Thermochimica Acta 546 (2012) 3243

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Thermochimica Acta
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Reaction kinetics in sodium silicate powder and liquid activated slag binders
evaluated using isothermal calorimetry
Deepak Ravikumar, Narayanan Neithalath
School of Sustainable Engineering and the Built Environment, Arizona State University, Tempe, AZ, United States

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

Article history: The kinetics of alkali activation of slag is highly dependent on the activator type and its chemical consti-
Received 23 February 2012 tution. This paper explores the early-age reaction kinetics of slag activated using powder sodium silicate
Received in revised form 15 June 2012 (which makes handling easier in practice) and compares it with that of waterglass (liquid sodium silicate)
Accepted 10 July 2012
activated slag pastes. The inuence of Na2 O-to-slag ratio and the activator modulus (SiO2 -to-Na2 O ratio)
Available online 28 July 2012
on the isothermal calorimetric response is presented. The powder sodium silicate activated slag pastes
show a calorimetric response similar to NaOH activated slag systems, with both demonstrating single
Keywords:
early-age reaction peaks. In contrast, the waterglass activated systems show a calorimetric response
Alkali activation
Slag
similar to those of OPC pastes, with a marked induction period. Kinetic modeling is used to quantify the
Sodium silicate differences in reaction kinetics. Jander equation is used to model the time-dependent degree of reaction
Isothermal calorimetry and to relate it to the rate controlling processes when different types of activators are used.
Reaction kinetics 2012 Elsevier B.V. All rights reserved.
Kinetic modeling

1. Introduction normal moist curing conditions, especially with precursor materi-

Alkali activation of aluminosilicate precursors such as ground
granulated blast furnace slag or y ash, which are waste or
by-product materials from other manufacturing processes, is estab-
lished as one of the methods of producing sustainable binders for
construction [14]. Alkali (Na or K) hydroxides or silicates are gen-
erally used as the activating agents. When a calcium rich starting
material (slag) is activated, CSH gel of low Ca/Si molar ratio is
the primary reaction product [57] whereas the activation of alu-
mina/silica rich precursors (Class F y ash, metakaolin) results in
the formation of alkali aluminosilicate gel [811]. Alkali activated
binders have been reported to exhibit mechanical and durability
characteristics similar to or superior than those of ordinary Portland
cement binders [1216].
The nature and type of the activating agent determines the
reaction rate and extent and the reaction products formed, thereby
exerting a signicant inuence on the early- and later-age prop-
erties of alkali activated binder systems [1720]. A number of
reported studies on alkali activated binder systems use alkali
silicate solutions with different silicate moduli (Ms , which is the
ratio of SiO2 -to-Na2 O) as the activator. This has been shown to be
an effective means of producing strong and durable binders under
Corresponding author. Tel.: +1 480 965 6023; fax: +1 480 965 0557.
E-mail addresses: Deepak.ravikumar@asu.edu (D. Ravikumar),
Narayanan.Neithalath@asu.edu (N. Neithalath).
als like slag that contain reactive calcium. However, one of the most
crucial practical concerns relate to the handling of these caustic
activator solutions. A potential alternative is to use the activators in
powder form so that it presents relatively lower handling hazards.
A few studies have reported the workability and mechanical prop-
erties of mortars activated using powder activators [21,22]. The
use of powder activators also presents the opportunity to develop
alkali activated binder systems that can be pre-packaged and
requires the use of water alone to initiate the reaction, in a manner
similar to ordinary Portland cements. Such an approach is likely to
increase the commercial acceptability of these materials also.
It is obvious that the reaction kinetics (and consequently the set-
ting process and strength development, which are very important
for eld implementation) will be different when powder or liquid
activators are used. Isothermal calorimetry is a well-accepted tech-
nique for the study of reaction kinetics and has been successfully
applied for cementitious systems. A very large body of literature
is available on the use of isothermal calorimetry to study the rate
and extent of ordinary Portland cement hydration, the inuence
of cement neness and composition, and incorporation of cement
replacement materials and admixtures. Refs. [2328] provide a
broad sampling of some of the recent studies in this eld. A few
studies have reported the reaction kinetics in liquid sodium silicate
(waterglass) and NaOH activated slag systems using isothermal
calorimetric studies [2931]. An earlier work [32] details calori-
metric studies on slags activated using a wide variety of activators
including alkali hydroxide, carbonate, and phosphate at different

0040-6031/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.tca.2012.07.010
 D. Ravikumar, N. Neithalath / Thermochimica Acta 546 (2012) 3243
Table 1
Chemical composition of slag.
SiO2 Al2 O3 CaO Fe2 O3 MgO Na2 O K2 O SO3
36.0% 10.5% 39.8% 0.67% 7.93% 0.27% 0.80% 2.1%
temperatures, and classies the heat evolution response based on
the number and location (in the time scale) of heat release peaks.
The differences in the heat evolution behavior of slag activated
using NaOH, waterglass, and a combination of NaOH and water-
glass has recently been provided in [30]. The faster initial reaction
in NaOH activated slag pastes as compared to waterglass activated
pastes has also been conrmed through isothermal calorimetric
measurements [33]. The isothermal calorimetric responses of slag-
metakaolin blends, slag being the dominant component, activated
using waterglass have been reported to be similar to those of slag
alone as far as the trends are concerned [31]. The inuence of alkali
cation (K or Na) on the geopolymerization process of metakaolin
evaluated using isothermal calorimetry is reported in [34].
The aforementioned studies have dealt with the use of liquid
activators to activate the precursor materials. Understanding the
effect of activator characteristics (including the activator type
powder or liquid, and alkalinity) on the reaction kinetics of alkali
activated slag is therefore the focus of this paper. Here, isother-
mal calorimetry is used to identify the fundamental differences
in early-age reaction kinetics when powder or liquid activators
are used to activate slag. This information is then used to model
the reaction kinetics in activated slag systems and obtain a better
understanding of the rate controlling processes facilitated by the
powder or liquid activators. The fundamental differences between
the powder and liquid activators, mostly related to the dissolution
effects of the powder, are brought out through the use of Fourier
Transform Infrared (FTIR) spectroscopy and electrical conductivity
measurements.
2. Experimental program
2.1. Materials
Type 100 ground granulated blast furnace slag (GGBFS) con-
forming to ASTM C 989 was used as the starting material for all
the mixtures. The oxide composition of the slag is given in Table 1.
Sodium silicate powder with a modulus Ms (SiO2 -to-Na2 O ratio,
mass-based) of 1.95, or liquid sodium silicate (waterglass) with an
Ms of 3.26 was used as the activator. Note that the molar and mass-
based Ms values of sodium silicate are very close to each other since
the ratio of molecular masses of SiO2 and Na2 O is 0.97. The sodium
silicate powder has a median particle size of 25 m and a pH of 12.6
(for a 50% (w/v) slurry in water). The waterglass used has a solids
content of 40%. Analytic reagent-grade sodium hydroxide (NaOH)
was used to facilitate changes in the Ms of the sodium silicate acti-
vator in both the cases. In the remainder of this paper, solid (or
powder) sodium silicate activator implies that the activator is a
combination of powder sodium silicate of Ms 1.95 (mass-based)
and requisite amounts of NaOH required to bring the Ms of the
activator to desired levels (between 0.6 and 1.5), and liquid acti-
vator (or waterglass) implies that the activator is a combination
of waterglass of Ms 3.26 and NaOH solution required to bring the
activator Ms to the desired levels (between 1.0 and 2.5). When only
waterglass (Ms of 3.26) or powder sodium silicate (Ms of 1.95) was
used as the activator, both the heat evolution and strength devel-
opment were extremely low and slow, rendering such mixtures not
practically useful. Blending the sodium silicate with NaOH [30,31]
reduces the Ms values to levels where the material develops its
structure and strength so as to be of practical use.
33
2.2. Mixtures
LOI The alkali activated paste mixtures were prepared in a com-
3.0% mercial laboratory mixer with the activator and binder mixed at
400 rpm for about 2 min. Two different n values (ratio of Na2 O-to-
slag, by mass) of 0.05 and 0.15, and two activator Ms values of 0.60
and 1.5 were used for the mixtures activated using the solid acti-
vator. These values were arrived at based on an extensive previous
study [35] that investigated the inuence of activator parameters
on the properties of powder sodium silicate activated slag binders.
Higher Ms and/or lower n in such cases resulted in insufcient acti-
vation and lack of property development. For slag activated using
the liquid activator, an n value of 0.05 (i.e., 5% Na2 O) only was used
while the Ms values used were 1.02.5 in increments of 0.50. To
provide an example for how the amounts of powder sodium sili-
cate and NaOH were determined, consider 1000 g of slag that needs
to be activated using an n value of 0.05 and Ms of 0.60. This neces-
sitates 50 g of Na2 O and 30 g of SiO2 . Since the sodium silicate is
the only source of silica, 30 g of SiO2 can be obtained from 46 g of
sodium silicate of Ms 1.95. This amount of sodium silicate gives 16 g
of Na2 O and hence the remaining amount (50 g 16 g = 34 g) can be
obtained through the addition of NaOH.
The sodium silicate powder + NaOH activator can be used in two
different ways to activate slag: (i) blending the requisite amounts
of powder activators (sodium silicate and NaOH) with slag and then
adding the desired amount of mixing water (which is convenient
for pre-packaged materials) or (ii) mixing the activator powders
(sodium silicate and NaOH) in water and then cooling to ambient
temperature before use. If the rst method is adopted, the exother-
mic dissolution of NaOH in water will lead to an extremely high
early peak in the calorimetry curves which is likely to mask the
effect of dissolution of ions from the slag. It was observed that the
early and later age compressive strengths were independent of the
activator addition method [35], and it can be assumed that a similar
degree of activation was achieved in both the cases. Hence for the
calorimetric studies reported in this paper, the second method was
used. The liquid-to-powder ratio used for all the mixtures was 0.50.
The liquid consisted of the water added (a part of which was used
to prepare the NaOH solution) and the water present in waterglass.
The powder part consisted of the sodium silicate powder (or the
solids fraction of waterglass if it is used), Na2 O from NaOH, and
slag.
2.3. Test methods
Isothermal calorimetry experiments were carried out in accor-
dance with ASTM C 1679. The pastes were mixed externally and
loaded into the isothermal calorimeter. The time elapsed between
the instant the activating solution was added to the powder and
the paste loaded into the calorimeter was around 23 min. The
tests were run for 72 h with the calorimeter set at three different
temperatures (25 C, 35 C, and 45 C). When temperatures other
than room temperature were used, the starting materials were
conditioned to the desired temperature before mixing. The setting
times of alkali activated pastes were determined using the Vicat
needle method, in accordance with ASTM C 191. The compressive
strengths of the mixtures at several ages were determined on acti-
vated slag mortar cubes. The mortar cubes were prepared using a
paste volume fraction of 0.50 and a liquid-to-powder ratio of 0.50.
River sand was used as the ne aggregate. At least three specimens
from each mixture were tested at the desired ages. The compressive
strengths of the cubes were determined in accordance with ASTM
C 109. Fourier Transform Infrared (FTIR) spectroscopy was carried
out on the activator solutions. For the solid sodium silicate acti-
vator, solutions were prepared by mixing the amounts of powder
sodium silicate and NaOH that would have been needed to obtain a
34 D. Ravikumar, N. Neithalath / Thermochimica Acta 546 (2012) 3243
Fig. 1. Vicat needle penetration depth as a function of time for slag pastes activated using: (a) powder sodium silicate and (b) waterglass.
desired Ms and an n value of 0.05 for 100 g of slag, with the amount
of water needed to provide a water-to-powder ratio of 0.50 in the
mixture. The solution was agitated thoroughly and allowed to rest
for 2 h. The supernatant solution was used for FTIR spectroscopy
and conductivity tests. A small amount of the solution was spread
between two infrared-transparent KBr lenses and the FTIR spectra
were obtained in the wavenumber range of 4000400 cm1 . The
conductivities of the activator solutions were measured using small
prismatic solution cells (the cell constant of which was determined
from the length and area of cross of section) with stainless steel
plates as the electrodes.
3. Results, analysis and discussions
3.1. Setting time and compressive strength of alkali activated slag
pastes
Fig. 1(a) and (b) shows the Vicat needle penetration depth as
a function of time after mixing for slag pastes activated using the
powder and liquid sodium silicate activators respectively. As men-
tioned earlier, for the powder activated slag, two n values of 0.05
and 0.15 were used whereas for the liquid activated slag only an
n value of 0.05 was used. Initial setting times for sodium silicate
powder activated slag pastes are found to vary between 15 and
30 min, with the longer times for mixtures with a lower n value,
as shown in Fig. 1(a). At a higher n value, the powder activated
pastes complete their nal setting also in about 20 min. This rapid
loss of workability necessitates the use of a set-retarding admix-
ture for efcient use of the powder sodium silicate activated slag
binders in practice. However, for repair applications where fast set-
ting and early strength gain is desired, these are robust materials
especially because the binder and the activator can be blended and
pre-packaged, requiring only the addition of water in the eld. The
initial setting times of liquid sodium silicate activated pastes of
n value of 0.05 varies between 80 min and 250 min and the nal
setting times between 220 and 450 min as can be observed from
Fig. 1(b), with the pastes activated using a high Ms activator show-
ing delayed initial setting. The initial and nal setting times for the
liquid activated slag binders are in the range of the corresponding
values reported for ordinary Portland cement pastes [36,37]. For
both the solid and liquid activated pastes, increasing alkalinity (as
represented by increasing n values or decreasing Ms values) results
in reduced setting times.
Compressive strengths of the activated slag mortar specimens
that were moist-cured were determined at ages of 12 h, and 1, 3,
14, and 28 days. Fig. 2(a) and (b) shows the compressive strengths
of the slag mortars activated using the powder activator, propor-
tioned using n values of 0.05 and 0.15 respectively. It can be seen
from these gures that the mixtures with an n value of 0.15 (high-
est Na2 O content) show the highest compressive strengths, at both
early (12 h 3 days) and later (1428 days) ages. This is because
an increase in the activator dosage increases the overall alkalinity
of the activator. The efciency of slag activation is dependent on
the pH of the activating medium. This is evident in the higher early
age strengths when activator with a lower Ms is used. The higher
activator alkalinity in this case solubilizes the water-impermeable
layer on the surfaces of slag particles leading to faster reaction rates
and formation of reaction products [7]. However, at later ages, the
strengths are higher for mixtures with a higher Ms , the reasons
for which have been elaborated in [35]. Compressive strengths in
the 1520 MPa range (for the lower n value mortars) and in the
3035 MPa range (for the higher n value mortars) are obtained
using the powder sodium silicate activator.
Fig. 2(c) shows the compressive strengths of waterglass acti-
vated slag mortars of different activator Ms at an n value of 0.05.
The compressive strengths of the waterglass activated mortars are
found to be signicantly higher than those of the mortars activated
using the powder activator. This is mainly a result of the reduced
levels of silica dissolution from solid activator, as will be quanti-
ed in a later section. The soluble silicates in waterglass facilitates
the formation of larger amounts of lower Ca/Si ratio C S H gel
whereas the reaction product composition is different in powder
activated mixtures where some high modulus sodium silicate gel
is also formed [35]. Mercury intrusion porosimetry studies have
shown that the overall pore volume in the liquid activated binders
are on an average 25% lower than those of the powder sodium sil-
icate activated binders [38], which also contributes to the higher
strength of the liquid activated mixtures.
3.2. Isothermal calorimetry studies on alkali activated slag pastes
3.2.1. Calorimetric response of pastes activated using solid
activator
Fig. 3(a) shows the heat evolution curves as a function of time
for the powder activated slag pastes proportioned using activator
Ms of 0.6 and 1.5 for both n values (0.05 and 0.15). The experiments
were carried out at 25 C. A higher alkalinity (achieved through the
 D. Ravikumar, N. Neithalath / Thermochimica Acta 546 (2012) 3243 35

Fig. 2. Compressive strength development for moist-cured mortars activated using: (a) powder sodium silicate and n value of 0.05, (b) powder sodium silicate and n value
of 0.15, and (c) waterglass and n value of 0.05. The error bars represent one standard deviation from the average strengths of three specimens tested.

use of a higher n-value and/or lower Ms ) results in a larger peak in
the heat evolution curves as shown in this gure. In this context, it
is desirable to combine the n and Ms values into a single parameter
that is related to the alkalinity. Hence the ratio of n to the Ms values
(n/Ms ), which is proportional to the square of the Na2 O content
of the activator, to which the early age compressive strengths of
powder activated mixtures has been adequately related to [35], is
used in this paper. An observation of Fig. 3(a) indicates that the
peak heights are proportional to n/Ms of the activator. For instance,
the pastes with n = 0.15 and Ms = 1.5, and n = 0.05 and Ms = 0.6 have
similar n/Ms values (0.10 and 0.083 respectively), and their major
heat release peak heights are also similar.
There is only one large peak that is observed in these systems
in the rst 72 h as seen from Fig. 3(a), and except for the mixture
with the lowest alkalinity (n = 0.05, Ms = 1.5), these peaks appear
in the rst 23 h. The initial heat release peak corresponds to the
particle wetting, beginning of the dissolution of slag particles, and
formation of (alumino-)silicate units and their complexation with
the alkali and calcium ions [31]. The dormant period which is typ-
ical in the hydration of ordinary Portland cements is absent in the
powder sodium silicate + NaOH activated systems. Since the mix-
ing was done externally, it is likely that the major heat release
peak observed here is a combination of both the initial and the
acceleration peaks. A higher alkalinity could have led to a rapid
dissolution and reaction product precipitation quite early so that
distinct pre-induction and induction periods are left undetected.
Such a one-peak behavior has been reported for slag systems acti-
vated using a high alkalinity activator [31]. In general, for ordinary
Portland cements, the nal setting time coincides approximately
with the end of the induction period or the start of the accelera-
tion stage. From Fig. 1(a), it is observed that the nal setting times
(when the needle penetration is zero) of the powder activated slag
pastes occur between 20 and 60 min depending on the alkalinity,
which falls in the major heat release peak. This shows that the dis-
solution and precipitation phases occur simultaneously in these
systems, which is represented by a single major heat release peak.
For the paste with the lower alkalinity (n/Ms of 0.03), a delay period
is observed in the heat evolution curve even when the setting of
this mixture happens relatively quickly. The setting times appear
towards the early part of the induction period in this case, showing
that the structure formation as evaluated using the Vicat test can-
not be condently related to isothermal heat release signatures for
alkali activated binders. The measured faster setting is due to the
formation of a Si Al rich layer on the surface of the slag particles,
36 D. Ravikumar, N. Neithalath / Thermochimica Acta 546 (2012) 3243
Fig. 3. Heat evolution of slag pastes activated using: (a) powder sodium silicate
activator and NaOH required to lower the Ms and (b) 4 M and 8 M NaOH solutions,
and powder sodium silicate (Ms of 1.95) without the addition of NaOH. Experiments
carried out at 25 C.
and the lower heat evolution and the delay is caused by the lower
levels of alkalinity not being able to penetrate this layer and cause
further reaction.
The calorimetric responses of slag activated using 4 M and 8 M
NaOH solutions are shown in Fig. 3(b). Only the rst 24 h are shown
in this gure because the system stays dormant with respect to
heat release after this period. The general shape of these curves is
similar to those of powder activated slag pastes, with the major heat
release peaks appearing at about 1.5 h in both the cases. However,
for the slag pastes activated using NaOH alone, a very early peak
that is lower in magnitude than the acceleration peak is noticed
immediately before the major peak (see the inset in Fig. 3(b)). The
precipitation of reaction products on the surface of slag leads to a
very reduced or even a non-existent induction period [30]. Fig. 3(b)
also depicts the heat ow rate for pastes activated using powder
sodium silicate alone (Ms = 1.95, no NaOH used) at n values of 0.05
and 0.15. These pastes did not develop compressive strengths of
more than 10 MPa. There is a very early dissolution peak observed,
similar to the ones observed for NaOH activated systems, but then
further acceleration does not happen for the lower n value paste
because of the lower alkalinity in the system. For the paste with
an n value of 0.15, an acceleration shoulder, roughly corresponding
to the time when the NaOH activated mixtures show their peak, is
also observed.
A simple means to quantify the effect of powder sodium silicate
in systems that are activated using combinations of powder sodium
Fig. 4. Heat evolution of slag pastes activated using waterglass. NaOH solution
added to lower the Ms values. Experiments carried out at 25 C.
silicate and NaOH is provided below. Consider the concentrations
of external NaOH added to powder sodium silicate to reduce the Ms .
It can be calculated based on the amount of water and additional
NaOH added to the system that, when the Ms is reduced to 0.60, a
2.02 M NaOH solution is present for an n value of 0.05, and 5.2 M
NaOH for an n value of 0.15. The contributions from the externally
added NaOH only is considered in the above calculations. If the peak
for a 5.2 M NaOH activated slag paste can be realistically assumed
to lie in between those for the 4 M and 8 M NaOH activated pastes
shown in Fig. 3(b), the calorimetric peak registered for the case
of paste with the activator characteristics n = 0.15 and Ms = 0.60 as
shown in Fig. 3(a) is about 50% higher than the former, attesting
to the activity of the powder sodium silicate. A similar explanation
holds true for the other mixtures also. In any case, a comparison of
Fig. 3(a) and (b) points to similarities in the calorimetric responses
of slag activated using powder sodium silicate and NaOH. The acti-
vator characteristics that possibly lead to such a response, through
the use of FTIR spectroscopy, and a quantication of the similarities
using kinetic modeling, are presented later in this paper.
3.2.2. Calorimetric response of pastes activated using liquid
activator
Fig. 4 shows the heat evolution curves for liquid activated slag
pastes at Ms levels of 1.0, 1.5, 2.0 and 2.5. These curves are different
from those of powder activated pastes in terms of the number of
peaks, peak heights, and peak locations. Instead of the single peak
system observed for the powder activated slag mixtures as seen in
Fig. 3(a), the liquid activated pastes show two peaks an intense
narrow peak within the rst few hours of mixing, attributed to the
wetting and dissolution of slag, and a dormant period followed by
the second peak corresponding to the reaction product formation
that appears in the 10- to 30-h period for most of the mixtures
evaluated in this study. Such a calorimetric signature is similar to
that of ordinary Portland cement hydration. When an activator Ms
of 3.26 (no NaOH was added and waterglass was used as such) was
used, the paste did not set or produce a signicant calorimetric
signal. Even when the Ms was reduced to 2.5, the response was
delayed and barely noticeable (nonetheless shown in Fig. 4). A fur-
ther reduction in Ms through the addition of NaOH resulted in the
shifting of the second peak to an earlier time suggesting an accel-
eration in reaction with increase in alkalinity as expected. This also
results in a peak of higher intensity. The changes in peak height
and the delay in appearance of the second peak appear to be well
related to the activator Ms values (note that n is kept constant for
these pastes). The differences in calorimetric signatures when slag
 D. Ravikumar, N. Neithalath / Thermochimica Acta 546 (2012) 3243
Fig. 5. Heat evolution of slag paste activated using solid sodium silicate and water-
glass, and its comparison with the heat evolution for a typical ordinary Portland
cement paste. Experiments carried out at 25 C.
is activated with powder and liquid sodium silicate activators sug-
gest that the type of activator inuences the kinetics of reaction and
possibly the type of reaction products that are formed. A forthcom-
ing section will shed more light onto the reaction kinetics, while a
recent study [35] has investigated the reaction product formation
in solid sodium silicate activated slag systems.
Fig. 5 shows a comparison of the isothermal heat evolution
curves of slag pastes activated using powder sodium silicate, NaOH
and waterglass. The mixtures with an n value of 0.05 are used,
along with the lower activator Ms cases (0.6 and 1.0 respectively
for the powder and liquid activators). As discussed previously, only
one major peak is observed for the powder sodium silicate acti-
vated slag paste whereas dissolution and acceleration peaks with a
noticeable induction period in between are observed for the water-
glass activated slag paste. The major peaks are similar in intensities
for both these mixtures, but wider (and therefore larger area under
the peak) for the waterglass activated paste, indicating better acti-
vation, as has been demonstrated using the compressive strength
results in the previous section. The heat release curve for a typi-
cal ordinary Portland cement paste made using a water-to-cement
ratio of 0.50 is also shown in this gure. The induction period for the
waterglass activated slag paste is longer than that of the tested OPC
paste as shown in this gure. The longer induction period in water-
glass activated pastes could be due to the time required for the
ionic species in the system to reach a critical concentration to form
reaction products [39]. Some shortening of the induction period, or
acceleration of the slag activation reaction can be achieved if the
water-to-powder ratio of the mixture is reduced, or the system is
heat cured.
3.3. An assessment of activator characteristics responsible for
calorimetric differences
The results presented in the previous section demonstrate that
the activator type whether solid or liquid inuences the reaction
kinetics of alkali activated slag systems. In order to understand the
activator characteristics, FTIR spectroscopy and electrical conduc-
tivity tests were carried out on the activators as described earlier.
Fig. 6 shows the FTIR spectra of the different activating solutions.
The plots labeled (a) and (b) show the spectra of the supernatant
solutions after solid sodium silicate activator having Ms values of
0.6 and 1.5 respectively were dissolved in water for 2 h. Both these
spectra look identical irrespective of the difference in Ms . The major
37
Fig. 6. FTIR spectra of activator solutions: (a) supernatant of the solid sodium sili-
cate + NaOH for a Ms of 0.6, dissolved in water; (b) same as in (a), but with a Ms of
1.5; (c) 4 M NaOH; (d) waterglass with a Ms of 1.0; and (e) waterglass with a Ms of
2.5.
bands that appear in these spectra are the stretching and bend-
ing modes of OH in water at around 34503500 cm1 and around
1600 cm1 respectively [40]. A broad band at about 620 cm1 also
appears in these spectra, which is attributable to weak bending
modes of Si O Si linkages. The strongest bands for the Si O Si
vibration that typically appears around 1000 cm1 [41,42] is notice-
ably absent in these spectra. A comparison with the spectra shown
in (c) of Fig. 6, which corresponds to a 4 M NaOH solution, suggests
that the solid sodium silicate activator (i.e., sodium silicate powder
of Ms 1.95 + NaOH added to obtain the desired Ms of 0.6 and 1.5) dis-
solved in water is similar to a NaOH solution, with the exception of
some amounts of dissolved silica (represented by the weak bending
of Si O Si linkages at 620630 cm1 ). The absence of the domi-
nant Si O Si peak (that typically appears in the 9701050 cm1
range [43]) from the spectra suggests that the silica from the solid
sodium silicate activator is not completely dissolved when the solid
activator is dissolved in water. The contribution of solid sodium sil-
icate in increasing the concentration of NaOH in the solution has
been discussed in a previous section. This explains the similarity
in the calorimetric signatures of solid sodium silicate and NaOH
activated slag pastes (Fig. 3(a) and (b)). In both cases, the high con-
centration of OH ions present aids in the breaking of Si O and
Al O bonds in addition to the Ca O and Mg O bonds. Elution of
CaO from slag in the NaOH activated slag system stops after a quick
early reaction due to the formation of a reaction rim around the
slag particles resulting in a single-peak calorimetric curve, but in
the case of waterglass activated slag systems, the elution of CaO
continues to a much longer time after the start of the reaction [44],
resulting in an extended induction period and a two-peak calori-
metric curve. Similar calorimetric curves for NaOH activated slag
pastes have been reported in [30,45].
The FTIR spectra (d) and (e) in Fig. 6 are for the waterglass solu-
tions of Ms 1.0 and 2.5 respectively. Contrary to the spectra (a) and
38 D. Ravikumar, N. Neithalath / Thermochimica Acta 546 (2012) 3243
Fig. 7. Conductivity of: (a) sodium silicate activator solutions as a function of Ms , and (b) NaOH solutions as a function of molar concentration.
(b), a distinct band at around 1000 cm1 representing the asymmet-
ric stretching vibration of Si O Si is observed here, demonstrating
the availability of larger amounts of silica in solution. Additional
Si O Si bending bands at around 470 cm1 are also noticed. The
presence of more amounts of dissolved silica results in its reaction
with Ca2+ from slag to form C S H gel when the Ca ion concentra-
tion reaches a critical value. The C S H layer formed around the
slag particles prolongs the inhibition period but does not hinder
further reaction beyond a day or so, as is evident from the second
heat peaks for the waterglass activated pastes in Fig. 4. This also
explains the better activation with waterglass that leads to much
higher compressive strengths.
While it is acknowledged that the pH of the activating solution
dictates the efciency of activation, the measurement of pH of such
highly alkaline solutions is difcult. Hence the electrical conduc-
tivity of the activator solutions is used as a surrogate parameter.
Since the OH ions have the highest equivalent conductivity among
the ionic species present in these systems (198 cm2 S/mol, com-
pared to 50.1 cm2 S/mol for Na+ [46], and 70 cm2 S/mol for aqueous
SiO2 [47]), the conductivity of these solutions can be used as an
indirect indicator of alkalinity. The conductivity of the waterglass
solutions of different Ms as well as the supernatant solutions after
solid sodium silicate activator was dissolved in water, as a function
of Ms is shown in Fig. 7(a). The conductivity of the solution when
solid sodium silicate is dissolved in water is higher than that of
waterglass for a given Ms . This is because the supernatant solution
resembles NaOH more than it does waterglass, as shown from the
FTIR spectra earlier. The higher alkalinity of the activator results in
faster initial dissociation and gelation, leading to the single-peak
calorimetric curve shown in Fig. 3(a) and (b). Fig. 7(b) relates the
conductivity of NaOH solutions to its molar concentrations. Using
solid sodium silicate corresponding to an n value of 0.05 and of Ms
0.6 (conductivity of 27.5 S/m from Fig. 7(a)) to activate slag is equiv-
alent to using approximately 3.4 M NaOH, according to Fig. 7(b). In
Section 3.2.1, it was shown that when only the contribution of addi-
tionally added NaOH is considered, the solution concentration for
this case should be 2.02 M. The difference then is contributed by the
powder sodium silicate. The peak heat ow for the solid sodium sil-
icate activated slag paste with n = 0.05 and Ms = 0.6 (3.4 M NaOH)
from Fig. 3(a) is only slightly lower than that of the slag paste acti-
vated using 4 M NaOH shown in Fig. 3, substantiating the fact that
all of the silica from solid sodium silicate does not go into solution,
and that it resembles activation using NaOH.5
3.4. Inuence of temperature on calorimetric response of powder
and liquid activated slag
In addition to the isothermal calorimetry tests conducted at
25 C, tests were carried out on all the activated slag pastes as well
as the OPC paste at 35 C and 45 C. This faciliates an understand-
ing of the inuence of temperature on the rate of reaction in solid
and liquid sodium silicate activated slag pastes, as well as enables
the extraction of the activation energy of these chemical reactions
as explained in a forthcoming section. Fig. 8(a) and (b) depicts the
calorimetric signatures for solid and liquid sodium silicate activated
slag pastes with an n value of 0.05. The activator Ms values used are
0.6 and 1.5 for the solid sodium silicate activated pastes and 1.0
and 1.5 for the waterglass activated pastes respectively. The heat
evolution curves at 25 C and 35 C are only shown in these gures.
The curves for 45 C are not shown here so as to not crowd the
graphs. The general trends are similar, where the peaks appear at
earlier times and the intensty increases with increasing tempera-
ture. Fig. 8(a) shows that an increase in temperature from 25 C to
35 C signicantly accelerates the time of occurrence of the solitary
peak, from about 6.5 h to 2 h, for the solid sodium silicate activated
paste with a higher Ms (lower alkalinity). The peak intensity is also
doubled and the peak has become sharper. For the paste with a
lower Ms , the time of occurrence of the calorimetric peak is not sig-
nicantly alterted, but the peak strength is doubled and the peak is
much sharper. It is found that increasing the reaction temperature
enhances the reactivity of the solid sodium silicate activated slag
pastes, and the effect is more prominent for pastes made with lower
activator Ms (i.e., higher silica content). For the waterglass activated
slag pastes, Fig. 8(b) shows that the induction period shortens and
the peak becomes slightly more intense and narrower with increase
in temperature. This is similar to that observed for OPC systems. A
comparison of these gures show that the effect of temperature is
more prominent for solid sodium silicate activated slag pastes.
3.4.1. Improving the efciency of powder sodium silicate through
heating
It was shown in Section 3.3 that the powder sodium silicate acti-
vated slag behaves similar to that activated using NaOH because of
the inadequate amounts of silica released from the solid activator
under ambient conditions. One of the means to ensure increased
solubility of solid sodium silicate in water is to heat the resul-
tant solution. FTIR spectrum of the solid sodium silicate and NaOH
 D. Ravikumar, N. Neithalath / Thermochimica Acta 546 (2012) 3243
Fig. 8. Temperature dependence of isothermal calorimetry responses of slag pastes
activated using: (a) powder sodium silicate and (b) waterglass.
activator dissolved in water and heated at 65 C for 6 h is shown
in Fig. 9(a). The activator parameters correspond to n = 0.05 and
Ms = 1.5. A distinct band at 1020 cm1 corresponding to the stretch-
ing vibration of the Si O Si linkages is observed here, attesting
to the fact that heating this activator makes it similar to that of
waterglass.
Heat ow curves of the solid sodium silicate activated slag pastes
(n = 0.05, Ms = 1.5) with the activator solution added without or
after heating are shown in Fig. 9(b), along with that of a waterglass
activated paste of similar n and Ms . The acceleration peak makes its
appearance for the paste made with the heated activator solution,
albeit after a longer induction period. In this regard, the activator
behaves similarly to waterglass. As shown in the gure in the inset,
the induction period can be controlled (reduced, in this case) by
changing the activator Ms .
3.5. Kinetic modeling of powder and liquid sodium silicate and
NaOH activated slag
The previous sections have shown that there is a fundamental
difference in the reaction kinetics between solid sodium silicate
and waterglass activated slag systems. In this section, an attempt is
made to quantify these differences through modeling of the reac-
tion kinetics of slag activation when different activator types are
used. In order to determine the degree of reaction (), which is
used in kinetic models, it is essential to model the cumulative heat
released from the activation reaction, which is detailed below.
39
Fig. 9. (a) FTIR spectrum of the solid sodium silicate activator dissolved in water and
heated at 65 C for 6 h, (b) heat ow curves of solid sodium silicate activated slag
pastes without and after heating the activator, compared to that of the paste acti-
vated with waterglass. For all cases, n = 0.05. Ms = 1.5. The inset shows the reduction
in induction period when Ms is reduced.
3.5.1. Determining the cumulative heat release and the model
parameters
The cumulative heat released, Q(t), is obtained by integrating
the heat ow curves, and is shown in Fig. 10(a) and (b) respec-
tively for the powder sodium silicate and waterglass activated slag
pastes maintained at 25 C. The cumulative heat release for the solid
sodium silicate activated slag pastes shown in Fig. 10(a) can be con-
sidered to be contributed by a single major reaction peak while
those for the waterglass activated pastes shown in Fig. 10(b), it is
the contribution of both the dissolution (the initial rising portion)
and the acceleration peak (the latter rising portion). The dormant
period in these pastes is represented by the relatively atter regions
in the cumulative heat release curve between the initial dissolution
rise and the latter acceleration rise. In line with the discussions
before, the mixtures with a higher alkalinity (lower Ms and/or
higher n) show a higher cumulative heat release during the isother-
mal calorimetry experiments.
The values of Qmax , which is the ultimate heat released, corre-
sponding to the completion of the reaction (or a degree of reaction
of 1.0) can be obtained by tting an exponential model [48,49] to
the Q(t) vs. t curve.
  

Q (t) = Qmax exp (1)
t
In the above equation,  and are the time parameter and the
shape parameter respectively. Representative ts of the Q(t) vs. t
curves for powder sodium silicate and waterglass activated pastes
(n = 0.05, Ms = 1.5) are shown in Fig. 11. While the Q(t)t relationship
for the powder sodium silicate activated pastes are well character-
ized by this equation, the presence of a dormant period in between
for the waterglass activated pastes results in the above equation not
40 D. Ravikumar, N. Neithalath / Thermochimica Acta 546 (2012) 3243

Fig. 10. Cumulative heat released for slag pastes activated using: (a) powder sodium silicate and (b) water glass. Tests carried out at 25 C. Increase in the reaction temperature
increases the cumulative heat produced.

for these mixtures have been presented in [38]. The Qmax values
and the other tting parameters are shown in Table 2.
The time-dependent degree of reaction can be represented as
a ratio of the cumulative heat released at time t to the total heat
available (Qmax ).

Q (t)
(t) = (2)
Qmax

The degree of reaction () is time and temperature dependent and

can be characterized using the equivalent age maturity method.
This methodology allows the determination of reaction rate at any
temperature based on the known reaction rate at a reference tem-
perature. The time t is converted using the equivalent age maturity
function [50] that converts the actual age at a certain tempera-
ture to an equivalent age (te ) at a reference temperature (Tr ). This
allows the determination of (te ), which is used in a kinetic model
described in the latter part of this section. The relationship between
Fig. 11. Exponential ts applied to the cumulative heats (at 25 C) of representative
(te ) and te can also be expressed in a form similar to that of Eq.
powder and liquid activated slag pastes. Symbols represent the experimental data (1) to extract the ultimate degrees of reaction. This is not reported
points (1 out of 100 shown) and the solid lines show the t of Eq. (1) to the data. in this paper, but can be found in [38]. The shapes of the (te )te
curves are similar to those of the Q(t)t curves shown in Fig. 10.
adequately capturing the cumulative heat release behavior during The equivalent age, based on the Arrhenius rate theory is
the early stages of the reaction. But it can be seen from Fig. 11 that, expressed as [51,50]:
after about 12 h or so, the adequacy of the t is very good. Since
the major intention of the effort here is to obtain the Qmax values, 
t  E  1 1

a
further analysis using a two-part Q(t)t relationship is not shown in te (Tr ) = exp t (3)
R Tc Tr
this paper. However, the details of two-part curve tting approach 0

Table 2
Activation energy, total heat released and t parameters of the three-parameter equation for degree of reaction.

Type of activator n Ms Ea (kJ/mol) Qmax (kJ/kg)  (h) Reaction grade (N)

0.6 52.9 141 1.23 1.44 1.38

0.05
1.5 56.1 98.6 1.91 1.32 1.43
Solid sodium silicate + NaOH
0.6 49.8 224 0.87 2.10 1.31
0.15
1.5 52.1 176 0.91 1.65 1.32

1.0 62.4 235 10.30 1.15 1.86

Waterglass + NaOH 0.05 1.5 76.1 184 12.41 1.19 1.91
2.0 72.8 169.6 17.43 1.32 1.89

Ordinary Portland cement 38.4 275.8 7.44 1.14 1.85

NaOH (8 M) 80.9 154.3 0.80 2.10 1.19
 D. Ravikumar, N. Neithalath / Thermochimica Acta 546 (2012) 3243
Ea is the activation energy, R is the universal gas constant
(8.31 J/mol/K), and Tc is the temperature of the paste (in K), which
for isothermal calorimetric experiments, is the temperature at
which the experiment is run. The reference temperature, Tr , is taken
as 294 K in this study.
The (apparent) activation energies, Ea , of the activated slag
pastes of varying n and Ms values were determined from the Arrhe-
nius equation and the isothermal calorimetry experiments carried
out at three different temperatures (25 C, 35 C, and 45 C, as
explained earlier). Based on the Arrhenius equation, the temper-
ature dependent rate constant, P(T), can be expressed as:
 E 
a
P(T ) = A exp (4)
RT
A is a pre-exponential factor that does not change much with tem-
perature. A plot of P(T) vs. 1/T gives a straight line with Ea as the
slope of the line. Table 2 shows the Ea values of the solid sodium
silicate and waterglass activated slag pastes. The activation ener-
gies for the solid sodium silicate activated slag pastes vary between
50 and 55 kJ/mol whereas those for the waterglass activated pastes
are found to be in the range of 6075 kJ/mol. These values are much
higher than that of the Type I/II OPC used in this study, the Ea of
which is 38 kJ/mol. When 8 M NaOH is used as the activator, the
activation energy is found to be the highest, at 80 kJ/mol.
3.5.2. A kinetic model for degree of reaction in activated slag
systems
Several studies have described the hydration process of
ordinary Portland cement as a combination of three separate
but sometimes simultaneously occurring processes dissolu-
tion/nucleation/growth, phase boundary reactions, and diffusion
[52,53]. The reaction rate controlling step is determined by the
slowest of these processes. The heat development curves that
consist of the dissolution peak, acceleration peak, and the nal
nearly plateau stages can be loosely related to these three pro-
cesses. Hence the degree of reaction time relationship can
also be reasonably represented using a sum of these three pro-
cesses.
The dissolution and acceleration stages of hydration of Portland
cements have been modeled using the well-known Avrami equa-
tion [5355]. In general, Avrami equation describes the nucleation
and growth reactions quite well and thus predicts the kinetics of the
early part of the reaction adequately [56]. However, for alkali acti-
vated slag systems, the faster reaction product formation around
the slag particles facilitated by the alkalinity of the system results in
diffusion being the dominant rate controlling process as reported in
[57]. The phase boundary reaction and diffusion through the reac-
tion product layer are represented using Jander equation, which
was initially developed for diffusion controlled reactions in solid
state sintering [58]. This equation, the general form of which is
represented in Eq. (5) [57,59], has also been used to describe the
pozzolanic reactions of rice husk ash [60] and metakaolin [61].
N
[1 (1 (te ))1/3 ] = kD te (5)
In the above equation, kD is the rate constant that implicitly
accounts for the diffusion coefcient and the parameter N repre-
sents the rate controlling mechanism. A value of N that is closer to
1.0 indicates that the phase boundary kinetics controls the reac-
tion rate while a value closer to 2.0 indicates a diffusion controlled
process [57]. Eq. (5) has been tted onto the (te )te relationships
for the powder and liquid sodium silicate activated pastes and the
corresponding N values obtained are shown in Table 2. The n values
for the solid sodium silicate activated slag pastes lie between 1.3
and 1.4 and the corresponding value for the NaOH activated paste
is 1.19. It was explained earlier in the paper, based on heat ow
41
curves, that the dissolution and reaction product formation hap-
pen almost concurrently for the solid sodium silicate and NaOH
activated slag pastes. The formation of the reaction product layer
around the slag particles, i.e., through reactions that occur on the
particle surfaces, controls the reaction rate. The fact that these
values are closer to 1.0 indicates that the early-age kinetic behav-
ior of these mixtures is mostly dominated by the phase boundary
reactions even though some diffusion of the reactants through the
reaction product layer could also happen. On the contrary, for the
waterglass activated slag pastes, the N value is about 1.9, indicating
the dominance of a diffusion controlled process, similar to that for
OPC pastes (N = 1.85). The acceleration peak after a distinguishable
induction period suggets a diffusion process that is rate controlling.
The N values of around 1.9 obtained here for waterglass activated
pastes is in agreement with those reported in [57]. The analysis pre-
sented here conrms the observations from the calorimetry studies
that the slag pastes activated using solid sodium silicate are similar
to those activated using NaOH and those activated using waterglass
are similar to normal OPC pastes as far as the dominant processes
that control the reaction rate are concerned.
4. Conclusions
A comparative analysis of the reaction kinetics in powder
sodium silicate and waterglass activated slag systems of varying
activator modulus (Ms ) and Na2 O-to-slag ratios (n) determined
using isothermal calorimetry has been presented in this paper. The
powder sodium silicate activated slag systems showed much faster
setting (nal setting times of 20 min to an hour) and isothermal
heat ow peaks at very early ages (order of 1 h or so), attributable
to the formation of a layer of reaction products around the slag
particles that impede further reaction. Only one major heat ow
peak was observed for these systems. Higher n and lower Ms values
resulted in larger peaks. For the pastes activated using waterglass,
the response was observed to be similar to that of OPC hydration.
The acceleration peaks shifted to earlier times with a reduction in
activator Ms . The calorimetric response of the powder sodium sil-
icate activated slag pastes were found to be very similar to that of
slag activated using NaOH, indicating that all the silica from solid
sodium silicate powder does not go into solution. FTIR spectra of the
activator solutions were used to conrm this. Electrical conductiv-
ity measurements were used to develop equivalence relationships
between the alkalinity (expressed using n and Ms values) of solid
sodium silicate dissolved in solution and NaOH of varying con-
centrations. It was observed that 28 day compressive strengths in
the range of 2035 MPa which are adequate for most general pur-
pose concretes are attained when powder sodium silicate is used as
an activator. The waterglass activated pastes showed much higher
strengths, contributed by the higher amounts of reactive silica in
solution that favors the formation of larger amounts of C S H
gel.
Kinetic modeling of the alkali activation reaction of slag using
powder and liquid sodium silicate has been carried out in this
paper in an attempt to discern the mechanisms responsible for
the observed calorimetric response. The cumulative heat released
was represented using a commonly used exponential model, which
helped extract the maximum heat of reaction and consequently
the time-dependent degree of reaction for the mixtures activated
using powder sodium silicate, waterglass, or NaOH. Jander equation
was used to infer the reaction rate controlling mechanism from the
time-dependent degree of reaction. Phase boundary reactions dom-
inate the process in solid sodium silicate and NaOH activated pastes,
quantifying the similarity in their heat evolution curves whereas
diffusion dominates in OPC pastes and waterglass activated slag
pastes.
42 D. Ravikumar, N. Neithalath / Thermochimica Acta 546 (2012) 3243
Acknowledgements
The authors are grateful to the New York State Energy Research
and Development Authority for the nancial support towards the
study carried out. The materials were provided by Holcim US and
PQ Corporation. The experimental studies were carried out at the
Advanced Cementitious Materials and Systems Laboratory at Ari-
zona State University. The support that has made the establishment
of this facility is acknowledged. The contents of this paper reect
the views of the authors who are responsible for the facts and accu-
racy of the data presented herein, and do not necessarily reect
the views and policies of the funding agency, nor do the contents
constitute a standard, specication, or a regulation.
References
[1] P. Duxson, J.L. Provis, G.C. Lukey, J.S.J. van Deventer, The role of inorganic poly-
mer technology in the development of green concrete, Cement Concrete Res.
37 (2007) 15901597.
[2] D.M. Roy, Alkali-activated cements: opportunities and challenges, Cement Con-
crete Res. 29 (1999) 249254.
[3] A. Palomo, M. Grutzeck, M. Blanco, Alkali-activated y ashes: a cement for the
future, Cement Concrete Res. 29 (1999) 13231329.
[4] H. Xu, J. Van Deventer, The geopolymerisation of alumino-silicate minerals, Int.
J. Miner. Process. 59 (2000) 247266.
[5] C. Yip, G. Lukey, J. Van Deventer, The coexistence of geopolymeric gel and cal-
cium silicate hydrate at the early stage of alkaline activation, Cement Concrete
Res. 35 (2005) 16881697.
[6] C. Yip, J. Van Deventer, Microanalysis of calcium silicate hydrate gel formed
within a geopolymeric binder, J. Mater. Sci. 38 (2003) 38513860.
[7] S. Song, D. Sohn, H. Jennings, T. Mason, Hydration of alkali-activated ground
granulated blast furnace slag, J. Mater. Sci. 35 (2000) 249257.
[8] T. Bakharev, Geopolymeric materials prepared using Class F y ash and elevated
temperature curing, Cement Concrete Res. 35 (2005) 12241232.
[9] F. Pacheco-Torgal, J. Castro-Gomes, S. Jalali, Alkali-activated binders: a review.
Part 2. About materials and binders manufacture, Constr. Build. Mater. 22
(2008) 13151322.
[10] A. Fernndez-Jimnez, A. Palomo, M. Criado, Microstructure development of
alkali-activated y ash cement: a descriptive model, Cement Concrete Res. 35
(2005) 12041209.
[11] J. Wang, X. Wu, J. Wang, C. Liu, Y. Lai, Z. Hong, J. Zheng, Hydrothermal synthesis
and characterization of alkali-activated slagy ashmetakaolin cementitious
materials, Micropor. Mesopor. Mater. 155 (2012) 186191.
[12] T. Bakharev, J.G. Sanjayan, Y. Cheng, Resistance of alkali-activated slag concrete
to acid attack, Cement Concrete Res. 33 (2003) 16071611.
[13] A. Fernndez-Jimnez, J.G. Palomo, F. Puertas, Alkali-activated slag mor-
tars: mechanical strength behaviour, Cement Concrete Res. 29 (1999)
13131321.
[14] S.A. Bernal, R. Meja de Gutirrez, J.L. Provis, Engineering and durability
properties of concretes based on alkali-activated granulated blast furnace
slag/metakaolin blends, Constr. Build. Mater. 33 (2012) 99108.
[15] G. Kovalchuk, A. Fernndez-Jimnez, A. Palomo, Alkali-activated y ash:
effect of thermal curing conditions on mechanical and microstructural
developmentPart II, Fuel 86 (2007) 315322.
[16] F. Pacheco-Torgal, Z. Abdollahnejad, A.F. Cames, M. Jamshidi, Y. Ding, Dura-
bility of alkali-activated binders: a clear advantage over Portland cement or an
unproven issue? Constr. Build. Mater. 30 (2012) 400405.
[17] F. Puertas, A. Fernndez-Jimnez, M. Blanco-Varela, Pore solution in
alkali-activated slag cement pastes. Relation to the composition and
structure of calcium silicate hydrate, Cement Concrete Res. 34 (2004)
139148.
[18] A. Hajimohammadi, J.L. Provis, J.S.J. van Deventer, The effect of silica availabil-
ity on the mechanism of geopolymerisation, Cement Concrete Res. 41 (2011)
210216.
[19] A.R. Brough, M. Holloway, J. Sykes, A. Atkinson, Sodium silicate-based
alkali-activated slag mortars: Part II. The retarding effect of additions
of sodium chloride or malic acid, Cement Concrete Res. 30 (2000)
13751379.
[20] S. Wang, K.L. Scrivener, P.L. Pratt, Factors affecting the strength of alkali-
activated slag, Cement Concrete Res. 24 (1994) 10331043.
[21] K.H. Yang, J.K. Song, A.F. Ashour, E.T. Lee, Properties of cementless mortars
activated by sodium silicate, Constr. Build. Mater. 22 (2008) 19811989.
[22] K.H. Yang, J.K. Song, Workability loss and compressive strength development
of cementless mortars activated by combination of sodium silicate and sodium
hydroxide, J. Mater. Civil Eng. 21 (2009) 119.
[23] M. Gerstig, L. Wads, A method based on isothermal calorimetry to quantify the
inuence of moisture on the hydration rate of young cement pastes, Cement
Concrete Res. 40 (2010) 867874.
[24] F. Ridi, E. Fratini, P. Luciani, F. Winnefeld, P. Baglioni, Hydration kinetics of
tricalcium silicate by calorimetric methods, J. Colloid Interface Sci. 364 (2011)
118124.
[25] Q. Xu, J.M. Ruiz, J. Hu, K. Wang, R.O. Rasmussen, Modeling hydration prop-
erties and temperature developments of early-age concrete pavement using
calorimetry tests, Thermochim. Acta 512 (2011) 7685.
[26] V. Kocaba, E. Gallucci, K.L. Scrivener, Methods for determination of degree of
reaction of slag in blended cement pastes, Cement Concrete Res. 42 (2012)
511525.
[27] R. Ylmn, U. Jglid, B. Steenari, I. Panas, Early hydration and setting of Portland
cement monitored by IR, SEM and Vicat techniques, Cement Concrete Res. 39
(2009) 433439.
[28] D.P. Bentz, T. Sato, I. de la Varga, W.J. Weiss, Fine limestone additions to regulate
setting in high volume y ash mixtures, Cement Concrete Compos. 34 (2012)
1117.
[29] C. Shi, R.L. Day, Some factors affecting early hydration of alkali-slag cements,
Cement Concrete Res. 26 (1996) 439447.
[30] E. Altan, S.T. Erdogan, Alkali activation of a slag at ambient and elevated tem-
peratures, Cement Concrete Compos. 34 (2012) 131139.
[31] S.A. Bernal, J.L. Provis, V. Rose, R. Meja de Gutierrez, Evolution of binder struc-
ture in sodium silicate-activated slag-metakaolin blends, Cement Concrete
Compos. 33 (2011) 4654.
[32] C. Shi, R.L. Day, A calorimetric study of early hydration of alkali-slag cements,
Cement Concrete Res. 25 (1995) 13331346.
[33] M. Ben Haha, G. Le Saout, F. Winnefeld, B. Lothenbach, Inuence of activator
type on hydration kinetics, hydrate assemblage and microstructural develop-
ment of alkali activated blast-furnace slags, Cement Concrete Res. 41 (2011)
301310.
[34] X. Yao, Z. Zhang, H. Zhu, Y. Chen, Geopolymerization process of alkali-
metakaolinite characterized by isothermal calorimetry, Thermochim. Acta 493
(2009) 4954.
[35] D. Ravikumar, N. Neithalath, Effects of activator characteris-
tics on the reaction product formation in slag binders activated
using alkali silicate powder and NaOH, Cement Concrete Compos.
http://dx.doi.org/10.1016/j.cemconcomp.2012.03.006.
[36] S. Aggoun, M. Cheikh-Zouaoui, N. Chikh, R. Duval, Effect of some admixtures on
the setting time and strength evolution of cement pastes at early ages, Constr.
Build. Mater. 22 (2008) 106110.
[37] N. Schwarz, M. DuBois, N. Neithalath, Electrical conductivity based charac-
terization of plain and coarse glass powder modied cement pastes, Cement
Concrete Compos. 29 (2007) 656666.
[38] D. Ravikumar, Property development, microstructure and performance of alkali
activated y ash and slag systems, Ph.D. Thesis, Clarkson University, 2012, pp.
1217.
[39] J. Provis, J. Van Deventer, Geopolymerisation kinetics. 2. Reaction kinetic mod-
elling, Chem. Eng. Sci. 62 (2007) 23182329.
[40] H.A. Al-Abadleh, V. Grassian, FT-IR study of water adsorption on aluminum
oxide surfaces, Langmuir 19 (2003) 341347.
[41] J.L. Bass, G.L. Turner, Anion distributions in sodium silicate solutions. Character-
ization by 29Si NMR and infrared spectroscopies, and vapor phase osmometry,
J. Phys. Chem. B 101 (1997) 1063810644.
[42] W. Lee, J. Van Deventer, Use of infrared spectroscopy to study geopolymer-
ization of heterogeneous amorphous aluminosilicates, Langmuir 19 (2003)
87268734.
[43] I. Garca-Lodeiro, A. Fernndez-Jimnez, M.T. Blanco, A. Palomo, FTIR study of
the solgel synthesis of cementitious gels: C S H and N A S H, J. Sol Gel
Sci. Technol. 45 (2008) 6372.
[44] J.C. Kim, S.Y. Hong, Liquid concentration changes during slag cement hydration
by alkali activation, Cement Concrete Res. 31 (2001) 283285.
[45] M.B. Haha, B. Lothenbach, G. Le Saout, F. Winnefeld, Inuence of slag chemistry
on the hydration of alkali-activated blast-furnace slag Part II: effect of Al2 O3 ,
Cement Concrete Res. 42 (2012) 7483.
[46] K. Snyder, X. Feng, B. Keen, T. Mason, Estimating the electrical conductivity
of cement paste pore solutions from OH-, K and Na concentrations, Cement
Concrete Res. 33 (2003) 793798.
[47] F.A. Shebl, A.B. Summan, F.M. Helmy, Conductance of tricalcium silicate in
water, Cement Concrete Res. 18 (1988) 121130.
[48] A.K. Schindler, K.J. Folliard, Heat of hydration models for cementitious materi-
als, ACI Mater. J. 102 (2005) 2433.
[49] N. Neithalath, Quantifying the effects of hydration enhancement and dilution
in cement pastes containing coarse glass powder, J. Adv. Concrete Technol. 6
(2008) 397408.
[50] G. De Schutter, Applicability of degree of hydration concept and maturity
method for thermo-visco-elastic behaviour of early age concrete, Cement Con-
crete Compos. 26 (2004) 437443.
[51] N.J. Carino, H. Lew, The maturity method: theory and application, Cement Con-
crete Aggr. 6 (1984) 6173.
[52] P. Dabic, R. Krstulovic, D. Rusic, A new approach in mathematical modelling of
cement hydration development, Cement Concrete Res. 30 (2000) 10171021.
[53] G. Baert, N. De Belie, G. De Schutter, Multicompound model for the hydration
of Portland cementy ash binders, J. Mater. Civil Eng. 23 (2011) 761.
[54] J.J. Thomas, A new approach to modeling the nucleation and growth kinetics of
tricalcium silicate hydration, J. Am. Ceram. Soc. 90 (2007) 32823288.
[55] D.R. Vollet, A.F. Craievich, Effects of temperature and of the addition of accel-
erating and retarding agents on the kinetics of hydration of tricalcium silicate,
J. Phys. Chem. B 104 (2000) 1214312148.
[56] P.D. Tennis, H.M. Jennings, A model for two types of calcium silicate hydrate in
the microstructure of Portland cement pastes, Cement Concrete Res. 30 (2000)
855863.
 D. Ravikumar, N. Neithalath / Thermochimica Acta 546 (2012) 3243 43

[57] A. Fernndez-Jimnez, F. Puertas, Alkali-activated slag cements: kinetic studies,
Cement Concrete Res. 27 (1997) 359368.
[58] E. Gartner, J. Young, D. Damidot, I. Jawed, Hydration of Portland cement, in: J.
Bensted, P. Barnes (Eds.), Structure and Performance of Cements, Spon Press,
New York, 2002, pp. 57-113.
[59] C. Shi, P.V. Krivenko, D. Roy, Alkali-Activated Cements and Concretes, Spon
Press, 2006.
[60] Q. Feng, H. Yamamichi, M. Shoya, S. Sugita, Study on the pozzolanic properties
of rice husk ash by hydrochloric acid pretreatment, Cement Concrete Res. 34
(2004) 521526.
[61] J. Cabrera, M.F. Rojas, Mechanism of hydration of the metakaolinlimewater
system, Cement Concrete Res. 31 (2001) 177182.