sample vial with cement paste into the
grammable to collect data at prescribed interval lengths or at calorimeter.
intervals that vary with the rate of change of power levels. Data
are collected more rapidly when power output is high than 9. Calculation
when it is low. If this flexibility is not a feature of the data 9.1 The total heat of hydration, Qt, is the integrated value of
acquisition component of the calorimeter, then collect readings the power versus time data, collected as described in 8.2
every 30 s throughout the length of the test (see Note 14). (Method A) or 8.3 (Method B).
NOTE 14—It is only necessary to collect data every 10 s through the 9.1.1 Remove Leading Edge Data—For both Methods A and
period of an early and short-lived heat evolution peaks. In portland B, there may be data collected during instrument setup and
cements this is over within approximately 30 min. Data collection every thermal equilibration that is not pertinent to the final determi-
10 min is adequate after this point. Adopting this practice will reduce the
size of data files.
nation. These data shall be removed.
9.1.2 Many data acquisition units and commercial calorim-
8.3 Method B—This method is used when cement paste is eters incorporate the calibration equation into the software and
mixed in the sample vial outside of the calorimeter using present the raw output data in units of J/g of cement. If this is
temperature equilibrated materials and then loaded into the not the case, then the output data will be in units of mV, and
calorimeter cell. In this procedure, a small amount of the early must be transformed into thermal power using the calibration
heat-of hydration data may be lost. For some rapidly hardening coefficients determined from Eq 2.
cements, the error could be more significant. Also, the baseline
may also be disturbed during the early period of the test due to P n 5 A1BVn (2)
spurious heat gains to the sample or losses from the sample where:
while outside of the calorimeter, for example, during mixing Pn = power input level used in the instrument calibration,
and handling. and
8.3.1 Conditioning Materials—The mix water shall be con- Vn = voltage output level used in the instrument calibration.
ditioned to the same temperature as the calorimeter within
0.2°C before mixing. All cementitious materials shall be 9.1.3 Calculation of Qt—The total heat of hydration of the
conditioned to the same temperature as the calorimeter within sample, Qt, is calculated by integrating the power/g versus time
1.0°C before mixing. data over the time interval of the test (t0 to te, in units of
seconds) as in Eq 3:
NOTE 15—It may be convenient to condition vials with mix water in the
te
active calorimeter cells several hours prior to mixing and charging of
cement paste. This will ensure that the mix water is at the same
Qt 5 *t5t 0
Pdt (3)
temperature as the calorimeter prior to mixing. Start logging the signal where:
after charging vials with water into the active calorimeter cells and
continue logging until the signal remains stable for several hours. t0 = the time the cement and water are mixed, taken as zero,
8.3.2 Start data collection, then mix the water with the and
cementitious materials to form a uniform paste, and collect te = the end of the test.
data as described in 8.2.2. 9.1.4 Operationally, the integration is executed by averaging
8.3.2.1 Mixing and Charging of Cement Paste—The mixing the power output from two consecutive readings and multiply-
of the cement paste shall be made in the sample vial in such a ing by the time interval of the reading, giving an output for

5
 C1702 − 15a
each time increment in units of J/g. The heat so calculated in 11. Precision and Bias4
each time increment is then summed over the duration of the 11.1 The precision of this test method is based on an
test, as in Eq 4. interlaboratory study conducted in 2012 (Note 18).

(S D
te
P ~ t i ! 1P ~ t i11 ! NOTE 18—The data and analysis of the interlaboratory study are
Qt 5 3 ~ t i11 2 t i ! (4) summarized in RR:C01-1013. The interlaboratory study involved 13
t5t 0 2
laboratories and 6 different types of cement. Laboratories reported
where: between 2 and 8 replicate determinations. In this test method a determi-
nation is also a test result. The analysis was based on the procedures in
P(ti) = the power output at the time ti, and Practice E691.
P(ti+1) = the power output at the next time interval (ti+1).
11.2 Single-Operator Precision and Multilaboratory
In Method A, t0 is taken as zero when water is added to the Precision—The single-operator and multilaboratory precision
cement. for Method A and Method B at 1, 2, 3, and 7 days are shown
in Table 1. The precision is calculated using a 95% confidence
10. Report interval. The results in Table 1 indicate the maximum expected
difference between two properly performed tests.
10.1 Test Report—Report the following information:
10.1.1 Cement sample identification. 11.3 Bias—At the time of the study, there was no accepted
reference material suitable for determining the bias for this test
10.1.2 Date and time when the test was performed.
method, therefore no statement on bias is being made.
10.1.3 Instrument used.
10.1.4 The mass of dry cement in sample. 12. Keywords
10.1.5 The name of the data file. 12.1 heat of hydration; hydraulic cement; isothermal con-
10.1.6 Date of the calibration used. duction calorimetry; portland cement
10.1.7 A figure showing the resulting thermal power curve. 4
Supporting data have been filed at ASTM International Headquarters and may
10.1.8 Calculated heat of hydration and the method (A or B) be obtained by requesting Research Report RR:C01-1013. Contact ASTM Customer
used. Service at [email protected].

6
 C1702 − 15a
TABLE 1 Precision Summary
C1702 C1702
Method A Method B
Age, days Multiple
Single Multiple Single
Laboratory,
Operator, % Laboratory, % Operator, %
%
1 3.5 10.5 3.4 15.8
2 3.7 9.7 3.2 14.6
3 4.1 12.0 3.2 14.5
7 6.1 21.1 3.6 17.5

APPENDIXES

(Nonmandatory Information)

X1. INSTRUMENT CALIBRATION OR CALIBRATION VERIFICATION USING A CEMENTITIOUS MATERIAL OR OTHER

HEAT RELEASING MATERIAL WITH KNOWN HEAT OF HYDRATION

X1.1 Procedure (2) For each cell to be calibrated, start data collection and
X1.1.1 Verify that the calorimeter equipment temperature is mix the water with the heat generating material to form a
within 0.2°C of target temperature with the proper mass of uniform paste. Collect readings at least every 30 s throughout
inert material charged in the reference cells no later than one the length of the test. Log data for at least 48 h after mixing.
day before performing a test. Determine that the calorimeter is X1.1.3.2 External Mixing—This method is used when the
at temperature equilibrium by verifying that the baseline is heat releasing material to be tested is mixed outside of the
stable over a period of 30 min or longer. calorimeter and then loaded into the calorimeter cell.
(1) Condition the mix water to the same temperature as the
NOTE X1.1—The time required to reach thermal equilibrium depends
on the instrument. Generally, it is recommended that the instrument should calorimeter within 0.2°C before mixing. Condition the heat
have been running at the target temperature for at least 18 h before testing. releasing material to be tested to the same temperature as the
calorimeter within 1.0°C before mixing.
X1.1.2 Baseline Calibration—Perform a baseline / offset
calibration for each active cell by charging an inert material (2) For each calorimeter cell to be calibrated, weigh or
conditioned to the same temperature as the calorimeter within determine volumetrically a mix water sample into a test vial
0.2°C, with the inert sample having a similar thermal mass as with the water mass required as if preparing a cementitious
you would use when testing a cementitious material for heat of paste sample at w/c 0.50, the mass recorded to the nearest 0.1
hydration. Log the signal for at least 48 h. g. Seal each vial with airtight lid. If possible use a rubber
stopper for small glass vials instead of a cramping tool to
NOTE X1.2—It may be convenient to use some of the water used for facilitate rapid sealing and opening of vials.
baseline / offset calibration as mix water for gains calibration, thereby (3) For each calorimeter cell to be calibrated, weigh an
ensuring that the mix water is at the same temperature as the calorimeter
prior to gains calibration. appropriate amount of the heat releasing material to be tested
into a test vial, the mass recorded to the nearest 0.01 g. Seal
X1.1.3 Gains calibration using an active material with
each vial with airtight lid. If possible use a rubber stopper for
known heat of hydration.
small glass vials instead of a cramping tool to facilitate rapid
X1.1.3.1 Internal Mixing—This method is used when an sealing and opening of vials.
instrument is configured so that the heat releasing material to (4) For each calorimeter cell to be calibrated, open the mix
be tested and water can be temperature equilibrated and mixed water vial and add the mix water to the corresponding vial with
while in place in the calorimeter cell. the heat releasing material to be tested; then mix water and heat
(1) Weigh an appropriate amount of the heat releasing releasing material to form a uniform paste. The mixing of water
material to be tested, the mass recorded to the nearest 0.01 g, and heat releasing material is done in the sample vial in such
and place in the calorimeter cell. Weigh or determine volu- a way that the time between the addition of water and the time
metrically water to give a suitable water-active material ratio of when the sample is put into the calorimeter is less than 60 s.
at least 0.50. It is essential that the water and the heat releasing Immediately after mixing, seal the sample vial with an airtight
material are separated before the start of the measurement as lid and load the sample vial with active material into the
water vapor absorption on the material can give rise to calorimeter. Log the signal for at least 48 h after mixing.
significant thermal powers. If a syringe is used to add water to
the heat releasing material, water migration / evaporation from NOTE X1.3—Use of a vortex-type mixing device (as commonly used for
the tips of the syringe needles must be avoided. Pull 0.5 mL of mixing materials in test tubes) has been found to generate adequate mixing
air into the syringe with water and then place a small drop of of heat releasing material and water in less than 60 s, for samples vials
smaller than 50 mL. Hand mixing using disposable spatulas has been
vacuum grease on the needle tip. Allow the calorimeter to found to generate adequate mixing of heat releasing material and water in
return to a stable baseline level before proceeding (this will less than 60 s, for samples vials larger than 50 mL. Cut off the part of a
normally take at least one hour). spatula that has been in contact with the sample and leave inside the vial

7
 C1702 − 15a
after mixing. Care should be taken that the incidental warming or cooling value of the signal in mV or V for an inert material (from
of the sample and the sample holder due to handling are minimal. measurements as described in X1.1.2), excluding initial parts
X1.2 Calculation that are not in thermal equilibrium.
X1.2.1 The total heat of hydration, Qt, is the integrated X1.2.2 A spreadsheet with instructions is available upon
value of the thermal power versus time data from the time of request for calculating offset and gains calibration for calorim-
mixing, collected as described in X1.1 without further correc- eters that generate raw data in units of V or mV.
tion as in Eq 3. The baseline / offset calibration is the average

X2. EVALUATION OF EXISTING CALIBRATION

X2.1 The procedure outlined in Appendix X1 can be used to hydration after 48 h for a heat releasing material with known
evaluate the accuracy of an existing calibration. An existing heat of hydration differs less than 10 J/g compared to the
calibration is considered accurate if the calculated heat of published or calculated value.

REFERENCES

(1) Poole, Toy S, Revision of Test Methods and Specifications for Isothermal Conduction Calorimetry for Measurement of 3 Days
Controlling Heat of Hydration in Hydraulic-Cement, PCA R&D Hydration.” This is an internet posting: http://epena.u-bourgogne.fr/
Serial No. 3007, Portland Cement Association, Skokie, IL, 2007. nanocem-calorimetry-group/literature-on-isothermal-cement
(2) Wadso L, Goldberg RN, Standards in Isothermal Microcalorimetry calorimetry/recent-round-robin-studies.
(IUPAC Technical Report), Pure Appl Chem 73, pp.1625-39, 2001. (5) VDZ, “Round Robin Heat of Hydration 2006,” Research Institute of
(3) Wadso L, Temperature Changes within Samples in Heat Conduction the German Cement Industry, Cement Chemistry Department,
Calorimeters, Thermochim. Acta 366, pp. 121-7, 2000 Dusseldorf, Germany, 2006.
(4) Wadso L. and Markus Arndt, “An International Round Robin Test of

SUMMARY OF CHANGES

Committee C09 has identified the location of selected changes to this test method since the last issue,
(C1702 – 15) that may impact the use of this standard. (Approved Aug. 1, 2015.)

(1) Added additional information on monitoring the effective-

ness of the vial sealing as Note 8 in 8.1.1.

Committee C09 has identified the location of selected changes to this test method since the last issue,
(C1702 – 14) that may impact the use of this standard. (Approved Jan. 15, 2015.)

(1) Revised subsections 8.1, 8.1.1, X1.1.2. (2) Revised Note 11.

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