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Influence of cement fineness and water-to-cement ratio on mortar early-age

heat of hydration and set times

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Construction and Building Materials 50 (2014) 657–663

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Influence of cement fineness and water-to-cement ratio on mortar

early-age heat of hydration and set times
Jiong Hu a,⇑, Zhi Ge b, Kejin Wang c
a
Department of Engineering Technology, Texas State University, 601 University Drive, San Marcos, TX 78666, United States
b
Department of Transportation Engineering, School of Civil Engineering, Shandong University, 17923 Jingshi Road, Jinan 250061, China
c
Department of Civil, Construction, and Environmental Engineering, Iowa State University, 492 Town Engineering Building, Ames, IA 50011, United States

h i g h l i g h t s

 Studied the influence of cement fineness on heat of hydration.

 Studied the influence of water-to-cement ratio on heat of hydration.
 Developed heat indexes to quantify heat of hydration process.
 Developed an innovative procedure to predict set times from calorimetry test.
 Compared set time predicted from the calorimetry method to the ASTM set time test.

a r t i c l e i n f o a b s t r a c t

Article history: In this study, hydration of mortars containing portland cement of three different finenesses and prepared
Received 19 July 2013 at four different water-to-cement ratios (w/c) were investigated using isothermal calorimetry tests.
Received in revised form 28 September Results showed that the hydration heat generated from cement with higher fineness was larger and faster
2013
compared to coarser cements in early ages. The lower w/c resulted in a higher heat of hydration rate at
Accepted 4 October 2013
Available online 5 November 2013
earlier hours but reduced after that. While the maximum heat of hydration rate was lower with higher
w/c, total heats of hydration within the first 24 h were found to be approximately the same, regardless
of the different w/c used. Initial and final set times determined from isothermal calorimetry were found
Keywords:
Hydration
to relate to set times determined from ASTM C403 penetration tests. The set times increased with the
Calorimetry increasing of the w/c and decreasing of the cement fineness. However, due to the very different mecha-
Isothermal nisms and test setups in determining setting times, the relationship between these two methods may
Water-to-cement ratio vary among different cements. Longer setting times were generally obtained from the calorimetry
Fineness method compared to the ASTM set time test.
Set time Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction quantities and characteristics of the concrete constituents, as well

Recently, activities and interests in monitoring heat evolution
from cement hydration in portland cement concrete have dramat-
ically increased. The development of early-age concrete properties,
such as workability, setting time, strength gain and thermal crack-
ing resistance, are predominantly influenced by the kinetics of ce-
ment hydration [1]. Hydration of cementitious materials in a
concrete mixture results in a number of exothermic chemical reac-
tions that liberate heat [2]. The heat evolution process is strongly
influenced by the chemical and physical properties of portland ce-
ment, water-to-cement ratio (w/c), mineral and chemical admix-
tures, concrete mix proportions, construction procedures and
curing conditions of concrete [3–8]. As a result, deviations in the
⇑ Corresponding author. Tel.: +1 512 2456328; fax: +1 512 2453052.
E-mail address: jiong.hu@txstate.edu (J. Hu).
as effects of construction conditions, can be detected [9]. Concrete
performance can also be predicted by monitoring the heat of ce-
ment hydration [10,11].
Different calorimetry test methods have been developed to
monitor cement hydration over time [12–15]. The calorimetry pro-
cedure has also been termed as the heat signature or thermal fin-
gerprint test since it measures a heat/temperature-related
property that is unique to a given concrete mixture. From a purely
theoretical standpoint, there are two major types of calorimetry
tests: semi-adiabatic and isothermal. In a semi-adiabatic calorime-
try test, the heat of hydration is measured by monitoring the tem-
perature of a specimen while the specimen is under an insulated
condition and has minimal heat loss. The isothermal calorimetry
test, on the other hand, measures the heat flow from a specimen
while both the specimen and surrounding environment are main-
tained at approximately the same constant temperature. Previous

0950-0618/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.conbuildmat.2013.10.011
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658 J. Hu et al. / Construction and Building Materials 50 (2014) 657–663

research showed that the two methods can both be successfully Table 1
used to reflect changes from different mix designs, including Chemical, mineral composition and fineness of portland cement.

chemical and mineral admixtures usage, through monitoring the Chemical and mineral composition A B C
heat of hydration [16]. Calcium oxide (CaO), % 64.77 63.01 64.40
Setting is typically defined as the onset of rigidity in fresh Silicon dioxide (SiO2), % 20.97 20.27 20.70
portland cement concrete, and is usually viewed as a transitional Aluminum oxide (Al2O3), % 5.59 4.73 4.50
period between states of true fluidity and true rigidity. Set time of Ferric oxide (Fe2O3), % 2.27 3.51 4.10
Alkalies (Na2O equivalent), % 0.19 0.54 0.30
concrete is important in concrete construction since it directly re- Magnesium oxide (MgO), % 1.92 3.15 1.10
lates to the timing of different processes of placing and finishing Sulfur trioxide (SO3), % 2.99 2.86 2.20
concrete. The initial set usually represents the approximate time Loss on ignition (LOI), % 0.82 1.56 1.10
when the fresh concrete can no longer be properly handled and Tricalcium silicate (C3S), % 54.98 57.51 62.48
Dicalcium silicate (C2S), % 18.64 14.73 12.21
placed, while final set approximates the time when the hardening
Tricalcium aluminate (C3A), % 10.97 6.60 4.99
begins or concrete starts to develop strength. The two methods Tetracalcium aluminoferrite (C4AF), % 6.91 10.68 12.48
that are usually used for set time determination are the Vicat Blaine fineness, m2/mg 399 364 302
needle based on ASTM C191 [17] and penetration resistance test
based on ASTM C403 [18] for cement paste and mortar samples,
respectively. Both Vicat and penetration resistance tests are
purely arbitrary measurements, which simply define initial and fi- 2.2. Experimental method and test procedure
nal set times based on subjective values of resistance from pre-
In the present study, an isothermal calorimeter (shown in Fig. 1a) was used to
pared paste and mortar samples, yet do not correspond exactly measure the heat generation of mortars with different cements and w/c. The iso-
to any specific change in concrete properties. In addition, the thermal calorimeter contains eight separate units, each holding a single specimen
two tests could many times be time consuming (in cases such during a test. As shown in Fig. 1b, each unit has an aluminum sample holder which
as tests for mixes with high amount of supplemental cementi- rests on a heat flow sensor (Peltier) that is placed on a common heat sink of a large
block of aluminum. On the other side of the heat sink is another heat flow sensor
tious materials) and not practical. Approaches including calorim-
and a piece of 129-g aluminum block. The aluminum block is used as a reference
etry set time models have also been developed to estimate setting to reduce the noise signal in this conduction calorimeter. In order to control the test
times from heat of hydration [19]. Besides potentially serves as an conditions, the isothermal calorimeter was placed in a temperature controlled
alternative method and automatic measurement of set time, this chamber. When a sample is placed in the unit, the heat produced by hydration
flows rapidly to its surroundings. The main route for heat exchange between the
new approach could provide a more accurate evaluation of the
sample and the surroundings is through the heat flow detector. The heat flow,
hydration process and early detection of incompatibility issues caused by the temperature difference across the sensor, creates a voltage signal pro-
[1,16]. portional to the amount of heat flow. A computer program was used to record the
While the water-to-cement ratio (w/c) is considered one of the voltage signal. This voltage signal was then converted to the rate of heat evolution
major variables influencing concrete strength, it is also a domi- by applying the calibration factor based on the reference material (aluminum).
Isothermal calorimetry tests (set at 23 °C) were performed to investigate how
nant factor that affects cement hydration since the w/c directly
the cement fineness and w/c may influence early-age heat of hydration within
controls the volume of water available for hydration for each unit the first 24 h. Mortars were mixed according to ASTM C305 [26]. Four samples from
volume of cement particle, as well as the interparticle spacing be- each mix, with weights of 100 ± 2 grams each, were placed into 125 ml plastic con-
tween them. On the other hand, since particle sizes of cement tainers and then loaded into the isothermal calorimeter (shown in Fig. 1) immedi-
ately after samples were ready. After samples were placed into the calorimeter, the
obviously affect the hydration rate, cement fineness incontrovert-
pre-programmed calorimeter started taking readings immediately. Readings were
ibly affects hydration. While effects of cement fineness and w/c taken every 30 s for 24 h. Rates of heat evolution per gram of cement were then cal-
on cement hydration has been well recognized, and studied by culated based on the mix design of the mortar, and average values from four sam-
several researchers, most of the studies were either based on ples of each mix were used for analysis.
qualitative description of hydration curves or parameters that Set times of mortars from the same mixes used for the isothermal calorimeter
tests were measured following the procedures described in ASTM C403 at a temper-
indirectly reflect hydration, such as set time and strength
ature of 23 ± 3 °C and relative humidity of 50 ± 5%. The ASTM set time measurement
[6,7,20–24]. A study is needed to accurately interpret the hydra- determines the set time of a mortar specimen, by means of penetration resistance
tion process and quantify effects of cement fineness and w/c on measurements on mortar. A mortar specimen is placed in a container and stored at
cement hydration. This study intends to evaluate the influence a specified ambient temperature. At regular time intervals, the resistance of the
mortar to penetration by standard needles is measured. From a plot of penetration
of portland cement fineness and w/c on heat of hydration within
resistance versus elapsed time, times of initial and final setting are determined as
the first 24 h. In addition to the six heat of hydration indexes the times when the penetration resistance equals 3.5 MPa and 27.6 MPa,
used to describe the hydration process, initial and final calorime- respectively.
try set times from isothermal calorimetry tests will also be calcu-
lated and compared with set times determined from the ASTM
C403 procedure [18]. 3. Isothermal thermal parameters

Isothermal calorimetry tests, often used in studying the kinetics

2. Experimental details
2.1. Materials and mix design
Three different kinds of portland cement, including one Type I cement (Cement
A), and two Type I/II cements (Cement B and Cement C) were used in the present
study. The information of oxide compositions, calculated Bogue phase composi-
tions, and Blaine finenesses are provided in Table 1. While the chemical and mineral
compositions of the three cements are similar, finenesses are very different. Cement
A has the highest fineness, Cement C has the lowest fineness, and Cement B falls be-
tween Cements A and C.
Mortar mixtures with the three different cements (A, B and C) at selected w/c of
0.35, 0.40, 0.50 and 0.60 were prepared with a constant sand-to-cement ratio of
2.20. Natural graded river sand with a specific gravity of 2.63, fineness modulus
of 2.92 and a gradation fitting the ASTM C33 [25] requirements was used in the
study.
of cement hydration, are conducted at a constant temperature.
Each specimen’s rate of heat evolution is directly measured by
monitoring the heat flow released (reaction rate). The total heat
evolution can be readily determined from the integration of the
measured heat flow rate over time. An example of the rate of heat
development versus hydration time curve is illustrated in Fig. 2.
The curve clearly shows the typical five stages of hydration reac-
tion as described in the literature [2], which are the initial reaction,
the induction period, the acceleratory period, the deceleratory per-
iod and the period of slow continued reaction. It is generally agreed
that setting takes place in the acceleratory period, during which
the silicates begin to hydrate rapidly, reaching a maximum rate.
The end of the acceleration period corresponds with the maximum
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J. Hu et al. / Construction and Building Materials 50 (2014) 657–663 659

(a) Inside look of isothermal test units

Aluminum Sample Holder

125 ml Plastic Cup
Heat Flow Detector (Peltier)
Mortar Sample

Aluminum Heat Sink

129 gram Aluminum Block

(b)Configuration of the isothermal test module

Fig. 1. Isothermal test device.

used to predict concrete performance as well as for concrete qual-

ity control [16].

3.1. Heat indexes

In the present study, six parameters (heat indexes) were used in

Fig. 2. Example of heat of hydration curve.
describing heat evolution curves. These parameters included the
five areas (A1–A4, and total area A) underneath the heat evolution
curve and the maximum rate of heat generation. As shown in
Fig. 3a, the areas underneath the curve represent heats generated
during different periods. The areas from 1 h to 6 h (A1), 6 h to
12 h (A2), 12 h to 18 h (A3), 18 h to 24 h (A4) and 1 h to 24 h (A)
were calculated. It should be noted that the data prior to one hour
was not used due to the fact that the calorimeter system required a
certain time to reach the equilibrium status after a sample was
loaded. In addition, the maximum rate of heat generation was also
used.

rate of heat evolution. During the deceleratory period, the reaction
makes a transition from the chemical control to diffusional control.
Based on above mentioned reasons, it is very important to inter-
pret the meaning of the heat evolution curve correctly and effec-
tively after a calorimeter measurement. In this study, heat
indexes and calorimetry set times were established to help inter-
pret results from calorimetry tests. These parameters can also be
3.2. Calorimetry set times
Generally speaking, setting of concrete is the transition period
between the fluidity and rigidity stage [10,27]. Concrete setting
behavior is controlled by its three-dimensional microstructure
development that involves new phase growth, nucleation, percola-
tion and networking of cement hydration products [28]. These
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660 J. Hu et al. / Construction and Building Materials 50 (2014) 657–663

4. Experimental results and analysis

4.1. Heat evolution curves and heat indexes

Calorimetry test results, including both rate of heat generation

and cumulative heat from the three different types of cements used
in this study, are shown in Figs. 4–6, respectively. The three figures
demonstrate that when different cements were used, the shape of
heat generation curves changed, but the trend of these curves with
different w/c remained similar, i.e., the maximum rate of heat gen-
eration decreases with increased w/c, while the time for mortar
mixtures to reach the maximum rate of heat generation increases
as w/c increases. One possible explanation is that a higher w/c
causes a relatively higher degree of dilution of cement in the ce-
ment–water solution, which may result in a lower rate of hydration
and reduced/retarded heat of cement hydration in early ages. The
results presented for Cement B here are fairly consistent with those
generated previously for mortars with w/c = 0.35 and 0.40 [7].
Heat indexes, including areas under heat evolution curves dur-
ing different test periods, are used to quantitatively describe the
effect of cement fineness and w/c on early age hydration. The cal-
culated areas of heat generated under different periods of time are
shown in Table 2. Results indicated that despite the difference of
cement fineness, most of the mortar showed similar trends on
the effect of w/c on the heat of hydration rate. The heat generation
was found to be higher in low w/c mixes at an early age; however,
with the hydration process in effect, the heat of hydration reduces
more quickly in low w/c mixes, and a higher hydration heat was
generally found at later ages in high w/c mixes. This is partially
due to the higher w/c mixtures having more space for the precipi-

Cement A (S/C=2.2) w/c=0.35

w/c=0.40
Rate of heat generation, mW/g

Fig. 3. Development of heat indexes and calorimetry set times. w/c=0.50

6 w/c=0.60
processes are significantly related to the cement hydration process,
which is often characterized by its heat evolution [29]. Therefore,
even though there is no scientific data available to support the cor- 4
relation between the rapid temperature rise and the beginning of
the formation of a percolated network, it is rational to believe that
the set time of a normal concrete mixture can be determined from 2
a heat of cement hydration curve. From a microscopic point of
view, concrete initial set is the time when cement hydration prod-
ucts, which initially surround individual cement particles, start to
0
form a network which could correspond to the beginning of a rapid
0 6 12 18 24
temperature rise in concrete that follows the dormant period [10]. Time, hour
Concrete final set is the time when a primary network of hydration
80
products has developed [27]. The final set can be related to the
time concrete heat evolution reaches its maximum rate during 70 Cement A (S/C=2.2)
Cumulative heat, J/g

the acceleration period, which corresponds to the approximate

midpoint of the major peak hydration process [10]. 60
In this study, a new procedure was developed to determine cal-
50
orimetry initial set and final set times based on the first derivative
w/c=0.35
of the heat evolution curve. A typical curve of first derivative of 40 w/c=0.40
heat evolution curve (d(q)/d(t)) derived from the original heat evo- w/c=0.50
30 w/c=0.60
lution test data is shown in Fig. 3b. The calorimetry initial set time
of the tested mortar is defined as the time when the first derivative
20
curve reaches its highest value. At this point, the increase in the
rate of heat generation is the fastest. After the calorimetry initial 10
set time, the first derivative value starts to decrease. The time
when the first derivative drops to zero is defined as the calorimetry 0
0 6 12 18 24
final set of the tested mortar. This point corresponds to the time Time, hour
when the highest rate of hydration is achieved, and after this point
the rate of hydration will be reduced. Fig. 4. Isothermal test results of mortar with Cement A.
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J. Hu et al. / Construction and Building Materials 50 (2014) 657–663 661

8 8
w/c=0.35 w/c=0.35
Cement B (S/C=2.2) w/c=0.40 Cement C (S/C=2.2) w/c=0.40

Rate of heat generation, mW/g

Rate of heat generation, mW/g

w/c=0.50 w/c=0.50
6 w/c=0.60 6 w/c=0.60

4 4

2 2

0 0
0 6 12 18 24 0 6 12 18 24
Time, hour Time, hour
70 60
w/c=0.35 w/c=0.35
60 Cement B (S/C=2.2) w/c=0.40 Cement C (S/C=2.2)
w/c=0.40 50
w/c=0.50 w/c=0.50
w/c=0.60
Cumulative heat, J/g

Cumulative heat, J/g

50 w/c=0.60
40
40
30
30

20
20

10 10

0 0
0 6 12 18 24 0 6 12 18 24
Time, hour Time, hour
Fig. 5. Isothermal test results of mortar with Cement B.
Fig. 6. Isothermal test results of mortar with Cement C.

tation and growth of hydration products and also to self-desicca-

Table 2
tion effects in these sealed calorimetry specimens, with the latter
Isothermal calorimetry heat indexes.
mainly for the w/c = 0.35 mortars. Another observation is that the
differences of heat indexes from the higher w/c mixtures (w/ w/c 0.35 0.40 0.50 0.60
c = 0.50 and 0.60) are relative small. The result is likely due to Cement A Area 1–6 h (A1), mW/g h 22.8 20.5 18.3 16.8
the effect of bleeding in these higher w/c mixes, which was ob- Area 6–12 h (A2), mW/g h 22.9 24.0 24.7 24.9
served in mixtures at w/c of 0.60. The bleeding effect likely resulted Area 12–18 h (A3), mW/g h 13.0 14.1 15.5 15.5
Area 18–24 h (A4), mW/g h 8.9 9.2 10.5 11.5
in similar test specimens from w/c = 0.60 mixtures comparing to Area 1–24 h (A), mW/g h 67.6 67.8 69.1 68.6
those from w/c = 0.50 mixtures, with the exception of bleeding Max rate, mW/g 5.8 5.5 5.2 5.1
water on the top of specimens. Meanwhile, results shown in Table 2 Cement B Area 1–6 h (A1), mW/g h 13.0 10.5 8.6 7.8
also demonstrated that with the cement and w/c used in the pres- Area 6–12 h (A2), mW/g h 27.1 26.0 24.9 24.7
ent study, total heats generated in the first 24 h were very close, Area 12–18 h (A3), mW/g h 13.1 15.3 17.2 18.5
regardless what w/c was used. The same trend can be confirmed Area 18–24 h (A4), mW/g h 6.8 7.4 8.4 9.3
Area 1–24 h (A), mW/g h 60.0 59.2 59.2 60.3
in the cumulative heat generated in the first 24 h after mixing.
Max rate, mW/g 4.9 4.6 4.3 4.4
Since the diminishing of the hydration rate is affected by the
Cement C Area 1–6 h (A1), mW/g h 11.2 10.5 8.6 7.4
depletion of cement particles, it is reasonable to believe that the
Area 6–12 h (A2), mW/g h 18.2 18.1 17.8 16.8
switch from the acceleratory period to the deceleratory period de- Area 12–18 h (A3), mW/g h 11.7 12.1 13.1 12.9
pends on the particle size of cement. In addition to the effect of w/c, Area 18–24 h (A4), mW/g h 7.6 8.1 9.0 8.9
it is generally expected that finer cement will have an increased Area 1–24 h (A), mW/g h 48.8 48.8 48.5 45.9
heat release rate, although the ultimate heat releases may be sim- Max rate, mW/g 3.4 3.3 3.1 2.9

ilar [30]. Results from the present study did show that the heat
generated from hydration was much lower at early hours when a
coarser cement was used, while the heat of hydration showed a
lower maximum heat of hydration rate and peaked later with the
increase of w/c. Since hydration occurs at the surface of cement
particles, finely ground cement has a higher specific surface area,
which means there is more area in contact with water and, in turn,
results in a higher rate of hydration. As expected, the amount of
heat generated in the first 24 h decreased with decreasing fineness.
Cement C showed a significantly lower hydration heat compared to
Cements A and B. The results were consistent with a similar study
with cement pastes conducted by Bentz with cement of two differ-
ent finenesses [31].
4.2. Calorimetry and ASTM set times
In addition to heat indexes related to the heat generation during
different periods of time, the calorimetry initial set and final set
times (which are determined from the first derivative of the rate
of heat evolution curves) were obtained. Results shown in Table 3
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662 J. Hu et al. / Construction and Building Materials 50 (2014) 657–663

Table 3
ASTM and calorimetry set times.

w/c ASTM set time, h Calorimetry set time, h

0.35 0.40 0.50 0.60 0.35 0.40 0.50 0.60
Cement A Initial set (IS) 1.99 2.63 3.96 4.19 2.58 3.01 3.42 3.63
Final set (FS) 3.00 3.90 6.02 6.14 4.80 5.35 6.00 6.33
Cement B Initial set (IS) 2.95 3.92 5.36 6.52 4.30 4.44 4.77 5.13
Final set (FS) 4.78 5.75 7.09 8.01 6.86 7.59 8.45 10.40
Cement C Initial set (IS) 3.20 3.94 4.60 5.50 3.09 3.27 3.86 4.17
Final set (FS) 5.15 6.23 6.76 7.92 6.57 6.97 8.10 8.45

indicated that both calorimetry initial and final set times increased
with the increasing of w/c, which signified a slower microstructure
build-up in mortar mixes. As expected, the finest cement (Cement
A) was found to have the shortest calorimetry initial and final set
times. Conversely, similar trends of calorimetry initial and final
set times were not observed from mixes with the two coarser ce-
ments used in this study (Cements B and C). The phenomenon
might be due to the fact that although the coarser cement particles
reduce the rate of hydration, it requires slightly less hydration to
achieve equivalent set than a finer cement due to the higher degree
of structure build-up from the bigger size of particles. Also, since
no high range water reducer was used in these mortars, the cement
participles would be highly flocculated.
Set times from mortar mixes were also obtained from ASTM
C403 and compared with the set times estimated from calorimetry
tests. Linear relationships between ASTM set times and calorimetry
set times of mortar mixtures made with different cements and w/c
are presented in Fig. 7. Results showed that within the four mix-
tures from each cement, the calorimetry set times obtained from
calorimetry curves are well correlated with the set times measured
according to ASTM C403, with a coefficient of determination (R2)
above 0.85, although the relationship is not one-to-one. However,
the equation for the linear relationship may not necessarily be
the same in each case. It should also be pointed out that almost
all points were above the equality line, which indicated that the
set times determined by the calorimetry methods were longer than
those from the ASTM methods. The differences between the two
test methods are primarily due to the fact that the two methods
have very different mechanisms of determining set times. The
ASTM C403 method is based on the penetration force against
microstructure development (a physical process), while the calo-
rimetry method is based on the heat generation (a measure of
chemical reaction). One other reason that the ASTM penetration
method resulted in shorter set times might be due to heat

Fig. 7. Relationship between ASTM and calorimetry setting times.

 Author's personal copy
J. Hu et al. / Construction and Building Materials 50 (2014) 657–663
built-up from the exothermic reaction from cement hydration,
which can lead to a certain degree of acceleration of hydration
from the increase in temperature on the specimen. Similar conclu-
sions have been reached from the mortars test in that an adequate
correlation can be observed between setting time (as measured by
ASTM C191) and the time of the first maximum in the derivative of
heat relate rate, yet they are not identical and cannot be used inter-
changeably [7]. The lower degree of determination (R2 of 0.63 and
0.77 for initial set and final set, respectively) from the overall re-
sults comparing to individual cements, as shown in Fig. 7, also indi-
cated that calibration could be required to determine the specific
correct relationship for each individual cement.
5. Conclusions
Studies have been conducted to evaluate the effect of cement
fineness and mortar water-to-cement ratio (w/c) on the heat of
hydration and calorimetry set times using isothermal calorimetry
tests with different mortar mixtures. The results have indicated
that:
 Due to the decreased surface area, heat generated from hydra-
tion of coarser cement during earlier ages was lower from the
slower rate of hydration. The initial and final set times from
both calorimetry analysis and ASTM C403 tests were, therefore,
found to be longer from cement with lower fineness.
 While the lower water-to-cement ratios result in a higher rate
of heat of hydration in early hours after cement contact with
water, the rate of hydration heat did slow down at a later age.
With the cement and w/c used in the present study, the total
heats of hydration within the first 24 h were found to be
approximately the same, regardless of the different water-to-
cement ratios used.
 The initial and final set times can be determined from isother-
mal calorimetry results, and the set times were found to relate
linearly with set times determined from the ASTM C403 pene-
tration test. However, due to the very different mechanisms
and test setups in determining setting times, longer setting
times were found from the calorimetry method compared to
the ASTM penetration test, and the relationship between these
two methods may vary when different cements are used.
Acknowledgements
The authors would like to acknowledge the support from Na-
tional Concrete Pavement Technology Center (CP Tech Center) at
Iowa State University. The authors also extend their appreciation
and gratitude to Mr. Dale Bentz from the National Institute of Stan-
dards and Technology (NIST) for providing two of the cements used
in this study and for his valuable input.
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