Using Isothermal Calorimetry to Assess the Water

Absorbed by Fine LWA during Mixing

Javier Castro1; Igor De la Varga2; and Jason Weiss, M.ASCE3

Abstract: Fine lightweight aggregate (LWA) is being increasingly used for the manufacture of internally cured concrete. Internally cured
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concrete can be viewed as a concrete that contains fluid (water) in the pores of the LWA (or other porous inclusions) that can be released to the
paste after setting. Most research performed on internally cured concrete assumes the LWA has been prewetted for some time before mixing
(generally lab studies use 24-h soaking, whereas this value varies in practice). The research described in this paper investigated the potential
for using aggregate that begins the mixing process from a different moisture state (i.e., not 24-h prewetting). Specifically, this paper considers
oven-dry aggregate as a worst-case scenario to determine how much water would be absorbed by the LWA during the mixing and placement
processes. To determine the amount of water absorbed by the LWA, isothermal calorimetry was used. Two different mixing scenarios were
investigated, showing that 56–71% of the 24-h water absorption could be achieved using the worst-case scenario of oven-dry aggregates.
Although the use of oven-dry aggregate would be extremely rare for a field application (except for possible application to bagged products),
this approach could be extended to include fine LWA with other initial moisture conditions. DOI: 10.1061/(ASCE)MT.1943-5533.0000496.
© 2012 American Society of Civil Engineers.
CE Database subject headings: Aggregates; Curing; Cement; Hydration; Mixing.
Author keywords: Lightweight aggregate; Internal curing; LWA absorption capacity; Calorimetry; Cement hydration.

Introduction development is owing primarily to issues associated with increased

Internal curing (IC) typically refers to the use of prewetted light-
weight aggregate (LWA) (or other water-filled inclusions, such as
super-absorbent polymers or cellulose fibers) that can release water
at the correct time to provide curing water throughout the cross
section of concrete. The idea that LWA can provide moisture to
the cement as it hydrates in concrete has been known for more than
5 decades (Klieger 1957). Bloem (1965) reported that “high
absorption lightweight aggregate (LWA) may have the beneficial
effect of supplying curing water internally.” Philleo (1991) dis-
cussed the potential for improved strength and durability as a result
of the beneficial release of water from LWA. Holm et al. (2004)
reported anecdotal evidence of reduced plastic shrinkage cracking
in LWA mixtures during high-rise construction. Although these ob-
servations have been made on the benefits of LWA for improved
curing, it is only recently that the use of LWA has been specifically
designed to improve the curing of concrete (Bentz and Snyder
1999; Jensen and Hansen 2001; RILEM 2007; Lopez et al.
2009; Henkensiefken et al. 2009; Castro et al. 2012). This
1
Pontificia Universidad Católica de Chile, School of Engineering,
Casilla 306, Correo 22, Santiago, Chile (corresponding author). E-mail:
jecastro@ing.puc.cl
2 be 0.83 (0:30∕0:36).
Graduate Research Assistant, School of Civil Engineering, Purdue
Univ., School of Civil Engineering, 550 Stadium Mall, West Lafayette,
IN 47907-2051. E-mail: idelavar@purdue.edu
3
Professor and Director of Pankow Materials Laboratory, Associate
Director of the Center for Advanced Cement Based Materials, Purdue
Univ., School of Civil Engineering, 550 Stadium Mall, West Lafayette,
IN 47907-2051. E-mail: wjweiss@purdue.edu
Note. This manuscript was submitted on June 3, 2011; approved on
February 1, 2012; published online on February 3, 2012. Discussion period
open until January 1, 2013; separate discussions must be submitted for in-
dividual papers. This paper is part of the Journal of Materials in Civil
Engineering, Vol. 24, No. 8, August 1, 2012. ©ASCE, ISSN 0899-
1561/2012/8-996–1005/$25.00.
observances of cracking in higher-strength, lower water-to-cement
ratio (w∕c) concrete (Weiss 1997; RILEM 2003).
The mixture proportioning approach for IC concrete uses a
methodology proposed by Bentz et al. (2005). This methodology
estimates the volume of IC water by relating it to volume of the
chemical shrinkage using Eq. (1)
C f × CS × αmax
M LWA ¼ ð1Þ
S × ϕLWA
where M LWA = mass (kg∕m3 ) of LWA (in a dry state) that needs to
be prewetted to provide water to fill in the voids created by chemi-
cal shrinkage; C f = cement content (kg∕m3 ) of the mixture; CS =
chemical shrinkage of the cement (mL of water∕g of cement),
which is considered 0:064 mL∕g of cement; αmax = expected
maximum degree of hydration, which owing to space limita-
tion is considered to be ðw∕cÞ∕0:36 for w∕c less than 0.36 and
1 for w∕c higher than 0.36; ΦLWA = absorption capacity
(kg of water∕k go dry LWA) of the LWA (taken normally as
the 24-h absorption value); and S = expected degree of saturation
of the LWA, expressed as a function of the taken absorption value
(ΦLWA ). In the case of a mortar prepared with a w∕c ¼ 0:30, as
described in this paper, the maximum degree of hydration will
It is well known that the absorption of water by the LWA takes
place over time (Landgren 1964; Holm et al. 2004). Castro et al.
(2011) reported a test to determine the time-dependent water
absorption and S values from the most widely used LWAs in North
America. Although this research proposed a generalized equation
to describe the rate of absorption, it was shown that LWA absorbs
65–80% of the 24-h absorption during the first 5 min of being
soaked in water. It also has been reported that the water absorption
can continue taking place over weeks, months, and even years at a
much lower rate (Landgren 1964; Holm et al. 2004). In cementi-
tious mixtures, the LWA may be able to continue absorbing water

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J. Mater. Civ. Eng. 2012.24:996-1005.

 from the mixture before set (Trtik et al. 2011), but as the LWA
is added to the batch in a prewetted condition, this additional
absorption is normally not considered to be significant for design
purposes. However, the concept of the aggregate absorbing water
before set will become relevant if the LWA was added to the mixer
from a dry condition.
As mentioned, internally cured concretes are generally designed
to be cast using prewetted LWA. In discussions with local industry
experts regarding the implementation of IC, some concern was
raised by some concrete producers regarding the potential chal-
lenges of batching of wet, fine LWA. This question was the result
of a potential concern that overwetted fine LWA may be difficult to
handle in a plant because it may “arch” and “stick” in the aggregate
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bins. Similar concerns have been expressed by some producers
with handling overwetted LWA during freezing conditions, which
can occur in some winter operations. Although some producers
have reported no problems, some found that increasing the volume
of the charge in the aggregate bins can help reduce the arching
(the increased mass helps to overcome arching), and others may
prefer to use the LWA in a less wet state. If the aggregate were
used in a drier state, some have raised questions whether this
may be able to provide the expected benefits of IC. A recent study
(Golias et al. 2012) measured the properties of IC concrete using
LWA with different amounts of water (i.e., different S values).
When the mixture proportioning was adjusted to account for the
actual amount of water absorbed, IC was found to be effective even
if oven-dry aggregates were used. This work seeks to provide an
improved understanding of the water that may be absorbed by the
LWA during mixing. This paper discusses a worst-case scenario in
which the LWA that is added to the batch is from a dry condition.
The impetus for using isothermal calorimetry to determine the
absorption of an IC agent comes from the work of Johansen et al.
(2009). Johansen et al. (2009) used isothermal calorimetry to study
the water absorption of pulp fibers by taking advantage of the
different heat signature associated with different w∕c systems.
Johansen et al. (2009) used the rate of heat evolution for pulp fibers,
whereas this paper uses an approach on the basis of the total heat
release at a specific time owing to the potential effect that chemical
admixtures may have on altering the rate of reaction at early ages in
the mixtures.
This paper describes a research program that used isothermal
calorimetry to estimate the amount of water that is absorbed by
dry LWA during mixing and placement. Although this approach
is used for oven-dry aggregate in this paper, this approach can
be extended to other initial moisture conditions for the aggregate.
These findings can improve how internally cured concrete mixtures
are proportioned, batched, and placed as this technology grows.
Experimental Program
Table 1 shows the testing matrix that was used in this investigation.
Five series of mixtures were considered. The first series consisted
of plain cement pastes with different w∕c. The second series
considers a single w∕c; however, the dosage of a water-reducing
(WR) admixture was varied. The third series consisted of plain
mortars with different w∕c. The fourth and fifth series are internally
cured mortar mixtures. The fourth series considers mixtures in
which the LWA was allowed to absorb water for 24 h before mixing
(referred to as prewetted). The fifth series of mixtures contains a
constant volume of oven-dry LWA, but different water absorptions
during mixing are assumed.
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J. Mater. Civ. Eng. 2012.24:996-1005.
Constituent Materials
This study used ASTM C150 (2011) Type I ordinary portland ce-
ment (OPC), with a Blaine fineness of 370 m2 ∕kg and an estimated
Bogue phase composition of 56% tricalcium silicate (C3 S), 16%
dicalcium silicate (C2 S), 12% tricalcium aluminate (C3 A), 7%
tetracalcium aluminoferrite (C4 AF) and a sodium oxide (Na2 O)
equivalent of 0.68% by mass. The sand used was natural river sand,
with a fineness modulus of 2.71, an apparent specific gravity
of 2.58, and water absorption of 1.0% by mass. Portions of the
normal-weight sand were replaced with expanded shale (Buildex,
Marquette,KS), with a fineness modulus of 3.10 and a specific
gravity of 1.45. The 24-h absorption of the LWA was determined
to be 17.5% according to the paper towel method [New York
Dept. of Transportation (NYDOT) 2008; Castro et al. 2011]. A
polycarboxylate-based high-range WR admixture (Glenium
3030, BASF, Cleveland) was added at variable dosage by mass
of cement to maintain the same (mini) slump in all mortars. Slump
was measured following the procedure of Kantro (1980). Mixture
proportions are shown in Table 1. Sieve analysis of the normal-
weight aggregate and LWA is shown in Table 2.
Mixing, Casting, and Sample Preparation
The mixing procedure used for the cement paste and plain mortars
(without LWA) was in accordance with ASTM C305 (ASTM 2006).
For the internally cured mortars prepared with prewetted LWA (de-
fined as LWA mortars), the LWA was oven dried, air cooled, and then
submerged in water for 24
1 h before mixing. The volume of water
used to submerge the LWA included both mixing water and the water
the LWA would absorb in 24 h. The excess water (water not absorbed
in 24 h) was then decanted and used as the mixing water. For the
internally cured mortars prepared with dry LWA (defined as dry
LWA mortars), the LWA was oven dried and air cooled before mixing.
Then two different procedures were used for mixing. In the first mix-
ing procedure (Mixing Procedure 1), all of the dry materials were
premixed in the mixer, then the water was added, in which case
the water is simultaneously being absorbed by the aggregate and re-
acting with the cement. In the second mixing procedure (Mixing Pro-
cedure 2), the dry LWA was allowed to soak in the water in the mixer
for 5 min before being put in contact with the normal-weight sand and
the cement. For all mixtures, the normal-weight sand was oven dried
and cooled for 24 h before mixing. The water and cement were con-
ditioned for 24 h at room temperature before mixing.
Testing Protocols
Surface Dry Absorption
As previously mentioned, it has been reported that water absorption
by the LWA can continue taking place over weeks, months, and
even years at a much lower rate (Landgren 1964; Holm et al.
2004); Holm et al. (2004) stated that because the prewetting of
LWA will fill only a fraction of the LWA pores, “the use of the
ASTM expression ‘saturated surface dry (SSD)’ is inappropriate
for LWA, theoretically inaccurate and analytically misleading.”
The authors fully agree with this statement and will use the term
“surface dry” (SD) throughout this paper.
To determine the SD condition for prewetted LWA, the paper
towel method was used. The paper towel method uses a test pro-
cedure from the NYDOT (2009). The paper towel method involves
immersing the aggregate in water [two conditions were used, either
submerged in water for 24 h or under vacuum for 1 h at 98.2 kPa
(737 mmHg), followed by keeping the aggregate under water
for the following 23 h], after which time the water is decanted
and the surface of the aggregate is patted dry. After prewetting,
 Table 1. Mixture Proportion of Mixtures Used in This Research
Water in
Normal-weight Lightweight Lightweight Water reducer
Cement Water aggregate, saturated aggregate, dry aggregate (g∕100 g of
Mixture designation w∕c (kg∕m3 ) (kg∕m3 ) surface dry (kg∕m3 ) (kg∕m3 ) (kg∕m3 ) cement.)
Paste 0.30 0.30 1,615.6 484.7 — — — —
Paste 0.33 0.33 1,540.8 508.5 — — — —
Paste 0.36 0.36 1,472.5 530.1 — — — —
Paste 0.39 0.39 1,410.1 549.9 — — — —
Paste 0.42 0.42 1,352.7 568.1 — — — —
Paste 0.45 0.45 1,299.9 584.9 — — — —
Paste 0.50 0.50 1,220.3 610.2 — — — —
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Plain mortar 0.30–0.0% 0.30 727.0 218.1 1,429.7 — — —

Plain mortar 0.30–0.6% 0.30 727.0 218.1 1,429.7 — — 0.6
Plain mortar 0.30–1.2% 0.30 727.0 218.1 1,429.7 — — 1.2
Plain mortar 0.30 0.30 727.0 218.1 1,429.7 — — 0.6
Plain mortar 0.33 0.33 693.3 228.8 1,429.7 — — 0.4
Plain mortar 0.36 0.36 662.6 238.6 1,429.7 — — 0.2
Plain mortar 0.39 0.39 634.5 247.5 1,429.7 — — —
Plain mortar 0.42 0.42 608.7 255.7 1,429.7 — — —
Plain mortar 0.45 0.45 584.9 263.2 1,429.7 — — —
Plain mortar 0.48 0.48 562.9 270.2 1,429.7 — — —
Plain mortar 0.51 0.51 542.5 276.7 1,429.7 — — —
Lightweight aggregate mortar 0.27 0.27 764.2 206.3 1,053.1 209.6 36.7 0.8
Lightweight aggregate mortar 0.30 0.30 727.0 218.1 1,031.5 221.6 38.8 0.6
Lightweight aggregate mortar 0.33 0.33 693.3 228.8 1,012.0 232.4 40.7 0.4
Lightweight aggregate mortar 0.36 0.36 662.6 238.6 994.2 242.3 42.4 0.2
Lightweight aggregate mortar 0.39 0.39 634.5 247.5 1,012.7 232.1 40.6 —
Lightweight aggregate mortar 0.42 0.42 608.7 255.7 1,029.7 222.6 39.0 —
Lightweight aggregate mortar 0.45 0.45 584.9 263.2 1,045.3 213.9 37.4 —
Dry lightweight aggregate 50% 0.30 727.0 218.1 1,031.5 221.6 19.4 0.6
Dry lightweight aggregate 55% 0.30 727.0 218.1 1,031.5 221.6 21.34 0.6
Dry lightweight aggregate 60% 0.30 727.0 218.1 1,031.5 221.6 23.28 0.6
Dry lightweight aggregate 65% 0.30 727.0 218.1 1,031.5 221.6 25.22 0.6
Dry lightweight aggregate 70% 0.30 727.0 218.1 1,031.5 221.6 27.16 0.6
Dry lightweight aggregate 80% 0.30 727.0 218.1 1,031.5 221.6 31.04 0.6

Table 2. Gradation of Lightweight (LWA) and Normal-Weight (NWA) Time-Dependent Absorption

Aggregates Used in this Research
To evaluate the absorption of water as a function of time, a volu-
NWA metric flask test was conducted (Castro et al. 2011). In this test, the
LWA Sieve number Percentage passing LWA (entire gradation shown in Table 2) is prepared by placing it in
an oven at 105
2°C for 24
1 h and is then cooled for 24 h. A
4 98.1% 99.7%
100
10 g of sample is placed in a 250-ml volumetric flask.
8 84.8% 93.0% Deionized water is added to approximately 80% of capacity of
16 56.4% 75.6% the flask. The flask is then manually agitated for 2–3 min to min-
30 34.0% 49.8% imize entrapped air bubbles between the aggregate particles. After
50 20.4% 19.3% agitation, the fine particles are allowed to settle to see the level of
100 11.9% 2.7% the fluid on the flask. Additional water is added to bring the water
Fineness modulus 2.94 2.60 level in the flask to its calibrated capacity. The total mass of the
flask, aggregate sample, and water is recorded 5 min after the water
was first in contact with the aggregate. As the aggregate continues
the aggregate was spread out, and the paper towel is laid across the absorbing water over time, the level of the fluid will decrease.
surface of the aggregates. This process of prewetting the aggregate Additional water is then added to the flask to keep the fluid at its
and using the paper towel to determine whether surface moisture is calibrated capacity at regular intervals, recording the total mass and
still present is repeated at different moisture contents (preferable the actual time of measurement. Each time before water is added,
near the SD condition). Once it appears that the paper towel is the flask is agitated for approximately 30 s to eliminate new air
no longer picking up moisture from the aggregate (as determined bubbles.
by visual inspection for a change in color from the paper towel) it is The procedure described in the previous paragraph does not cap-
assumed that an SD condition has been reached, and the aggregate ture the water absorption during the first 5 min after water is placed
moisture can be determined. in contact with the aggregate. However, by assuming the absorption

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J. Mater. Civ. Eng. 2012.24:996-1005.

 value at 24 h is the same as the 24-h absorption obtained by
the paper towel method, the difference between both values can
be used to back-calculate the absorption that occurs during the
first 5 min of this test.

Lightweight Aggregate Desorption

The loss of water from the LWA pores during drying can be
described through a desorption isotherm [a plot of normalized mass
loss as a function of relative humidity (RH) at a constant temper-
ature]. A dynamic vapor desorption analyzer was used to enable the
sorption behavior to be evaluated under carefully controlled
temperature and humidity conditions. Additional information about
the procedure can be found in Castro et al. (2010, 2011).
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Fig. 1. Time-dependent water absorption of lightweight aggregate

For the dynamic vapor desorption tests, aggregate particles that
passed the #8 sieve and retained on the #16 sieve were used. The
LWA particles were prepared by placing them in an oven at 105

2°C for 24
1 h, cooled for 24 h, and placed in deionized water for
the desired time before testing, which was 6 h, 24 h, and 9 days in
this study (the same aggregate particles were used in each of the
three tests). Once the prewetting of the aggregate was complete, the
LWA was removed from water, “patted to SD” using absorbent tow-
els, and placed in a tared 180-mL quartz pan. The pan containing
the sample was then suspended from the balance (
0:001-mg ac-
curacy) and placed in the RH chamber to equilibrate at 23:0

0:05°C and 98
0:1% RH for up to 48 h or until the sample
had achieved a stable mass (mass change < 0:001%∕15 min).
After the sample equilibrated, the RH in the chamber was changed
in 1% RH steps to 80% RH, allowing the sample to equilibrate at
the new humidity (mass change < 0:001%∕15 min or 48 h of
exposure, unless noted otherwise). After equilibrating at 80%
RH, the samples were dried to 0% RH at 23
0:05°C for up to
48 h or until the sample had achieved a stable mass.
Although the desorption analysis was performed on one size
aggregate in this study, it has been shown that the desorption of
this aggregate corresponds well with a full gradation of aggregates,
as those shown in Table 2 (Pour-Ghaz et al. 2011).
Isothermal Calorimetry
The IC supplies additional water that can increase hydration of the
cement (Henkensiefken et al. 2009), and densify the microstructure
at the surface of the LWA (Elsharief et al. 2005; Peled et al. 2010).
To measure the potential increase in hydration, an isothermal
calorimeter (TAM Air by AS Instruments) was used as previously
reported by Pane and Hansen (2005), Poole et al. (2007), Johansen
et al. (2009), and Lura et al. (2010). Approximately 10 g of exter-
nally mixed mortar were placed into each vial, with two replicates
for each mixture. The cumulative heat of hydration was measured
during the first 7 days after mixing. Detailed instructions about the
use of the isothermal calorimeter can be found in the equipment
operator’s manual (TA Instruments 2008).
Fig. 2 shows the normalized desorption response for the LWA
that was presoaked for three different lengths of time: 6 h, 24 h, and
9 days. From Fig. 2 it can be observed that a substantial portion of
the moisture is lost at high relative humidities, indicating that
the pore size of the aggregate is large enough that the water can
be easily given to the paste as needed during hydration. Further
more, extension of the presoaking period produces a difference
in the amount of water that is held in the pores of the LWA
(absorption) at high relative humidities, but it does not appear to
appreciably change the amount of water that is held in the pore
at relative humidities lower than 98% (desorption).
Isothermal Calorimetry
Fig. 3 shows the measured heat of hydration during the first 7 days
for plain paste mixtures with seven different values of w∕c (0.30,
0.33, 0.36, 0.39, 0.42, 0.45, and 0.50). Fig. 3(a) shows the rate of
heat release during the first 18 h, whereas Fig. 3(b) shows the
cumulative heat release. Before setting (i.e., before approximately
4 h, depending on the w∕c owing to particle spacing), the rate of
heat release is very similar. Even during the first 18 h, the hydration
rates are not dramatically different (although the 0.30 mixture
appears to be slightly influenced by the admixture used, and the
0.50 mixture may be slightly retarded). This is consistent with
results reported by Bentz et al. (2009) and Bentz (2010). At later
times, however, the rate of heat release (and cumulative heat)
begins to diverge, and a higher cumulative heat release is observed
for higher w∕c pastes. This increased heat can be interpreted as an
increase in the degree of hydration, which is in agreement with
measurements on the basis of nonevaporable water reported by
Taplin (1959), although Taplin’s measurements were made at later

Experimental Results

Aggregate Absorption and Desorption

Fig. 1 shows the normalized water absorption of the LWA (normal-
ized to the 24-h absorption) as a function of time. According to
Fig. 1, the LWA absorbs nearly 63% of the 24-h absorption in
the first 5 min of being soaked under water. The y-axis for Fig. 1
can be thought of as the saturation coefficient that is described in
Eq. (1) (Castro et al. 2011). It is also shown that the 24-h absorption
Fig. 2. Moisture desorption of lightweight aggregate presoaked for
of water is substantially less than the absorption determined from
different periods of time
vacuum saturation (98.2 kPa).

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J. Mater. Civ. Eng. 2012.24:996-1005.


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Fig. 3. Effect of water-to-cement ratio on hydration of cement paste,
expressed as (a) rate of hydration; (b) cumulative heat of hydration
ages. Similar behavior has been observed by Schindler and
Folliard (2005).
Fig. 4 shows the heat of hydration for a series of mortar mixtures
(w∕c ¼ 0:30) that were intentionally prepared with different
amounts of WR admixture in dosages expressed as percentage
of the cement mass. Differences in the dosage of WR can alter
(delay or accelerate) the reaction of the cement. At early ages,
the measured heat of hydration is dependent on the dose of chemi-
cal admixtures; however, by an age of 72 h, all of the mixtures have
Fig. 4. Effect of addition of water reducer on heat of hydration of
cement
1000 / JOURNAL OF MATERIALS IN CIVIL ENGINEERING © ASCE / AUGUST 2012
J. Mater. Civ. Eng. 2012.24:996-1005.
a similar heat release (heat of hydration). This is important because
it indicates that measures of the total heat of hydration at a later age
(e.g., > 48 h) may be less prone to variations in the rate of heat
release owing to the use of chemical additives. By reducing the
potential influence of chemical admixtures on the value used to
determine absorption, the later age value may (for some cases in
which the admixture dosage varies) provide information that is a
more direct representation of the w∕c when using calorimetry to
detect the amount of water absorbed by LWA.
Fig. 5 shows that when a hydrating system receives additional
water from curing (either internal or external), it generates
additional heat, which can be interpreted as additional cement
hydration. Fig. 5 also shows the measured heat of hydration for
a plain cement paste and a plain mortar mixture, both prepared with
a w∕c of 0.30 and without additives. The mixtures show a very
similar behavior. These data enabled confidence that good
dispersion was obtained in the mixing procedure.
Fig. 5 also shows the heat of hydration for a plain mortar and
an internally cured mortar (LWA mortar) mixture, both prepared
with a w∕c of 0.30 and without WR additive. At early ages, the
hydration is similar. However, the mixture with LWA demonstrates
slightly more hydration after approximately 12 h, which can be
interpreted as an increase in the degree of hydration. This is
consistent with the findings of Geiker (1983) and Lura et al.
(2010).
Fig. 5 shows the measured heat of hydration for a cement paste
and a cement paste with additional curing water on the top. Both
mixtures were prepared with a w∕c of 0.30 and without WR addi-
tive. At early ages, the hydration is similar. However, the mixture
with water on the top demonstrates greater hydration after approx-
imately 24 h, which can be interpreted as an increase in the degree
of hydration.
In Fig. 5, the second y-axis shows the cumulative heat of hydra-
tion normalized by the theoretical maximum heat of hydration. This
maximum theoretical value (476 J∕g of cement) was calculated
considering the heat released by the hydration of the cement
compounds (measured in the cement), as reported by Bensted
and Barnes (2002). The values used for each of the primary
cement compounds were C3 S ¼ 490 J∕g, C2 S ¼ 225 J∕g,
C3 A ¼ 1160 J∕g, and C4 AF ¼ 375 J∕g.
Figs. 6 and 7 show the measured heat of hydration for sealed
mortars made using normal-weight aggregate and sealed mortars
made with IC. The results show that initially (before approximately
18 h), all the mixtures demonstrate a similar rate of heat release,
irrespective of the w∕c (again recalling that mixtures prepared with
Fig. 5. Hydration of cement on cement paste and mortar and effect of
internal and external curing on cement hydration
 6 Discussion of Initial Results
5
(10-3 W / g of cement)
Observations and Hypothesis
Rate of Hydration

4
A few observations can be drawn on the basis of the data provided
3 Plain Mortar 0.51 in the previous section. First, although the cumulative heat release
Plain Mortar 0.48
Plain Mortar 0.45 curves are approximately similar, irrespective of w∕c at early ages
2 Plain Mortar 0.42 (i.e., up to approximately 18–24 h), they begin to diverge at a later
Plain Mortar 0.39
1 Plain Mortar 0.36 age with higher w∕c, exhibiting a higher heat release. This is
Plain Mortar 0.33 consistent with results provided by Bentz et al. (2009) and with
Plain Mortar 0.30
0 measurements on the basis of nonevaporable water provided by
0 3 6 9 12 15 18 Taplin (1959) and Mills (1966). This is likely the result of addi-
(a) Time (h)
tional space in the microstructure of the higher w∕c materials
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300
(i.e., more space between particles) and the increased access to
fluid for hydration (i.e., a higher internal RH). Second, the systems
Cumulative Heat of Hydration

(Heat/Max. Theoretical Heat)

0.5
250 that contain additional water (either through supplying water at the

Degree of Hydration
surface of the sample or through IC) show a higher cumulative heat
(J / g of cement)

0.4
200
release when compared with mixtures of the same w∕c mixture at
150
Plain Mortar 0.51 0.3 the same age. This implies that the presence of additional water
Plain Mortar 0.48
Plain Mortar 0.45 helps to promote additional hydration. This has also been noticed
100 Plain Mortar 0.42 0.2 by Geiker (1983), Bentz and Snyder (1999), and Lura et al. (2010).
Plain Mortar 0.39
Plain Mortar 0.36 Third, when chemical admixtures are used, the rate of heat release
50 0.1
Plain Mortar 0.33 can be altered; however, the cumulative heat of hydration is similar
Plain Mortar 0.30
0 0.0
at later ages (i.e., 72 h in Fig. 4).
0 12 24 36 48 60 72 This paper intends to estimate how much water is absorbed by
(b) Time (h) an oven-dry LWA when it is added during the mixing process.
On the basis of the information shown in Fig. 1, it can be assumed
Fig. 6. Effect of water-to-cement ratio on hydration of plain mortar that the water absorbed by the LWA in the mixing process would
systems, expressed as (a) rate of hydration; (b) cumulative heat of be less than the amount of water absorbed if the LWA is stored in
hydration water for 24 h.

Variations in Water-to-Cement Ratio and Paste Volume

on the Basis of Lightweight Aggregate Absorption
Variations
Fig. 8 shows volumetric proportions for cases in which different
assumptions are made regarding the extent of water absorbed
by the LWA and the amount of water added to the mixture.
Fig. 8(a) shows an ideal proportioning condition in which it is
assumed that the w∕c in the paste is maintained at 0.30 and the
LWA with 17.5% absorption. Although Fig. 8(a) shows an ideal
case, Figs. 8(b) and 8(c) show less-than-ideal cases.
Fig. 8(b) shows that the aggregate absorbed less water than was
assumed in the design (assume an extreme in which where no water
was absorbed by the LWA, S ¼ 0). As a result, more water would
remain in the paste, and the w∕c of the mixture would be higher
than the design of 0.30. In addition to the higher w∕c, the volume of
the paste would also be higher than the designed system (i.e., the
Fig. 7. Effect of water-to-cement ratio on hydration of internal cured mixture would overyield). Conversely, Fig. 8(c) assumes that
mortar systems the aggregate absorbs more water than what is assumed in the
design. It can be assumed that in this case the value of S is similarly
extreme, with a value of 1.3. As a result, the volume of the paste
(underyielding) would be less than the designed mixture, and the
lower w∕c contain a higher dosage of WR, which may slightly w∕c would be less than 0.30.
retard the cement hydration). It can be observed that after the first Fig. 9 shows how the w∕c would vary using the relative fluid
18–24 h, a difference begins to be noticed in the cumulative heat absorption of the aggregate at 24 h (S) on the basis of the aggregate
release between the different w∕c mixtures. This is similar to what properties, chemical shrinkage, and w∕c used in this paper. It is
is shown in the paste specimens (Fig. 3). Mixtures with a higher shown that the w∕c would vary between 0.28–0.35 depending
w∕c show a greater heat release. This is consistent with lower w∕c on the amount of water absorbed by the aggregate.
mixtures having a reduction in their hydration owing to a lack of
water and a lack of space for hydration products to form, which is Heat of Hydration: Influence of Water-to-Cement Ratio
also consistent with the information shown in Figs. 3 and 5. Spec- and Additional Water Supply
imens with IC show increased heat release owing the additional The cumulative heat release at 24 and 72 h is shown in Fig. 10 for
mixing water, as shown in Fig. 5, which is consistent with the re- plain and internally cured mortar mixtures. Although the heat re-
sults presented by Lura et al. (2010). lease at 24 h represents an approximately 37% degree of hydration,

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J. Mater. Civ. Eng. 2012.24:996-1005.

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Fig. 8. Effect of lightweight aggregate absorption on volume proportion of internally cured mortar systems

350

(Heat/ Maximum Theoretical Heat)

Cumulative Heat of Hydration

0.60
300

Degree of Hydration
(J/ g of cement)

0.50
250

0.40
200

LWA Mortar at 72 h
150 0.30
Plain Mortar at 72 h
LWA Mortar at 24 h
Plain Mortar at 24 h
100 0.20
0.24 0.27 0.30 0.33 0.36 0.39 0.42 0.45 0.48 0.51 0.54
water to cement ratio

Fig. 10. Plot of cumulative heat release at 24 and 72 h as a function of

water-to-cement ratio

Fig. 9. Effect of lightweight aggregate absorption on effective water-

to-cement ratio

270

it is similar for all of the mixtures, irrespective of the w∕c or if IC is

used. The mixtures with a higher w∕c have a greater amount of total 260
Heat of Hydration
(J / g of cement)

heat release at 72 h. Although the cumulative heat of hydration

increases with increasing w∕c, a plateau begins to develop for
higher values of w∕c. This plateau begins to shift to the right at 250

later ages (Taplin 1959). In addition to w∕c, the heat of hydration

is related to the amount of IC water for the samples at later ages.
240 Plain Mortar, without LWA
IC Mortar, 24h soak LWA
Heat of Hydration: Role of Water Volume Dry LWA Mixtures, assuming 55% absorption

Although it may be tempting to assume initially that the water 230

absorbed during mixing would immediately enable complete IC 0 25 50 75 100 125 150 175
to occur, it must be remembered that a sufficient volume of IC Volume of Internal Curing Water / g of Cement (%)
water must be supplied, and the water must be well distributed
Fig. 11. Plot of cumulative heat release at 72 h as a function of water-
throughout the paste. This can be shown quantitatively in Fig. 11
to-cement ratio
that when no water is available for IC, the cumulative heat is the

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J. Mater. Civ. Eng. 2012.24:996-1005.

 lowest. If IC water is available, the measured cumulative heat rises
with increasing IC water. This increase occurs until the volume of
IC water and spatial distribution of this water are sufficient, at
which point the heat of hydration appears to reach a plateau at
256 J∕g for the cement used in these tests.

Determining Water Absorbed by Dry Lightweight

Aggregate during Mixing

Test Procedure
A test procedure was developed to determine how much water was
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absorbed by the oven-dry LWA during mixing. This test procedure

consists of preparing mixtures with aggregate in two different
moisture conditions. The first aggregate moisture condition
(24 h prewetted LWA) was used in a reference mixture. The second
aggregate moisture condition was used in mixtures prepared with
oven-dry LWA. The oven-dry LWA mixtures are designed assum-
ing different volumes of water would be absorbed during the
mixing process (i.e., incrementally from 50%–80% of the 24-h
absorption).
The test procedure compares the heat release in the reference
mixture (the 24-h prewetted aggregate) with the heat release by
the samples made with the oven-dry LWA. To understand the pos-
sible results that can be obtained in comparing the heat release from
the mixtures mentioned previously, it is important to consider three
potential outcomes (similar to those shown in Fig. 8). First, if the
oven-dry LWA absorbs exactly the amount of water that has been
assumed to be absorbed, the w∕c will be the same as the reference
case, IC will be provided, and the cumulative heat release will be
the same. The second case assumes that the oven-dry LWA absorbs
less water than that assumed to be absorbed. In the second case, the
w∕c of the actual mixture with the oven-dry LWA will be higher
than the reference mixture, and the cumulative heat released, for
the mixture with the oven-dry LWA will be higher than the refer-
ence case. The third case assumes that the oven-dry LWA absorbs
more water than what was assumed. In the third case, w∕c in the dry
LWA mixture will be lower than the reference case, and the cumu-
lative heat release will be lower than the reference case. This
implies that if the heat release from the reference mixture is com-
pared with the heat release from a series of mixtures made using
the oven-dry LWA, there will be one case in which the heat release
is the same, which would correspond to the correct aggregate
absorption and w∕c.
The assumption that the additional heat resulting from IC in the
oven-dry LWA mixtures is the same as the one provided in the
prewetted mixture is valid if the demand for IC water is lower than
the water stored in the LWA pores. This happens if the degree of
hydration of the cement (water demand) is lower than the water
absorbed for the dry LWA (water stored). For the cement used
in this research, at 72 h the degree of hydration of the internally
cured mortar with a w∕c of 0.30 is 49% (Fig. 7). Then the dry
LWA absorption calculation will be valid if the absorption is higher
than 49% of the 24-h LWA absorption. This is consistent with the
results shown in Fig. 12.
Mixing Procedures for Dry Lightweight Aggregate
The approach described in the previous section was used to evalu-
ate the water absorption of dry LWA using two different mixing
procedures. Mixing Procedure 1 consisted of placing all of the
dry materials in the mixer, premixing the materials, and then adding
the water to the mixture. In Mixing Procedure 2, the dry LWA was
allowed to soak in the mixing water for 5 min before it was placed
Fig. 12. Determination of the dry LWA absorption during mixing
in contact with the other components of the mixture (i.e., normal-
weight sand and cement).
Fig. 12 shows the heat of hydration of both procedures as a func-
tion of the assumed LWA absorption (normalized by the heat
released at 72 h for the reference mixture containing the 24-h pre-
soaked LWA). Fig. 12 shows that the heat released by the dry
LWA mixtures at 72 h follow linear relationships with the
assumed LWA absorption. The actual aggregate absorption can
be determined when the heat release for the mixtures with the
dry aggregate equals the heat release for the reference mixture
(24-h presoaked LWA). This occurs when the normalized value
of heat release equals 1. Using this approach, the LWA absorption
was determined to be 56 and 71% of the 24-h absorption for Mixing
Procedures # 1 and 2, respectively. The absorption obtained using
Mixing Procedure 2 is higher, likely because of the time that
the LWA had to absorb water while soaking before the cement
was added to the mixture.
Summary and Conclusions
This paper described a series of tests that evaluate the heat of hy-
dration of cement paste and mortars using an isothermal calorim-
eter. Cement paste prepared with different w∕c were analyzed.
Results show that although the cumulative heat release curves
are similar, irrespective of the w∕c before and slightly after set, they
begin to diverge at a later age (approximately 18–24 h in this
paper), with higher w∕c exhibiting a higher heat release. This is
owing to the additional space for hydration and the additional
amount of fluid available for hydration. Tests performed on mortar
specimens containing different amounts of a polycarboxylate-based
WR show that these additions can alter the rate of reaction of the
cement at early ages; however, this effect seems to significantly
diminish by 72 h. By comparing the heat of hydration of mixtures
prepared with dry LWA with that of a mixture prepared with a 24-h
presoaked LWA, it is possible to determine the amount of water that
is absorbed during the mixing process by the dry LWA. The amount
of absorbed water depends strongly on the mixing procedure. For
the two mixing procedures used, it was found that the oven-dry
LWA will absorb between 56% (for immediate mixing) and 71%
(when the water was in contact with the dry LWA for 5 min before
mixing) of the 24-h absorption value. This is in general agreement
with the normalized absorption of the LWA at 5 min, which was

JOURNAL OF MATERIALS IN CIVIL ENGINEERING © ASCE / AUGUST 2012 / 1003

J. Mater. Civ. Eng. 2012.24:996-1005.

 found to be 63%. This paper shows that aggregates with different
initial moisture conditions can be used for IC. Mixtures that use
LWA that is more dry will tend to require more LWA than mixtures
with a prewetted LWA. As such, prewetting is still recommended,
except for very specific circumstances.
Disclaimer
Certain commercial products are identified in this paper to specify
the materials used and procedures employed. In no case does such
identification imply endorsement or recommendation by Purdue
University, nor does it indicate that the products are necessarily
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the best available for the purpose.
Acknowledgments
This work was supported in part by the Expanded Shale, Clay and
Slate Institute (ESCSI) and by the Joint Transportation Research
Program administered by the Indiana Department of Transportation
and Purdue University (Project SPR 3211), and the authors grate-
fully acknowledge that support. The contents of this paper reflect
the views of the authors, who are responsible for the facts and the
accuracy of the data presented and do not necessarily reflect the
official views or policies of the Indiana Department of Transporta-
tion or ESCSI, nor do the contents constitute a standard, specifica-
tion, or regulation. The experiments reported in this paper were
conducted in the Pankow Materials Laboratories at Purdue Univer-
sity. The authors acknowledge the support that has made this
laboratory and its operation possible.
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