Cite this article Research Article Keywords: alkali-activated cements/

Hoyos-Montilla AA, Puertas F and Tobón JI Paper 1900025 calorimetry/kinetics

Study of the reaction stages of alkali-activated cementitious materials using microcalorimetry. Received 07/02/2019; Revised 04/05/2019;
Advances in Cement Research, Accepted 05/05/2019
https://doi.org/10.1680/jadcr.19.00025
ICE Publishing: All rights reserved

Advances in Cement Research

Study of the reaction stages

of alkali-activated cementitious
materials using microcalorimetry
Ary Alain Hoyos-Montilla Jorge Ivan Tobón
Group of Materials, Construction School at Universidad Nacional Cement and Construction Materials Group, Department of Materials and
de Colombia, Medellin, Colombia (corresponding author: Minerals at Universidad Nacional de Colombia, Medellin, Colombia
aahoyosm@unal.edu.co) (Orcid:0000-0001-5115-7233) (Orcid:0000-0002-1451-1309)
Francisca Puertas
Eduardo Torroja Institute for Construction Sciences (IETcc – CSIC),
Madrid, Spain (Orcid:0000-0002-4215-0184)

The roles of sodium hydroxide, calcium hydroxide and temperature on heat flow evolution and its relation to the reaction
stages of alkali-activated coal fly ash were evaluated. The response surface method was used to analyse data. Both the
heat flow and kinetic parameters were determined by the deconvolution of microcalorimetric signals at 25, 35 and 45°C.
The studied factors were found to have a strong influence on the dissolution of ash rich in aluminium units, on the
diffusion–nucleation processes and its growth, both initial and final. A sodium hydroxide concentration of 8 M
guaranteed optimal reorganisation of the dissolved units to form the reaction products. Calcium hydroxide altered the
aluminium distribution in the paste, acting as nucleation spots and intervening in the formation of initial and final reaction
products. High temperatures were found to favour the efficiency of the alkali activation, increasing the rate constant and
simplifying the expiration of energy barriers. Knowledge of the heat flow evolution in these kinds of cementitious
materials will allow manipulation of the characteristics of the mixtures in both the fresh and hardened state.

Notation estimated that the global production of OPC emits about 6% of

A frequency factor anthropogenic carbon dioxide emissions and, together with the
Aj area of peak j aggregates needed for concrete manufacture, requires around
Dj duration of peak j 32% of the energy used in the production of the most
E apparent activation energy used materials in the world (Mehta and Siddique, 2016;
F test statistic Ruiz-Santaquiteria et al., 2016; Turner and Collins, 2013). One
Hj maximum height of heat flow of peak j way to avoid these adverse effects on the environment is to
k rate constant reduce OPC consumption by mixing OPC with AAC, generat-
n form parameter ing so-called hybrid alkaline cements (García-Lodeiro et al.,
p-value predefined significance 2012, 2016b). AAC, the products of coal fly ash alkali activation
Q(t) heat released at a time t by sodium hydroxide, are an alternative that has demonstrated,
Qmax total heat released individually and when mixed with OPC, mechanical and
R universal gas constant durability properties equal or higher to those of OPC
R2 coefficient of determination (Du Toit et al., 2017; García-Lodeiro et al., 2012; Palomo et al.,
T absolute temperature 2014). The characteristics of hybrid cements have been explained
tj time to reach maximum heat flow of peak j through the interaction between C–S–H (calcium silicate
to time parameter hydrates) and N–A–S–H (sodium aluminosilicate hydrates),
X1, X21 pure linear and quadratic components of the main generated during the hydration and activation of OPC and
effect produced by calcium hydroxide, respectively AAC, respectively. Nonetheless, in these cementitious materials,
X2, X22 pure linear and quadratic components of the main calcium hydroxide or portlandite is also generated in the
effect produced by sodium hydroxide, hydration of calcium silicates from OPC. One of the interests of
X1 X2 double interaction between calcium hydroxide and this study is to determine the effect of calcium hydroxide
sodium hydroxide on AAC.

Introduction The reaction products obtained from mixing aluminosilicates

Alkali-activated cementitious materials (AAC) can be used as with alkaline cations, as in geopolymers, are described as
partial or total replacements of ordinary Portland cement (Davidovits, 2008)
(OPC), with such replacements thus contributing to a decrease

in the energy consumption and carbon dioxide emissions 1: Mn – ðSiO2 Þz –AlO2 n ; wH2 O
generated during OPC manufacture (Provis, 2016). It is

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 Advances in Cement Research Study of the reaction stages of
alkali-activated cementitious
materials using microcalorimetry
Hoyos-Montilla, Puertas and Tobón

where n is the degree of polymerisation, z takes values of 1, 2,
3 or higher, M represents the alkaline cation and wH2 O is the
number of water molecules.
The processes involved in the generation of these products
integrate stages of destruction, coagulation, condensation and
crystallisation (Glukhovsky, 1994). During the destruction–
coagulation stages, the network-forming elements, which
are obtained from the aluminosilicates, remain free due to the
presence of the alkali activator. During the condensation–
crystallisation stages, the disintegrated products come together
to form dimers, trimers and tetramers, thus shaping the cemen-
titious material. Recent studies have described the process
of alkali activation conceptually: initially there is chemical
attack from the activator on the aluminosilicate, followed by a
dissolution process; subsequently, an aluminium-rich gel pre-
cipitates (this gel is also enriched in silicon); finally, polycon-
densation and growth processes occur (Duxson et al., 2006;
García-Lodeiro et al., 2016b; Xu and Van Deventer, 2000).
Coal fly ash activation by sodium hydroxide in the presence of
calcium hydroxide generates an interaction between
the network-forming elements (aluminium (Al) and silicon
(Si)) obtained from the coal fly ash and the network-modifying
elements (sodium (Na) and calcium (Ca)) present in the
sodium hydroxide and calcium hydroxide. This interaction
brings, as a consequence, the precipitation of cementing
materials formed by C–(A)–S–H (aluminium-incorporating
calcium silicate hydrates) gels or (N,C)–A–S–H (calcium-
incorporating sodium aluminosilicate hydrates) (García-
Lodeiro et al., 2011, 2016a). The formation of either one
depends on the pH as well as the sodium hydroxide and
calcium hydroxide concentrations (Khater, 2012). In alkali-
activated systems, calcium hydroxide intervenes in the for-
mation of amorphous and crystalline phases, participates ions
in the charge balance, supplies nucleation spots and favours
the presence of aluminium in the resulting gels (Guo and
Shi, 2015; Khater, 2012; Prasittisopin and Sereewatthanawut,
2017). Therefore, it is assumed that the stages that occur
chronologically to obtain AAC formed from coal fly ash and
sodium hydroxide in the presence of calcium hydroxide are
& dissolution of ash rich in aluminium units
& dissolution of ash rich in silicon units
& the first formation of gel rich in aluminium
& diffusion processes of the dissolved units and the activator
through the coal fly ash and the initial gel
& generation of pre-nuclei and possible nuclei with the
participation of calcium hydroxide
& growth and formation of the reaction products.
In studies of alkali-activation stages it is common to measure
and quantify the heat flow generated when the liquid and solid
parts come into contact (Chithiraputhiran and Neithalath,
2013; Wang and Lee, 2012; Zhang et al., 2013). The inter-
action between coal fly ash and sodium hydroxide causes an
exothermic calorimetric profile composed of two maximums
and a minimum between them. The processes that affect the
formation of the first maximum are grouped as the so-called
initial period, those that participate in the formation of the
minimum are grouped as the latent period and those that par-
ticipate in the formation of the second maximum are grouped
as the growing period (Wadsö, 2001; Zhang et al., 2012). This
profile makes it possible to describe a general alkali-activation
process through a series of steps shown in a linear and con-
secutive manner, but which are actually overlapped and
develop simultaneously (Zhang et al., 2012).
This motivation of this study was to present a detailed analysis
of the heat flow variations of the individual stages of alkali
activation, rather than a general analysis (as is currently done),
under modifications of the concentrations of sodium hydroxide
and calcium hydroxide and curing temperature. It is important
to know the energy exchange of cementing pastes with the
environment due to its relation with the kinetics and quantity
of reactions that are taking place. This study complements
knowledge on the thermal behaviour of alkali-activation pro-
cesses using statistical tools, such as analysis of variance
(Anova), in the study of heat flow and mathematical tools,
such as deconvolution, to separate the stages of alkali acti-
vation from microcalorimetric signals.
Materials and methods
Materials
The coal fly ash used in this study was obtained a power gener-
ation plant for the textile industry and was classified as class F
according to ASTM C618 (ASTM, 2017a). The sodium hydrox-
ide used was analytical grade with 99–100% purity and was
purchased in the form of caustic soda flakes. The calcium
hydroxide was of industrial type with a purity level of 95·6%
(weighted-profile R value, Rwp, at 12.5%). Deionised water was
used for preparation of the pastes. The chemical compositions,
in terms of major oxides, of the coal fly ash and calcium
hydroxide are presented in Table 1. X-ray fluorescence (Philips
PW-1004 spectrometer) was used to determine the elemental
composition by preparing pellets. X-ray diffraction analysis was
Table 1. Chemical composition of raw materials
Coal Calcium
fly ash hydroxide
Silicon dioxide (SiO2): wt% 55·26 0·18
Aluminium oxide (Al2O3): wt% 26·95 0·08
Calcium oxide (CaO): wt% 1·00 99·14
Ferric oxide (Fe2O3): wt% 5·66 0·10
Magnesium oxide (MgO): wt% 1·78 0·50
Sodium oxide (Na2O): wt% 0·44 —
Potassium oxide (K2O): wt% 0·75 —
Titanium dioxide (TiO2): wt% 2·28 —
Other: wt% 1·51 —
Loss on ignition at 950°C: wt% 4·37 —

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 Advances in Cement Research Study of the reaction stages of
alkali-activated cementitious
materials using microcalorimetry
Hoyos-Montilla, Puertas and Tobón

conducted using a D8 Advance diffractometer (Bruker AXL)
with an ultra-fast Lynxeye X-ray detector, 2·2 kW copper anode
without monochromator, with the addition of an internal stan-
dard of 20 wt% high-purity aluminium oxide. For quantification
by the Rietveld method, GSAS software was used.
The weight percentage (wt%) of reactive silica in the coal
fly ash was determined following the procedure described in
UNE 80225 2012 (AENOR, 2012). The vitreous phase content
(wt%) was found using an attack with 1% HF hydrofluoric
acid (Arjuman et al., 1997). The particle size distribution was
measured using a Mastersizer 2000 (Malvern Panalytical) laser
granulometer. The air permeability was determined by the
Blaine test and the density was measured using a Le Chatelier
flask. The results of these tests are provided in Table 2.
Design of mixtures
For the design of the experimental plan, an Anova was used in
combination with the response surface technique
(Montgomery, 2001). Two factors were studied – the calcium
hydroxide percentage (wt% of fly ash) and the molar concen-
tration of sodium hydroxide. The response surface method
requires that the amount of tests be distributed in three por-
tions, a factorial portion, centre points and an axial portion.
Taking into account the most common values reported in the
literature (Hoyos-Montilla et al., 2017; Khater, 2012; Peng
et al., 2015; Rattanasak and Chindaprasirt, 2009), the centre
point was determined to be 10% of calcium hydroxide and
8 M of sodium hydroxide, and the working intervals were
6–10 M for sodium hydroxide concentration and 5–15% for
calcium hydroxide percentage. The centre point and the
working intervals were used to determine the number of tests
and the proportions of the samples (Hoyos-Montilla et al.,
2017; Montgomery, 2001). Table 3 shows the experimental
plan and the proportions by weight. The water-to-cementitious
materials (w/cm) ratio used was 0·3, guaranteeing complete
wetting and adequate workability of the mixtures. The cementi-
tious materials comprised sodium hydroxide, calcium hydrox-
ide and coal fly ash.
Methods
The samples were studied using isothermal conduction micro-
calorimetry (Tam Air Thermostat 90/3116-1). ASTM C1679
(ASTM, 2017b) and ASTM C1702 (ASTM, 2017c) were used
as standards. 2·5 g of raw materials (sodium hydroxide + cal-
cium hydroxide + fly ash) were prepared with a w/cm ratio of
0·3. The sodium hydroxide was dissolved in water to form the
liquid part and the solid part (calcium hydroxide + fly ash) had
been previously homogenised. Once the solid part was placed
in the microcalorimeter, the liquid part was added with the
help of an admix device. The mixing time was 150 s at a speed
of 55 rpm. The ambient temperature was maintained at
25 ± 2°C. Each signal had, as a reference, distilled and deio-
nised water and the time of permanence was until asymptotic
behaviour with a slope <5 μW/h was achieved. Samples were
tested at 25, 35 and 45°C with three replicates for each
temperature.
Each signal obtained was deconvolved to separate the overlap-
ping peaks, a technique that has been successfully used for the

Table 2. Chemical characteristics and physical properties of raw materials

Reactive silica: Vitreous phase: Average particle Blaine fineness: Density:
wt% wt% size: μm m2/kg kg/m3

Coal fly ash 42·20 65·71 30 490·95 2160

Calcium hydroxide — — 5 705·67 2143

Table 3. Experimental plan and mix proportions of alkali-activated fly ash–calcium hydroxide
Weight per 100 g of cement: g

Number Sample Calcium Sodium Coal Calcium Sodium

Portion of tests number hydroxide: % hydroxide: M fly ash (FA) hydroxide (CH) hydroxide (SH)

Factorial 4 5 5 6 88·38 4·42 7·20

6 5 10 83·81 4·19 12·00
9 15 6 80·70 12·10 7·20
13 15 10 76·52 11·48 12·00
Centre pointsa 5 2, 3, 4, 7, 11 10 8 82·18 8·22 9·60
Axial 4 1 17·07 8 77·22 13·18 9·60
8 10 5·17 85·27 8·53 6·21
10 10 10·83 79·1 7·91 12·99
12 2·93 8 87·83 2·57 9·60

a
The response surface technique requires five centre points, one of the model plus one for each sample of the factorial portion. Each had the same proportions –
calcium hydroxide content of 10% (wt% of fly ash) and sodium hydroxide concentration of 8 M

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Table 4. Assignment of alkali-activation stages to each peak
product of the deconvolution
Stage Assignment
Dissolution of ash with greater presence of Al–O–Al Peak a
Dissolution of ash with greater presence of Si–O–Si Peak b
Formation of initial gel rich in aluminium Peak c
Diffusion–nucleation processes Peak d
Formation of reaction products (amorphous Peak e
and crystalline phases) to peak i
study of nuclear magnetic resonance and Fourier transform
infrared spectra (Kauppinen et al., 1981; Pérez et al., 2014).
The position and number of overlapping peaks were deter-
mined by the first and second derivatives of the signal that
is going to be deconvolved. Based on the reaction stages
assumed to obtain AAC from coal fly ash and sodium hydr-
oxide in the presence of calcium hydroxide, each peak was
assigned a stage of the reaction mechanism, named in alpha-
betical order from peak a to peak i, as shown in Table 4.
Each deconvolved peak generated four response variables
for the Anova – the maximum height of the heat flow (Hj ),
the time to reach the maximum heat flow (tj ), area (Aj ) and
duration (Dj ) – as shown in Figure 1. Hj and Aj are, respect-
ively, associated with the quantity of reactions and the total
released energy; tj is associated with the reaction kinetics and
Dj with the time in releasing the total energy (Wadsö, 2001,
2010).
The model associated with each response surface is of the form
2: Yi ¼ β0 þ β1 X1 þ β2 X2 þ β11 X12 þ β22 X22 þ β12 X1 X2 þ ε
Hj
Aj
Heat flow
Dj
tj
Time
Figure 1. Schematic diagram of the response variables for each
deconvolved peak: Hj, maximum height of heat flow; tj, time to
achieve Hj; Aj, area under the curve (in %); Dj, duration of the
peak (in units of time). The subscript j represents the deconvolved
peak from peak a to peak i
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Study of the reaction stages of
alkali-activated cementitious
materials using microcalorimetry
Hoyos-Montilla, Puertas and Tobón
where Yi are the response variables and βi are unknown con-
stants. X1 and X21 are, respectively, the pure linear and quad-
ratic component of the main effect produced by calcium
hydroxide and X2 and X22 are those corresponding to sodium
hydroxide. The factor X1X2 corresponds to the double inter-
action between calcium hydroxide and sodium hydroxide. ε is
the random error.
In order to determine whether the study factors are significant,
a predefined level of significance of 0·1 was chosen. Its value
was defined taking into account the little previous evidence
on the research topic and looking for the lowest risk of mis-
interpretation in the analysis of the results. Hence, any value
of calculated significance ( p-value) less than 0·1 was con-
sidered to have a significant effect on the response variable.
The rate constant, activation energy and frequency factor
were determined in order to analyse the changes produced
in the alkali-activation stages when the curing temperature
was increased. These parameters were obtained from the
equation developed by Knudsen (1984) and Knudsen and
Geiker (1985)
kðt  to Þn
3: QðtÞ ¼ Qmax
1 þ kðt  to Þn
where Q(t) is the heat released at a time t, Qmax is the total
heat released, k is the evolution rate constant of the heat flow
at temperature T and to and n are time and form parameters,
respectively. Knudsen found that the rate constant k is equal to
the reciprocal of 50% of the time to achieve maximum heat
release; that is, for deconvolved peaks, k = Dj/2. By identifying
the rate constant of each peak and linearising the Arrhenius
equation
 
E
4: kðTÞ ¼ A exp
RT
the apparent activation energy E and the frequency factor A
were calculated for each of the deconvolved peaks.
Results and discussion
Figure 2 shows the first of three replicas of the microcalori-
metric signals emitted by samples described in Table 3, for
each temperature. It can be seen that peaks occurred in the
initial, latent and growing periods. Variations in the tempera-
ture and hydroxides concentration modified the height and
time of formation of each period. On average, at higher temp-
eratures, the maximum height of the heat flow in each period
increased whereas the time to achieve it decreased. To deter-
mine the effects of the hydroxides and temperature in each
reaction stage, each signal was deconvolved.
As an example, the deconvolution of sample 2 at 25°C is
shown in Figure 3. The figure shows the alkali-activation
 Advances in Cement Research Study of the reaction stages of
alkali-activated cementitious
materials using microcalorimetry
Hoyos-Montilla, Puertas and Tobón

7 7 7 7
1 25°C 7 25°C
6 2 6 8

Heat flow: mW/g

Heat flow: mW/g

5 3 5 9
6 Initial 6 Initial
4 4 10
period period
3 3
4 11 7
5 2
5
5 2
12
Heat flow: mW/g

Heat flow: mW/g

1
6 Initial period
1 1 13 Initial period
8
Latent 0 2 Latent 0 9
4 period 0 5 10 15 20 25 30 4 period 0 5 10 15 20 25 30
Time: min 3 Time: min 10
0·3 0·3 11
1 2 3 4 7 10
3 3

Heat flow: mW/g

Heat flow: mW/g

5 12
0·2 0·2
6 8 9 13
2 Growing Growing period
2 Growing
0·1 4 5 6 0·1
period period
1 0
1 0 11 12 13 Growing period
2 4 6 8 10 2 4 6 8 10
Time: d Time: d
0 0
0 5 10 15 20 0 5 10 15 20
Time: d Time: d

10 35°C 10 7 35°C
10 1 10
Heat flow: mW/g

Heat flow: mW/g

2 8 8
Initial Initial 9
6 3 6
period period 10
8 4 4 8 4 11
5 12
2 2
13 7
Heat flow: mW/g

Heat flow: mW/g

6
Initial period
1 Initial period
Latent 0 Latent 0 8
6 2 6 period
period 0 5 10 15 20 25 30 0 5 10 15 20 25 30 9
1·6
Time: min 3 Time: min
10
1·6
1 4 11
Heat flow: mW/g

Heat flow: mW/g

1·2 2 7 8 9 1011 12 13
4 3
5 4 1·2 12
4 6
Growing 0·8 Growing 0·8 13
period 5
6 period
0·4 0·4 Growing period
2 Growing period 2
0 0
1 2 3 4 5 1 2 3 4 5
Time: d Time: d
0 0
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7
Time: d Time: d

12 12
45°C 12 12 7 45°C
10 10 8
1
Heat flow: mW/g

Heat flow: mW/g

Initial Initial 9
8 2 8
10 period 3 10 period 10
6 6
4 11
4 4 12
5 7
8 2 8
Heat flow: mW/g

Heat flow: mW/g

Latent 1 Latent 2 13
6 Initial period
period 0 Initial period period 0 8
2
0 5 10 15 20 25 30 0 5 10 15 20 25 30 9
6 Time: min 3 6 Time: min
4 4 10
1 4
Growing Growing 11
Heat flow: mW/g
Heat flow: mW/g

2 5 7 8 9 10
period period 12
4 3
6 4
2 4 5 6 2 11 12 13 13
Growing period Growing period
2 2
0 0
0·5 1·0 1·5 0·5 1·0 1·5
Time: d Time: d
0 0
0 1 2 3 4 0 1 2 3 4
Time: d Time: d

Figure 2. First replica of the signals emitted by the microcalorimeter at 25, 35 and 45°C. A full-colour version of this figure can be found
on the ICE Virtual Library (www.icevirtuallibrary.com)

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 Advances in Cement Research Study of the reaction stages of
alkali-activated cementitious
materials using microcalorimetry
Hoyos-Montilla, Puertas and Tobón

8 0·6 0·4

6
e
Heat flow: mW/g

c
4 0·3 0·2

a
f
g
2
h
b d
i

0 0 0
0 15 30 45 60 0 10 20 30 40 0 7 14 21 28
Time: min Time: h Time: d

Reorganisation
Dissolution Reorganisation Reaction products
Dissolution
Dissolution
Activation
reaction

Peak a Breakage Al–O–Al Peak c Initial gel Peaks e-i Growth, polymerisation
Peak b Breakage Si–O–Si Peak d Diffusion–nucleation and crystallisation

Initial period Latent period Growing period

Figure 3. Evolution of heat flow at 25°C during alkali activation for a sample with 10% calcium hydroxide and 8 M sodium hydroxide.
The peaks obtained in the deconvolution processes are named from peak a to peak i. Each deconvolved peak is associated with a stage
of the reaction mechanism in its respective period

stages as listed in Table 4 and their contribution to the heat
flow released for each period. The initial period comprised by
two peaks, peak a and peak b. The latent period consisted of
peaks c and d, while peaks e to i form the growing period. The
heat flow signals for the other replicas, composition and temp-
eratures showed a similar number of peaks. The changes are
evident in the response variables (Figure 1), with the most rel-
evant ones now explained.
Considering that the trends of the effects of sodium hydroxide
and calcium hydroxide on the response variables were identical
for the three study temperatures, averages of the calculated par-
ameters are reported. Table 5 presents the Anova results for
Hj, tj, Aj and Dj for the deconvolved peaks where sodium
hydroxide and calcium hydroxide had the greatest effect. The
first four rows of Table 5 present the parameters that indicate
the quality of the response surface models (standard deviation

Table 5. Anova of the experimental plan for deconvolved peaks where sodium hydroxide and calcium hydroxide had the most significant
effects. The peaks produced by the deconvolution are: peak a, dissolution of ash with the greater presence of Al–O–Al; peak d, diffusion–
nucleation processes; peaks e, h and i, reaction products
Response variable

Hj: mW/g tj: d Aj: % Dj: d

Peak a Peak d Peak e Peak i Peak a Peak d Peak e Peak h Peak d Peak h Peak i

SD 0·83 0·12 0·56 1·93 0·39 2·26 3·53 2·81 0·32 1·60 2·90
R 2: % 68·33 83·10 82·90 89·54 70·28 72·66 63·13 74·08 63·22 75·64 78·27
F 17·09 38·97 38·38 67·86 18·73 21·05 13·57 22·64 13·62 24·60 28·55
p-value <0·001 <0·001 <0·001 <0·001 <0·001 <0·001 <0·001 <0·001 <0·001 <0·001 <0·001
p-value of study factors
X1 0·016 0·358 0·366 0·025 <0·001 <0·001 0·043 0·397 <0·001 0·883 0·925
X2 <0·001 <0·001 <0·001 <0·001 0·003 <0·001 0·617 <0·001 0·707 0·001 <0·001
X1X2 0·500 0·022 0·076 0·739 0·101 0·124 0·143 0·018 0·224 0·110 0·057
X12 0·394 0·434 0·353 0·998 0·046 0·003 0·724 0·513 0·519 0·105 0·168
X22 0·625 0·344 <0·001 <0·001 0·304 0·001 <0·001 0·311 <0·001 0·060 0·172

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(SD), R 2, F and p-value) while the other rows show the
p-values of the main effects and double interactions. The
R 2 values close to 70% and low values of SD confirm that
the parameters generated a good degree of reliability in the
models’ quality. The p-values of less than 0·1 established not
only the effect of the linear components (X1 and X2), but also
the pure quadratic components (X21 and X22) and the double
interaction (X1X2) of calcium hydroxide (X1) and sodium
hydroxide (X2) on the response variables. Based on the results,
it was determined that sodium hydroxide and calcium hydr-
oxide generated the most significant changes during the dis-
solution of the ash rich in aluminium units (peak a), in the
processes of diffusion–nucleation (peak d) and growth of pro-
ducts in initial (peak e) and final (peak h or peak i) reactions.
The results were not registered for peaks b, c, f and g. These
peaks have in common that none or just one of the study
factors was significant. Additionally, the response variables
with the greatest magnitude of the test statistic (F) were taken
into account, since this is where sodium hydroxide and calcium
hydroxide had the greatest effect. Nonetheless, to maintain a
sequence in the analysis of the results, a general description of
the behaviour of the unregistered peaks was made. The deter-
mination from the statistical analysis that the study factors
were not significant at certain stages established that they
proceed as long as previous stages have begun; this can help in
detecting limiting stages.
Table 6 shows the variations in Ha, Hd, Dd, Ae, te and ti. Each
response variable is accompanied by the trends due to vari-
ations in sodium hydroxide concentration, calcium hydroxide
percentage and temperature, symbolised by arrows. max rep-
resents the maximum values. The trends were obtained from
the response surfaces and temperature plots, which are also
shown in Table 6. Each point on the temperature graph is a
representation of a response surface. The models associated
with the average surfaces are shown in the last column of the
table.
As shown in Table 6, the heat flow generated by the dissol-
ution of the ash with a greater presence of Al–O–Al (Ha)
decreased with an increase in calcium hydroxide. Due to the
greater interaction of aluminium with calcium compared with
that of silicon (Papadakis et al., 1992; Shi and Day, 2000) it
is possible that, during the dissolution process, calcium hydr-
oxide, in the form of a complex (CaOH+) (Pallagi et al., 2012)
penetrates the aluminosilicate rings with a greater presence
of aluminium and thus generates more stable and less active
compounds for a complete dissolution, decreasing the quantity
of heat released. Following peak a, the dissolution processes
of the ash with the greater presence of Si–O–Si (peak b) and
formation of initial gel rich in aluminium (peak c) begins;
these two peaks did not show significant changes due to the
presence of the hydroxides or an increase in temperature, pro-
viding evidence that the heat flow of the same is triggered
when peak a begins.
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Study of the reaction stages of
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Hoyos-Montilla, Puertas and Tobón
The units released from the dissolution diffuse and generate
nuclei. The variation in heat flow (Hd) and energy release
duration (Dd) of these processes is shown in Table 6. With an
increase in calcium hydroxide, Hd went from decreasing to
increasing behaviour due to a greater sodium hydroxide con-
centration. Dd tended to decrease with the presence of calcium
hydroxide, generating a maximum value for sodium hydroxide
concentrations around 8 M. It is clear that if there are enough
units released during dissolution, calcium hydroxide favours
the diffusion and nucleation of such units while generating
a greater number of reactions (Hd) in less time (Dd). A sodium
hydroxide concentration of  8 M guarantees that the dur-
ation of the latent period is the maximum, which significantly
affects the time of molecular and atomic reorganisation for gel
formation.
After the initial and latent periods, the growing period begins.
Considering the p-values shown in Table 5, it is evident that
sodium hydroxide and calcium hydroxide were significant at
the beginning (peak e) and end (peaks h or i) of this period.
High hydroxide concentrations minimised the growth time of
the first gel (peak e), while accelerating due to a greater
presence of calcium hydroxide (te). A greater permanence of
the system in the latent period (Dd), which was achieved for
a sodium hydroxide concentration of 8 M, led a maximum
percentage of released energy (Ae). te tended to the minimum
value because calcium hydroxide contributes to nucleation of
a heterogeneous nature (Khater, 2012; Temuujin et al., 2009),
which accelerates the formation of the first gel. The maximum
Ae at 8 M suggests that, at this peak, more complex struc-
tures are formed, which requires the release of the maximum
percentage of energy. Different sodium hydroxide concen-
trations generate structural changes that modify the heat
capacity of the gel (Zhang et al., 2017), decreasing the percen-
tage of released energy. Several studies have shown that, in
the activation of ash, the best compressive strength values are
obtained for concentrations of 8 M (Hoyos-Montilla et al.,
2018; Majidi, 2009; Peng et al., 2015; Rattanasak and
Chindaprasirt, 2009). This research shows that, for this con-
dition, the system remained in the latent period for as long as
possible and the formation of the first gel released the
maximum amount of energy, allowing optimal organisation of
the gels and their mechanical behaviour.
The peaks between peak e and peak h or peak i have in
common that, of the main effects, only the activator concen-
tration was significant. This indicates that the growth must
start from a nucleation of apparent homogeneous nature, since
it depends only on sodium hydroxide.
Sodium hydroxide and calcium hydroxide were again found
to be significant in the growth of the later gels. Calcium
hydroxide again affected the time but, unlike for peak e,
slowed down the reactions to achieve the maximum heat flow,
as shown for ti in Table 6. An increase in time indicates lower
7
 8

Advances in Cement Research

Table 6. Variations in Ha, Hd, Dd, te, Ae and ti due to changes in sodium hydroxide (SH), calcium hydroxide (CH) and temperature (T )
RV SH CH T Response surface Temperature graph Mathematical model

Ha " # " 8 646  0196  CH þ 0008  SH þ 00036  CH2 þ 0013  SH2

þ 001  CH  SH

Heat flow, Ha: mW/g

8
7

Heat flow, Ha: mW/g

7
7·81
6·60
6
6
5·39

11
5
5

10
3

9
6
25 35 45

8
CH 9 :M
:

7
12 SH
% Temperature: °C

6
15

5
Hd " " " 18 0·8 048  0025  CH  0053  SH  000048  CH2
! þ 00036  SH2 þ 00047  CH  SH
#

Heat flow, Hd: mW/g

0·63
0·6
Heat flow, Hd: mW/g

0·54
0·45
0·36 0·62 0·4
0·38
0·27
0·14

Hoyos-Montilla, Puertas and Tobón

materials using microcalorimetry
alkali-activated cementitious
Study of the reaction stages of
0·18 0·2
11
10
3

9
6

CH
9

:M 25 35 45
:
7
12

% SH
6
15

Temperature: °C
5
18

Dd max # # 1·2 − 51·4 + 17·71  SH + 0·0252  CH2 − SH2 − 0·16  CH  SH

1·00 1·0
Duration, Dd: d

0·83
0·8
Duration, Dd: d

0·98
0·67 0·52
0·07 0·6
0·50
0·33 0·4
0·17
0·2
11
10
3

9
6

CH
9

: :M 25 35 45
7
12

% SH
6
15

Temperature: °C
5
18

(continued on next page)

Advances in Cement Research

 Advances in Cement Research
te # # # 3 694 þ 007  CH  123  SH þ 00026  CH2 þ 007  SH2
 0016  CH  SH
2·5
2

Time, te: d
2·0

Time, te: d
1·5 2·92
1·79 1
1·0 0·65

0·5

11
10
3

9
6

8
CH 9
:M 25 35 45
:

7
% 12 SH

6
Temperature: °C
15

5
18
Ae max " # 18  1287  04  CH þ 66  SH  00063  CH2  046  SH2
! 16 þ 0087  CH  SH

Energy released, Ae: %

# 14
14
Energy released, Ae: %

12
12

10 14·02 10
10·10
8 6·18 8

Hoyos-Montilla, Puertas and Tobón

materials using microcalorimetry
alkali-activated cementitious
Study of the reaction stages of
6
11

6
10
3

9
6

CH
9

M 25 35 45
: H:
7
12

% S
6
15

Temperature: °C
5
18

ti # " # 14 277 þ 0018  CH  460  SH  000002  CH2 þ 022  SH2

10
12
þ 001  CH  SH
10
8
Time, ti: d

8
Time, ti: d

10·94 6
6
7·30 4
3·66
4 2
11
10
3

0
9
6

CH
9

:% :M 25 35 45
7
12

SH
6
15

Temperature: °C
5
18

RV, response variable

", !, # and max represent the relationship between the RV and SH, CH or T (respectively increase, constant, decrease and maximum)
The mathematical model corresponds to the average values of the three working temperatures (25, 35 and 45°C)
9

Advances in Cement Research

 Advances in Cement Research Study of the reaction stages of
alkali-activated cementitious
materials using microcalorimetry
Hoyos-Montilla, Puertas and Tobón

reaction kinetics. It is possible that, in these final peaks, the 18

interaction between coal fly ash and calcium hydroxide is more T: °C
significant, giving rise to slower reactions of the pozzolanic 15 25
type (Dunstan, 2011; Papadakis et al., 1992). 45

Released energy, Aj: %

12
The temperature graphs in Table 6 show how the maximum heat
flows Ha and Hd increased at higher temperatures, while the par- 9
ameters related to time (Dd, te and ti) and released energy per-
centage (Ae) decreased. Taking into account that to determine 6
the area of each peak (Aj ), the other response variables (Hj, tj
and Dj ) are included, the effect of temperature on the decon- 3
volved peaks can be summarised by a plot of Aj as a function of
temperature at its extreme values. Such plots are shown in
0
Figure 4, along with those for sodium hydroxide concentration a b c d e f g h i
and calcium hydroxide content for the most significant peaks. Peak
(a)
As shown in Figure 4(a), an increase in temperature led to an
increase in the percentage of released energy up to peak d, but Sodium hydroxide
20
decreases from peak e onwards. For an increase in the amount concentration: M
5·17
of hydroxides (Figures 4(b) and 4(c)), the tendency of Aj in
both peak a and peak d is to decrease while, from peak e 16 10·83
Released energy, Aj: %

onwards, the tendency is for Aj to increase. It is thus clear

that the hydroxides and temperature optimise energy release 12
differently. A high concentration of hydroxide implies a greater
availability of chemical constituents, accelerating the reactions
8
in the initial period (peak a) and the latent period (peak d),
generating a decrease in Aj. An increase in temperature
increases the number of reactions in the same periods, thus 4
increasing Aj. In the growing period, the functions are
reversed: a greater quantity of hydroxides increases the number
0
of reactions (thanks to the availability of chemical constituents) a d e h
while an increase in temperature accelerates the reactions. Peak
(b)
Estimations of the rate constant, activation energy and fre-
quency factor based on Equations 3 and 4 allowed specifica- Calcium hydroxide
24
tion of the behaviour of the reaction stages with a variation content: %
in temperature. Figure 5 shows the values of the rate constant 2·93
20
k for each of the stages of the activation process. 17·07
Released energy, Aj: %

16
In the first two stages of dissolution (peaks a and b) no signifi-
cant changes in k were observed as the temperature was
12
increased (Figure 5(a)). At each stage, the time for the reaction
was the same and did not depend on the temperature, revealing
8
that the processes are mainly physical in nature. During
reorganisation and formation of the reaction products (from
4
peak c onwards), k increased with temperature (Figure 5(b));
in other words, the processes were accelerated. Compared with
0
its neighbours, peak d at 35°C and 45°C had a lower value a d e h
of k, confirming a reduction in heat flow when the system Peak
enters the latent period, mainly due to diffusion–nucleation (c)
processes. Once the growth reactions begin, the k values
increased considerably from one temperature to another, corro- Figure 4. Variation of released energy Aj as a function of
borating the results in Figure 4(a). This is because the viscosity (a) extreme values of temperature T, (b) extreme values of
sodium hydroxide concentration and (c) extreme values of calcium
of a medium decreases with increasing temperature and, being
hydroxide content
inversely proportional to the nuclei growth rate (Gutzow et al.,

10
Advances in Cement Research
 Advances in Cement Research Study of the reaction stages of
alkali-activated cementitious
materials using microcalorimetry
Hoyos-Montilla, Puertas and Tobón

1985), the reactions are accelerated. For any temperature, the
rate constant decreased as the reaction mechanism advanced
and, from 35°C, there was an increase in the k value of peak e,
indicating that the system had entered the growth period,
giving rise to the formation of reaction products. From the
values of k and through linearisation of the Arrhenius
equation (Equation 4) when possible, the activation energies
(E) and frequency factors (A) were obtained for each peak.
The calculated values and their graphical representations
5·0 × 10–3
4·0 × 10–3
Rate constant: 1 s–1
are shown in Table 7 and Figure 6, respectively. These
results clearly show seen how E increases as the activation
mechanism advances, making the need for a higher tempera-
ture to overcome these energies evident. In the growing
period, the activation energy increased much more slowly
(ΔYe–i  24 kJ/mol) than in the initial alkali-activation pro-
cesses (ΔYc–e  84 kJ/mol), indicating the need to maintain the
temperature at least until peak e. On the other hand, the fre-
quency of molecular collisions (A) increased as the alkali-acti-
vation progressed; therefore, sufficiently energetic collisions for
the reactions to occur decreased, generating a loss in the effi-
ciency and reaction rate.
25°C
35°C
45°C
The variations in the heat flow of each stage of coal fly ash

alkali activation with sodium hydroxide in the presence of

calcium hydroxide by varying the concentrations of the hydrox-
3·0 × 10–3 ides and curing temperature have been presented in a new way.
Through the exchange of energy and its relationship with the
2·0 × 10–3 quantity and kinetics of the reactions, it was possible to deter-
mine the interaction between the network-forming elements
(aluminium and silicon) and network-modifying elements
1·0 × 10–3
(sodium and calcium). It was determined that, in hybrid
cements, there is an interaction between calcium hydroxide and
0 AAC that can affect the properties of the cementing material.
a b c d e f g h i
Peak The best results were obtained for calcium hydroxide content of
(a) 10% and sodium hydroxide concentrations of 8 M. These
proportions generate an adequate amount of chemical constitu-
2·5 × 10–4
25°C
ents ensuring the latent period begins without the network-
35°C forming and network-modifying elements being hindered latent
2·0 × 10–4 45°C period begins without the network-forming and network-modi-
Rate constant: 1 s–1

fying elements being hindered (Hoyos-Montilla et al., 2017).

1·5 × 10–4 For the initial growth, it is possible that the formed gel is of
the (N,C)–A–S–H type, taking into account the greater inter-
1·0 × 10–4
action of calcium hydroxide with aluminium and its function
as a nucleation spot. The heat flow of the gels formed after the
initial growth period was not altered by the calcium hydroxide
5·0 × 10–5
content. This suggests the growth of N–A–S–H gels. Finally,
calcium hydroxide, when interacting with coal fly ash in the
0 later stages of growth, probably constitutes type C–(A)–S–H
c d e f g h i gels. The morphology of these gels will depend on the perma-
Peak
nence time of their chemical constituents in the latent period,
(b) which will directly affect both the fresh and hardened proper-
ties. Therefore, the temperature in the curing process becomes
Figure 5. (a) Variation of the rate constant of the deconvolved paramount since the mechanism of activation, as it advances,
peaks as a function of temperature. (b) Expansion of the variation is less efficient. Knowing the heat flow in each stage of alkali
of the rate constant from peak c onwards
activation more precisely allows for manipulation of the

Table 7. Activation energy E and frequency factor A for each peak product of the deconvolution
Peak c Peak d Peak e Peak f Peak g Peak h Peak i

E: kJ/mol 19·78 62·11 104·22 102·46 109·39 118·17 128·32

A: s−1 1·82  107 6·76  1014 9·56  1016 6·14  1016 2·03  1017 3·41  1017 3·76  1017

For the working temperatures at peak a and peak b, linearisation of the Arrhenius equation was not possible, possibly due to the greater presence of physical reactions

11
Advances in Cement Research
 Advances in Cement Research
140
120
Activation energy: KJ/mol
100
80
60
40
20
c d e f g h i triggered by the beginning of the dissolution stage of the
Peak
Figure 6. Variation of activation energy and frequency factor of
molecular collisions for the deconvolved peaks
characteristics of mixtures from their manufacture, with design
additives to further optimise the formation of the cementing
material; for example, enhancing the first dissolution because
the next two stages depend on it, expanding the permanence of
the mixture in the latent period, guaranteeing reorganisation of
the chemical constituents and decreasing the activation energies
to be overcome to improve the efficiency of the alkali-activation
stages. The deconvolution of microcalorimetric signals contrib-
utes to an understanding of know how energy is released in
each reaction stage, making it possible to understand and
control the hydration reaction for AAC and another types of
cements. This allows for control of the properties of cement-
based materials in both the fresh and hardened states.
Additionally, it allows one to identify the slowest stage, the
fastest stage, the one with the highest energy release and so on,
giving the researcher the option to manipulate the reaction in a
specific stage to obtain a definite result.
Conclusions
The most significant conclusions from of this study are sum-
marised as follows.
(a) Study of the heat flow in fly ash based cementitious
materials due to variations in sodium hydroxide
concentration, calcium hydroxide content and
temperature showed that it is governed by dissolution of
the ash rich in aluminium units and the diffusion–
nucleation processes as well as their initial and final
growth.
(b) Changes in the hydroxides and temperature led to
different optimisations of the release of energy. An
adequate concentration of sodium hydroxide (8 M) and
calcium hydroxide content (10%) produced a greater
availability of chemical constituents and accelerated the
reactions in the initial processes and increasing them
during the growth stages. An increase in temperature
increased the number of reactions in the initial and
12
Advances in Cement Research
Study of the reaction stages of
alkali-activated cementitious
materials using microcalorimetry
Hoyos-Montilla, Puertas and Tobón
latent periods, and accelerated the reactions in the
4 × 1017
growing period.
Frequency factor: 1 s–1
(c) No significant changes were observed in the rate
3 × 1017 constants of the dissolution processes, indicating
that these processes are mainly of a physical nature.
2 × 1017 However, during the reorganisation and formation of
reaction products, the rate constant increased with
1 × 1017 temperature, indicating that the reactions were
accelerated.
0 (d) Heat flow in the dissolution stage of the ash rich in
silicon units and in the stage of initial gel formation was
ash rich in aluminium units. The intermediate reaction
products, which rely only on sodium hydroxide, owe their
heat flow to the growth generated from nucleation of
apparently homogeneous nature.
(e) During the dissolution of calcium hydroxide, due to
its cationic form, it penetrated the aluminosilicate rings
with a greater presence of aluminium and generated
more stable and less active compounds for complete
dissolution, thus decreasing the quantity of heat released.
The calcium hydroxide also acted as nucleation spots,
took part in the formation of the initial gel and
interacted with the coal fly ash in the final stages of the
growth period.
(f ) For sodium hydroxide concentrations of 8 M, the
permanence time of the chemical constituents in the
latent period and the percentage of released energy in the
growth stage of the first gel were maximised,
guaranteeing optimal reorganisation of the dissolved
units.
(g) The stages of alkali activation became less efficient as
they progressed because the rate constant and the
number of sufficiently energetic collisions decreased,
while the activation energy increased. High-temperature
curing conditions accelerated the reactions and
contributed to overcoming these barriers.
Acknowledgement
The authors would like to thank the Ministry of Economy,
Industry and Competitiveness of Spain for subvention of the
project BIA2013-47876-C2-1-P, within which some of the tests
in this study were carried out.
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