Construction and Building Materials 113 (2016) 917–926

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Influence of the long term curing temperature on the hydration

of alkaline binders of blast furnace slag-metakaolin
Oswaldo Burciaga-Díaz a,⇑, Lauren Y. Gómez-Zamorano b, José Iván Escalante-García a
a
Cinvestav Saltillo, Ceramics Engineering Group, Av. Industria Metalúrgica No. 1062, Parque Industrial, Ramos Arizpe, Coahuila, MX, C.P. 25900 Saltillo, Coahuila, Mexico
b
Centro de Investigación y Desarrollo Tecnológico, Universidad Autónoma de Nuevo León Pedro de Alba s/n, Ciudad Universitaria, San Nicolás, N.L., Mexico

h i g h l i g h t s

 Alkali activated binders based on metallurgical slag and metakaolin were studied.
 Analysis of variance provided insights on the significance of the parameters of activation.
 Curing temperature plays a major role on the properties; it improved early strength.
 In the long term higher temperatures did not favor strength and limited the reactions.
 The reaction products were amorphous and included C-N-(A)-S-H, N-A-S-H and silica gel.

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

Article history: This study analyzed the effect of the curing temperature on the long term properties and reactions of
Received 1 November 2015 silicate-activated slag-metakaolin binders. Cubic specimens were permanently cured at 20, 60 and
Received in revised form 5 March 2016 70 °C for up to 520 days evaluating the compressive strength and microstructural evolution. The treat-
Accepted 20 March 2016
ment of fresh pastes at elevated temperatures accelerates the strength development at early ages but
Available online 28 March 2016
in the long run, curing at 20 °C is more advantageous. For 100% slag pastes, increasing the curing temper-
ature from 20 to 60 °C favored an intense dissolution of the slag particles and the formation of a strong
Keywords:
microstructure that reached 100 MPa, this contrasted with the pastes of 100% metakaolin and
Alkali-activated slag
Metakaolin
composites of 50% metakaolin. X-ray diffraction and Scanning Electron Microscopy revealed that higher
Long-term curing temperatures resulted in higher incorporation of Al in the outer products of slag pastes, while in pastes
Compressive strength with 50% metakaolin silica rich phases condensed from the unreacted activating solution forming a
Microstructural evolution matrix of intermixed products of C-(A)-S-H and N-A-S-H type gel. The total heat released by the
silicate-activated binders was lower than that reported for the hydration of Portland cement.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction However, as a response to improve some drawbacks exhibited by

The current global trends in scientific research on cementitious
materials focus on the reuse of industrial by products to preserve
natural resources and to reduce the environmental footprint of
the Portland cement (PC) industry [1,2]. Granulated blast furnace
slag (GBFS), a glassy by-product formed after the production of
iron, has been used in the construction industry as a partial or total
replacement of PC for the last decades [3–5]. As a total replacement
in alkali activated cements, the GBFS has resulted in concretes with
very good mechanical performance, durability and reduced
environmental footprint relative to PC-based materials [1,6,7].
⇑ Corresponding author at: Instituto Tecnológico de Saltillo, Blvd. Venustiano
Carranza # 2400, Col. Tecnológico, C.P. 25280 Saltillo, Coahuila, Mexico.
E-mail address: oburciaga@itsaltillo.edu.mx (O. Burciaga-Díaz).
such binders, including rapid carbonation, efflorescence, drying
shrinkage and cracking [8–10] new formulations of composite
binders with less Ca content have been recently reported by the
addition of aluminosilicate-rich materials, such as fly ash (FA)
[11–15] and metakaolin (MK) [16–20]. FA is a byproduct from
the combustion of pulverized coal in thermal power plants, while
MK is an amorphous aluminosilicate that results from the calcina-
tion of kaolinite at 500–800 °C and is highly reactive under
alkaline conditions [21,22].
In the case of alkali-activated GBFS-MK binders, it has been rec-
ognized that under the proper activation conditions, some draw-
backs noted for the activation of the individual GBFS or MK, are
counterbalanced, so the blends benefit from a synergy, resulting
in cements and concretes with good properties in fresh and hard-
ened state [4]. In general, the inclusion of GBFS in the blends

http://dx.doi.org/10.1016/j.conbuildmat.2016.03.111
0950-0618/Ó 2016 Elsevier Ltd. All rights reserved.
918 O. Burciaga-Díaz et al. / Construction and Building Materials 113 (2016) 917–926
reduces the water demand, which benefits the compressive
strength of pastes and concretes; while increasing the MK content
usually delays the setting times, enhances the workability, and
although it reduces the strength, it improves the carbonation per-
formance [17–19,23,24]. It is believed that such properties result
from stable coexistence of complex and chemically different reac-
tion products as the high Al-substituted calcium silicate hydrate
(C-N-(A)-S-H)-type gel and the alkali aluminosilicate gel N-A-S-H
[20,25].
The C-N-(A)-S-H is a mechanically strong gel composed by a
combination of crystalline tobermorite-like structures and
amorphous cross-linked products with a relatively high content
of silicon in the form of Q1, Q2 and Q3 sites that promote the
densification of the microstructures [26–29]. Additionally,
Q3(1Al) and Q4 (4Al) units are also present suggesting that the
C-N-(A)-S-H in alkali-activated slag cements may contain disor-
dered nanoparticulate zeolite-like products [30,31]. On the other
hand, the N-A-S-H gel is a highly amorphous and cross-linked
binding phase with silicon appearing in a wide variety of Q4(nAl)
(n = 0, 1, 2, 3 and 4) environments [32,33].
Among the factors affecting the properties of alkali-activated
cements, numerous publications have shown that the curing
temperature greatly affects the kinetics of reactions as well as
the distribution, density, nature and properties of the reaction
products [34–36]. While the effect of temperature on the
microstructure and properties has been reported for alkali acti-
vated GBFS [5,34,37–39] and MK [36,40–43] cements, no reports
were found about the influence of this parameter on the long-
term mechanical properties and microstructural features of
alkali-activated blended binders based on GBFS–MK. High curing
temperature and its effects on the reactions of alkali-activated
cements is relevant to understand the behavior of such systems
under different environmental conditions and also to design or
formulate modern cements with good stability and improved
properties. Therefore, the aim this research was to analyze the
evolution of the strength and the microstructure of composite
alkali-activated binders of GBFS-MK, subjected to permanent
curing temperatures of 20 °C, 60 °C and 70 °C up to 520 days.
2. Experimental procedure
2.1. Materials
Granulated blast-furnace slag (GBFS) and a metakaolin (MK), were used as pre-
cursors, and their chemical composition determined by X-ray fluorescence is shown
in Table 1. Laser diffraction indicated that the GBFS had a mean particle size of (d50)
= 11.77 lm and 10% had a particle size smaller than 2 lm, the Blaine fineness was
of 4653 cm2/g. The MK was obtained after calcination of commercially available
high purity kaolin at 800 °C for 6 h; the Blaine fineness of the MK was of
9469 cm2/g with a mean particle size (d50) of 7.6 lm and also 10% had a particle
size smaller than 2 lm. Both raw materials were predominantly amorphous to
Table 1
Chemical composition by XRF (mass%) and Blaine fineness of the solid GBFS and MK
used.
Oxide (mass%) GBFS
SiO2 33.4
Al2O3 11.3
Fe2O3 0.5
CaO 37.8
TiO2 1.4
Na2O 0.5
K2O 0.9
MgO 8.9
MnO 0.5
SO3 3.4
Blaine (cm2/g) 4653
X-ray diffraction, nevertheless the GBFS showed traces of crystalline phases as aker-
manite (Ca2MgSi2O7), gehlenite (Ca2Al2SiO7), and merwinite (Ca3MgSi2O8), while
MK showed quartz (SiO2) and anatase (TiO2).
The alkaline chemicals used as activators were blends of sodium silicate
(SiO2 = 29.5%, Na2O = 14.7% and H2O = 55.8%) modulus SiO2/Na2O = 2 and sodium
hydroxide flakes, both of industrial grade.
2.2. Sample synthesis and test procedures
In order to elaborate the pastes for the investigation, the starting powders were
mixed in GBFS-MK proportions (mass%) of: 100-0, 80-20, 50-50, 20-80 and 0-100;
this nomenclature was used throughout the paper. The alkaline solutions had a
modulus Ms = 1 and the Na2O was added in concentrations of 5, 10 and 15 mass%
with respect to the sum of the GBFS + MK. This range of activation conditions has
been identified as resulting in GBFS-MK binders with high compressive strength
and acceptable workability [18,19]. The water/solids ratio was adjusted to obtain
flowable pastes of similar workability suitable for casting into the molds.
The pastes were cast in cubic molds with sides of 50 mm, which were vibrated
for 45 s to eliminate air bubbles. The samples were left covered with a thin plastic
film for 24 h at 20 °C. Afterwards, the demolded cubes were covered with plastic
bags and then stored in plastic boxes to continue with a process of permanent cur-
ing in isothermal chambers at 20, 60 and 75 °C for up to 520 days. The compressive
strength (CS) was statistically analyzed as described later, testing four samples
cured for 1, 3, 7, 14, 28, 90, 180, 360, and 520 days using an automatic hydraulic
machine (Controls Sercomp 7) with a constant loading rate of 500 N/s. The results
were statistically analyzed as described later.
For the characterization of selected samples, the reaction process was stopped
at various ages by submerging fragments of pastes in acetone for 2 days, and then
drying them in a vacuum oven (VWR 1430M) at 40 °C for 48 h. The samples were
then ground in a planetary mill (PM 400/2; Restch, Newtown, PA), using agate
media, to pass the #100 sieve. The ground powders were characterized by X-ray
diffraction (XRD, Philips D-Expert, Netherlands) in a range of 7–60°(2h) with a step
size of 0.03° and a count time of 2 s per step, using CuKa (1.542 Å) radiation. For
scanning electron microscopy (SEM) analysis, pieces of dried samples were
mounted in resin and polished using diamond pastes down to 1/4 lm. Further car-
bon coating was necessary to make the samples conductive under the microscope
(ESEM Philips XL30, Eindhoven, the Netherlands) accessorized with energy-
dispersive X-ray spectroscopy (EDS). Representative backscattered electron images
of microstructures were taken at 500 magnifications in high vacuum mode using an
accelerating voltage of 20 kV, spot size of 4–5 and a working distance of 9.8–10 mm.
EDS spot analyses were collected throughout the microstructure at 5000 magnifica-
tions, the microscope was operated at 20 kV and the time of analysis was of 50 s.
For selected formulations, the early progress of the chemical reactions was
investigated by following the evolution of the rate of heat of reaction, by means
of an isothermal conduction calorimeter. For the test, 15 g of raw GBFS + MK were
placed in an isolated cell tests accessorized with a propeller for manual agitation,
the powder was contained by a cling plastic film, and placed on a thin electrolytic
copper foil that was in contact with the Peltier device used as heat flow sensor. The
required amounts of activating solutions for each studied formulation were
weighed in syringes. The insulated containers bearing the samples were then sub-
merged in water in an isothermal bath (ISOTEMP 3028 at 20 °C and 60 °C ± 0.01 °C)
altogether with the syringes. Once the thermal equilibrium was achieved, the solu-
tion was injected to the powders and the paste was mixed for 40 s sufficient to
achieve proper homogenization of the pastes, as determined from a series of pre-
liminary tests). Data logging (National Instruments Model SCXI-1303) was started
along with the injection of the solution and continued for up to 40 h. Calibration
was performed afterwards to convert the signals from mV to kJ/kg.h.
2.3. Statistical analysis of the compressive results
In order to investigate the effect of the variables and their interactions on the
development of the compressive strength in composite GBFS-MK pastes, a complete
factorial experimental design (52  32) was conducted for each age studied follow-
ing the methodology explained in a previous work [18]. A total of 45 compositions
were evaluated by modifying various factors or independent variables. The nomen-
clature used to identify the factors was A – GBFS/MK ratio; B – %Na2O; C – Temper-
ature, and D – curing time. The factorial experimental design (52  32) means that
MK two factors (GBFS/MK ratio and Curing time) were evaluated at five levels and two
51.05 (%Na2O and the Temperature) at three levels, Table 2 summarizes the factors and
45.26
0.34
0.10 Table 2
1.76 Factors and levels considered for the ANOVA.
0.06
0.15 Factors Levels
— A = GBFS/MK ratio 100/0; 80/20; 50/50; 20/80; 0/100
— B = % Na2O 5%; 10%; 15%
— C = temperature (°C) 20; 60; 75
9469 D = curing time (Days) 1; 28; 90; 180; 520
 O. Burciaga-Díaz et al. / Construction and Building Materials 113 (2016) 917–926
their levels. For the experimentation, the response variable (dependent) was the
compressive strength at 1, 28, 90, 180 and 560 days, and a total of 225 data of
strength were acquired and statistically treated.
The statistical significance of each factor and their binary interactions, over the
strength development was quantitatively determined using an analysis of variance
(F-ANOVA) considering a confidence level of 95%.
3. Results and discussion
3.1. Compressive strength
Fig. 1 presents the generalized effects that resulted from the
analysis of variance (F-ANOVA) after 520 days of curing. From
Fig. 1(a) it is noteworthy that binders with 100%GBFS (100-0) with
approximately 38% Ca, developed the highest compressive strength
of about 70 MPa, similar to that previously reported for samples
cured only at 20 °C [18]. Also, the strength was reduced with the
addition of MK [23]; the pastes with 50%MK (50-50) or 100%MK
(0–100) showed average strengths of around 45 and 20 MPa
respectively, which are acceptable for different applications. The
results indicated that the gradual incorporation of aluminosilicates
in the binders demands higher concentrations of alkalis in the
solution in order to promote the dissolution of the Si-O-Si and
Si-O-Al bonds, and the subsequent precipitation of cementitious
reaction products [18,24]. This also means that, the lower demand
of activator by the 100%GBFS pastes, which is the more expensive
component in these compositions, makes them of lower costs of
production and of a smaller CO2 footprint relative to binders with
additions of MK. Nonetheless, it is possible that although the incor-
poration of MK reduces the strength in the composites, other prop-
erties like the durability can be improved making these
compositions suitable for special applications where a combina-
Fig. 1. Influence of the factors A (a); B (b); and CD (c) on the development of compressive strength.
919
tion of good durability and optimum strength can be required
[24] and unpublished data from the authors [44].
Fig. 1(b) confirmed that regardless of the curing temperature
and ratio BFS-MK, the strength development is highly influenced
by the %Na2O; i.e., 10% of Na2O in the activating solution resulted
in pastes with the higher mean strength of 50 MPa after 520 days.
On the other hand, Fig. 1(c) shows that temperature and curing
time had a strong influence on the development of compressive
strength. After 1 day of curing at 75 and 60 °C the mean strengths
were of 50 and 45 MPa, respectively, while curing at 20 °C resulted
in less than 20 MPa. After 28 days, the specimens cured at 20 °C
showed a higher rate of strength gain, that the pastes cured at
75 °C but less than those cured at 60 °C (55 MPa). The samples
cured at 20 °C gained strength after 90 days, whereas the opposite
was noted for the pastes cured at 60 and 75 °C; the latter showed
slight strength losses that stabilized at 47 and 43 MPa, after
520 days respectively; this behavior could be related to the contin-
uous dehydration of microstructures and formation of microcracks.
This could be explained by considering that during the early ages,
higher curing temperatures enhanced the dissolution of GBFS and/
or MK and the heterogeneous condensation of reaction products
mechanically strong in the matrix. Furthermore, the high curing
temperatures may have caused a rapid evaporation of water,
which, together with a relatively rapid densification of the
microstructure, inhibited the further diffusion of species, limiting
the progress of the reactions and consequently the development
of strength. In contrast, the samples cured at low temperature
(20 °C) underwent the opposite effect, in which a slow dissolution
of the reactive species took place, resulting in a more homoge-
neous condensation of reaction products due to the increased
water retention within the microstructures; at 20 °C the diffusion
processes and the formation of products continued over time to a
920 O. Burciaga-Díaz et al. / Construction and Building Materials 113 (2016) 917–926
point in which the densification of the matrix and the consumption
of reactants became the limiting factors for the advance of the
reaction processes.
Table 3 indicates that from the four factors considered, there is
a strong influence of the factors A (BFS/MK ratio) and B (%Na2O)
and their interaction on the compressive strength since early ages
of curing. This is coherent, because the demand of Na2O depends
strongly on the physical and chemical characteristics of the raw
materials used; generally, higher MK contents will demand higher
%Na2O. Additionally, as the reaction time increases, from 28 to
520 days, the CD (temperature-time) interaction became more
important while the individual factor D (Curing time) became sta-
tistically less important; this implies that the binary interactions
AB and CD are statistically the most important variables on the
development of strength for the studied formulations.
3.2. Hydration products
Fig. 2 shows XRD results of binders 100-0, 0-100 and 50-50 acti-
vated with Ms = 1, 10%Na2O and cured for 180 days at 20, 60 and
75 °C; the values of compressive strength were included. Fig. 2(a)
shows the GBFS (100-0) spectra for samples cured at 20 °C, where
the main crystalline phases were gehlenite (Ca2Al2SiO7; PDF# 01-
089-5917) merwinite (Ca3MgSi2O8; PDF# 035-0591) and akerman-
ite (Ca2MgSi2O7; PDF# 079-2424), contained in the unreacted slag;
other crystalline reaction products were calcite (CaCO3 at 29.07°
2h; PDF# 01-083-0577) and calcium silicate hydrate (C-S-H at
29.57° 2h) with a riversideite 9 Å type structure (Ca5Si6O17
H2O;
PDF# 029-0329), previously reported for slags with different
chemical compositions [23,45]. The latter phases are commonly
observed when the GBFS is activated with sodium silicate solutions
[46] and the calcite indicates the carbonation of the samples
during the preparation or storage of the samples. Hydrotalcite
(Mg6Al2CO3(OH)16
4H2O; PDF#014-0191) was also observed as
secondary reaction product [46,47]. After curing at 60 and 75 °C,
sharpening and intensification of hydrotalcite and C-S-H (29.57°
2h) can be identified, indicating that higher temperatures favored
the formation of more crystalline C-S-H or that the amount of such
hydrate was greater than in samples cured at 20 °C. The latter is
more feasible as higher temperatures resulted in higher strength,
this is consistent with previous reports indicating that high curing
temperatures enhance the reactivity of the GBFS, at early ages, as
the energy of activation of the GBFS is relatively high [34]. How-
ever, when a binder that has free water is subjected to elevated
temperatures during the first hours, the reactions are effectively
enhanced, but the water will also tend to evaporate promoting
the cracking and limiting the reactivity and thus restricting
strength the strength gain as observed in the samples cured at
75 °C.
On the other hand, Fig. 2(b) shows the spectra of geopolymer
binders containing 100% MK (0-100) with only traces of quartz
(SiO2; PDF# 00-074-0764) and anatase (TiO2; PDF# 01-083-2243)
even after the activation at 20, 60 and 75 °C, suggesting that such
phases remained inert. The patterns evidenced the presence of a
large halo in the 15–35° 2h range, originated from the formation
of alkali aluminosilicate N-A-S-H type gel [43,48]. In this case,
Table 3
Order of importance of the factors at different age of curing.
Curing time (days) Statistical significance of the factors
28 C < AB < B < D < A
90 CD < D < AB < B < A
180 D < CD < AB < B < A
520 D < CD < AB < B < A
the increase in the temperature did not cause significative changes
in the XRD patterns, and the N-A-S-H reaction products preserved
an amorphous nature. However in contrast with binders 100-0, the
increase in the temperature reduced the compressive strength,
which was due mostly to unfinished reactions of the MK, the con-
tinuous dehydration and possibly the formation of microcracks
produced by the evaporation of water.
It is interesting that in the XRD patterns of the binder 50-50 in
Fig. 2(c), the shape of the amorphous hump around 20–40° 2h was
different to that observed in binders 100-0 and 0-100, but it also
appears as the superposition of the 100-0 and 0-100 gels, this sug-
gests the condensation of reaction products based on a intermix-
ture of C-S-H and N-A-S-H gels with a more complex atomic
structure than those of the products formed by the individual acti-
vation of GBFS or MK. Regardless of the curing temperature, quartz,
anatase, akermanite and gehlenite reflections remained in all the
patterns. The C-S-H peak at 29.57° 2h did not show any variation
with the curing temperature but it was sharper and more intense
than that detected in the binder 100-0, denoting a higher crys-
tallinity promoted by the inclusion of Al. It was noted that the
presence of 50% MK inhibited the formation of CaCO3 previously
observed in 100-0 binders, which is in agreement with results
reported by Bernal et al. [24]; however, similar to that observed
in the formulation 0-100, an increased temperature limited the
gain of compressive strength.
3.3. Microstructures and chemical composition of reaction products
Fig. 3 presents the microstructures, obtained by scanning elec-
tron microscopy in backscattered electron imaging mode, of bin-
ders 100-0, 0-100 and 50-50 activated with sodium silicate
Ms = 1, 10%Na2O and cured for 180 days at 20 and 60 °C.
The microstructure of the binder with 100%GBFS (100-0) cured
at 20 °C, showed cracks and unreacted GBFS particles distributed in
a reaction products matrix of darker gray tone (outer products, OP)
for which EDS showed high contents of Si and Ca. The formation of
cracks in silicate activated GBFS binders could be related to the
evaporation of uncombined water as the samples tend to dry under
the vacuum of the microscope column that causes substantial
shrinkage and therefore microcracking [49].
The content of unreacted GBFS grains correlates well with the
lower strength shown at 20 °C, and the higher temperature
resulted in a matrix apparently more compact, with less unreacted
slag (more fully reacted slag grains) and mechanically stronger
than at 20 °C. At 60 °C many slag grains were completely reacted
and some appeared partially reacted with rims of reaction prod-
ucts, such reaction products appeared of a darker shade; these fea-
tures were not noted after curing at 20 °C, which suggest different
mechanisms of reaction of the slag. At 20 °C the predominant
mechanism of the reaction was the dissolution of the glassy struc-
ture and subsequent precipitation of the hydration products in the
spaces initially occupied by the activating solution; while at 60 °C
the reactions occurred also via a solid state mechanism in which
the reactants diffused through the reaction products and formed
more products, consuming the BFS grains inwards. This indicates
that although a high temperature may contribute to a rapid loss
of moisture, it is also favorable for the reactivity of the GBFS.
For the 100%MK binders (0-100) cured at 20 °C a dense
microstructure was noted, which explains the relatively high
strength. According to XRD and EDS results, the outer products
(OP), consisted of an amorphous aluminosilicate gel (N-A-S-H)
with high concentration of Si, Al and Na; such products are identi-
fied by the darker gray tone in the microstructures. Curing at 60 °C
reduced the progress of the dissolution-condensation processes;
which was evidenced with a higher content of unreacted MK par-
ticles. This indicates that in contrast to the binder 100-0, the
 O. Burciaga-Díaz et al. / Construction and Building Materials 113 (2016) 917–926
Fig. 2. X-ray diffraction patterns of pastes with Ms = 1 and 10%Na2O; (a) 100-0, (b) 0-100 and (c) 50-50, at different temperature and 180 days of curing.
increasing in the temperature hindered the reaction processes [50],
and it appears that the retention of free water in the microstruc-
ture seems to be more important for the dissolution of MK and
condensation products of high strength [43].
On the other hand, the microstructure of the composite sam-
ple with 50%MK cured at 20 °C indicated the presence of unre-
acted GBFS and MK particles distributed in a matrix of reaction
products. The OP matrix appeared dense regardless of the cracks
present. Nevertheless the high curing temperature decreased the
strength, as at 60 °C the condensed OP had greater porosity and
were coarser. At 60 °C it was difficult to identify particles of unre-
acted MK, as these had a similar tone that the OP. This means
that the high curing temperature probably produced the evapora-
tion of water, which increased the average atomic number of the
OP making them appear with a lighter gray tone in the
micrographs.
It is noteworthy that both microstructures showed dark zones
rich in Si, which were more abundant at 60 °C. This suggests that
a high temperature limited the dissolution reactions, resulting in
the condensation of silica gel from the unreacted activating solu-
tion. In the microstructures the presence of two separate phases,
indicating the formation of C-(A)-S-H and N-A-S-H gel was not
observed, as reported by [25] for similar binders containing 60%
GBFS-40% MK and activated with a sodium silicate solution of
Ms = 1.2. However, the XRD results previously discussed showed
the presence of crystalline C-S-H intermixed with amorphous com-
pounds, probably N-A-S-H type gels and/or C-(N-)A-S-H.
Fig. 4 presents microanalyses (SEM-EDS) from the sample 100-0
activated with 10%Na2O and cured for 180 days at 20 and 60 °C.
The data are plotted in ternary diagrams of Ca-Si-Al and Ca-Al-
Mg, normalized to 100 at.%. The results are classified in outer prod-
ucts (OP) and inner products within the GBFS particles (IP-BFS). In
921
the Ca-Si-Al diagram at 20 °C, the chemical composition of the OP
the points gathered around a composition of 50% Ca, 10% Al and
50% Si, with an average ratio Ca/Si = 0.82 similar to that commonly
reported for alkali activated slag cements [51,52]. At 60 °C, the
analyses showed slight dispersion towards zones with a higher
content of Ca and therefore less Si; this confirms that curing at
60 °C resulted in a higher dissolution of the GBFS particles with
the consequent condensation of C-(A)-S-H gel (enriched in Ca) with
Ca/Si = 0.87. The reduction in the Si/Al ratio (from 4.56 at 20 °C to
4.30 at 60 °C) suggest that increasing the curing temperature from
20 to 60 °C increased the Al uptake in the OP. On the other hand,
the IP-BFS showed higher Ca/Si, Al/Ca and Mg/Al ratios than the
OP, indicating differences among the hydration products formed
in both areas. It has been reported that for sodium silicate acti-
vated slag pastes with content of MgO content >5%, as the one used
in this research, high concentrations of Mg and Al were confined in
the IP-BFS within the boundaries of the GBFS particles
[28,45,47,53]. It appears that during the slag dissolution the Mg
has a limited mobility and therefore it hinders the diffusion of Al,
as the latter is necessary to form of hydrotalcite-type phases
around the slag grains [46].
In the Ca-Al-Mg diagram, the data of the IP-BFS and OP followed
a linear correlation; nonetheless they plotted separately, indicating
hydrated products of different chemical composition. The IP-BFS
had higher Ca/Si and Mg/Al ratios than the OP, in agreement with
the previously described. The average Mg/Al ratios in the IP-BFS
were of 1.76 and 1.86 for 20 and 60 °C, respectively, lower than
those reported for the ideal formula of hydrotalcite of 2.4 [54].
As the temperature increased, a more intense dissolution of GBFS
favored the dissolution of Mg to form hydrotalcite finely inter-
mixed with the C-(A)-S-H on a nanometer length scale as noted
by the XRD results [23].
922 O. Burciaga-Díaz et al. / Construction and Building Materials 113 (2016) 917–926

Fig. 3. Scanning electron microscopy in backscattered imaging mode of pastes 100-0, 0-100 and 50-50 cured for 180 days at 20 and 60 °C.

Fig. 4. Energy dispersive microanalyses of binder 100-0, cured 180 days at 20 and 60 °C.
 O. Burciaga-Díaz et al. / Construction and Building Materials 113 (2016) 917–926
Fig. 5. Energy dispersive microanalyses of binder 0-100, cured 180 days at 20 and
60 °C.
Fig. 5 presents the EDS results plotted in a ternary diagram
Na-Si-Al for the 100%MK (0-100) binder. In general, the results
from 20 and 60 °C gathered close to each other; however the
tabulated results indicate that increasing the temperature
modified the Si/Al ratio from 1.34 to 1.60. This could have been
caused by a higher incorporation of Si or by a lower integration
of Al in the OP. The latter is more likely, since the augment of
temperature appears to have limited the dissolution of the MK
particles, which are the main source of Al. The foregoing is
evidenced by calculating the average composition (in at.%) of the
condensed aluminosilicate gels, which was of 20% Na, 34% Al and
46% Si at 20 °C and 20% Na, 30% Al, and 50% Si at 60 °C.
In the Ca-Si-Al diagram from Fig. 6, it is noteworthy that for the
binder 50-50, the increase of the curing temperature changed the
composition of the OP towards higher content of Ca and lower
Fig. 6. Energy dispersive microanalyses of binder 50-50, cured 180 days at 20 and 60 °C.
923
content of Si. This suggests that, as noted for binders 100-0, a high
curing temperature dissolved faster the GBFS particles than those
of the MK. This was also evidenced by the higher and lower con-
centration of Ca and Al respectively, incorporated in the reaction
products which presented chemical compositions (at.%) of 13%
Ca, 17% Na, 27% Al and 43% Si at 60 °C, and 5% Ca, 20% Na, 31%
Al and 44% Si at 20 °C. On the other hand, the analyses taken from
the dark zones (see Fig. 3) of samples cured at 60 °C for the binder
50-50, showed a high variability in Al content and a trend towards
areas of Si greater than 70%. These dark zones had ratios Si/
Ca = 16.88, much higher than that observed in the OP (Si/
Ca = 3.47), indicating an incomplete chemical reaction processes
that promoted the condensation of silica gel rich phases from the
activator solution.
The Na-Si-Al diagram in Fig. 6, showed a preferential incorpora-
tion of Na (probably as charge balancer of Al) [55] in the frame-
work of the OP of samples cured at 20 °C compared with those at
60 °C, due probably to the acceleration of the reactions processes
promoted by the retention of water in the pastes. However, in
the dark areas, the concentration of Na had high variability and
the average chemical composition (in at.%) of the condensed gel
was 7% Ca, 27% Na, 15% Al and 20% Si, evidencing the formation
of phases with high content of Si and Na and limited concentration
of Ca and Al.
3.4. Early reaction processes
Fig. 7 shows the heat liberation rate from pastes of alkali-
activated 100%GBFS (100-0), 100%MK (0-100) and 50%MK (50-
50). In general, the curves are consistent with previous reports
for silicate activated slag and MK binders [5,45,56–58], where dur-
ing the first few minutes of contact of the activator solutions with
the powders, an intense peak is observed, which corresponds to the
initial heat release associated with the particle wetting and the
start of dissolution of the raw materials. Afterwards a high intense
acceleration-deceleration period (second peak) of complexation of
species and condensation of reaction products was noted. For all
the binders the initial peak appeared at similar time (<0.5 h),
regardless the curing temperature and type of raw material; how-
ever, the peak was more intense at the higher temperature [5].
After the initial peak, a short period of induction of limited heat
release appeared and its length was reduced as the temperature
increased from 20 to 60 °C [23]. During the induction period occurs
924 O. Burciaga-Díaz et al. / Construction and Building Materials 113 (2016) 917–926
Fig. 7. Heat release rate and cumulative heat of hydration at 20 °C and 60 °C from binders (a) 100-0, (b) 0-100 and (c) 50-50 with MS = 1 and 10%Na2O.
the gelation of species giving time to manipulate the fresh pastes
before their solidification, which is consistent with the behavior
of conventional Portland cements [59–61].
The end of the induction period determined the onset of a
second peak of acceleration and then deceleration of the reactions,
which seems to be highly dependent of the curing temperature and
the composition of the binder [5,57,58,60].
For the 100% GBFS binder (100-0) in Fig. 7a, the second peak
showed a maximum at 52 min for 20 °C, which shifted to
37 min and became more noticeable at 60 °C. These indicated
that an increased temperature led to faster reactions and a more
rapid dissolution of the slag particles, and consequently to faster
precipitation reaction products like C-N-(A)-S-H type gel, which
is noted because the curve of acceleration-deceleration is extended
to longer times (from 50 min to 9 h) compared with the sample
cured at 20 °C [23,28,59]. These results are coherent with those
discussed in the SEM section, which showed a more effective dis-
solution of slag particles and a greater degree of precipitation of
reaction products at 60 °C.
Fig. 7b depicts the rate of heat release response for geopoly-
meric binders containing 100%MK cured at 20 and 60 °C. At
20 °C, the curves revealed a long induction period of 4.5 h fol-
lowed by a broad and relatively weak exothermic period of
acceleration-deceleration which extended from 5 to 35 h, evidenc-
ing the gradual advance of the reaction processes. During this per-
iod, OH anions begin the attack on Si-O and Al-O bonds resulting
in an intense dissolution of MK particles and formation of complex
hydroxide species of Al-Si which continue reacting to produce
more complex species [50,62,63]. According with Provis et al. [4],
the dissolved species gradually reduce the pH of the system, lead-
ing to the further condensation of a homogeneous microstructure
formed by polymerized amorphous N-A-S-H gel. The results show
that at 60 °C a more intense heat release peak was observed, reach-
ing values even higher than those of the 100% GBFS sample, the
second peak occurred right next to the first peak without any
induction period (as shown by the insert in the graph); this sug-
gests the occurrence of a rapid dissolution of the MK at early ages;
however, in contrast with the 100%GBFS, the degree of condensa-
tion of mechanically strong reaction products could be more lim-
ited by rapid evaporation of water produced by the high curing
temperature [64]. This is in agreement with the microstructure
of the binder that evidenced a high content of unreacted MK parti-
cles even after 180 days of curing at 60 °C.
The results of Fig. 7(c) for pastes with 50%GBFS-50%MK (50-50)
indicated that the heat release rate was affected by the ratio of raw
materials GBFS-MK [23]. In this case the reaction of the sample
cured at 20 °C was more intense than in the binder 0–100. It is pos-
sible that the alkalinity of the activating solutions promoted an
early strong dissolution of the raw materials (GBFS-MK), to subse-
quently enter into a relatively short induction period similar to the
observed for the 100-0 binder [65]. After 1.5 h, a weak second
event of acceleration-deceleration occurred at times analogous to
the binder 100-0 and at earlier times than in the geopolymer 0-
100. This could suggest that the main acceleration-deceleration
peak is due mostly to the reaction of the GBFS, and the second
overlapped weak peak is from the MK showing low reactivity in
this period as noted in Fig. 7(b). On the other hand, an increase
in the reaction temperature from 20 °C to 60 °C, accelerated the
reactions resulting in a very short induction period weakly noted;
the acceleration-deceleration peak was also intensified and
appeared at earlier times similar to the alkali-activated slag binder
100-0, but with lower intensity [36,57,58].
Fig. 8 shows cumulative heat of hydration results versus time
for samples cured at 20 and 60 °C. For the slag binder (100-0) the
cumulative heat of hydration increased with the temperature; this
effect was observed since the first hour of hydration and after 12 h
the difference of released heat between both curing temperatures
was of 200 kJ/Kg.
For binder 0-100 the cumulative heat of hydration increased
during the first 10 h with the curing temperature; the curve at
20 °C reached a steady state of 200 kJ/kg after 30 h and the curve
at 60 °C stabilized at about 225 kJ/kg after 10 h, indicating that
 O. Burciaga-Díaz et al. / Construction and Building Materials 113 (2016) 917–926
Fig. 8. Cumulative heat of hydration at 20 °C (a), and 60 °C (b) from binders 100-0, 0-100 and (c) 50-50 with MS = 1 and 10%Na2O.
for both curing temperatures, similar amounts of heat are released,
but more rapidly at high temperatures. In contrast, the composite
binder 50-50 showed the lowest heat of hydration of the three for-
mulations; nonetheless, the increase of temperature accelerated
the reactions and the values of heat released were higher at
60 °C (65 kJ/kg) than those of the binder cured at 20 °C (35 kJ/kg).
Clearly, the total heat released by the 3 formulations is less than
that reported for the hydration of the PC at 50 °C (325 kJ/kg)
[5,60], and it is of special interest the low heat released by the com-
posite 50-50, considering the compressive strength and reduced
carbonation shown by such formulation.
4. Conclusions
The temperature strongly influenced the gain of compressive
strength of all the alkali-activated binders studied. The analysis
of variance shows that curing at high temperature was favorable
for a rapid strength gain, however, at later ages, the highest com-
pressive strengths were observed after curing at 20 °C. Considering
the individual formulations, curing at 60 °C was beneficial for slag
binders forming dense microstructures, while the opposite
occurred in metakaolin geopolymers and in the composite binders
with 50% metakaolin. Higher temperature favored the initial reac-
tions but caused water evaporation, which affected the reaction
processes. Although after 90 days the trend of samples cured at
60 and 75 °C was to reduce their strength, all the samples assessed
showed mechanical strength higher than 43 MPa after 520 days of
curing, which can lead to produce mortars and concretes with suit-
able properties for many applications.
The 100% BFS binders cured at 60 °C showed outer products
(OP) with higher Al content than those formed in samples at
20 °C, indicating the formation of highly cross-linked C-(N-)A-S-H
gel. The geopolymeric pastes of 100% MK exhibited the formation
of N-A-S-H gel, with an increase in the Si/Al ratio with the curing
temperature. Curing at 20 °C was advantageous for the compres-
925
sive strength, since at 60 °C the dissolution of MK was limited
resulting in coarse microstructures with lower strength. Composite
binders with 50% metakaolin were also affected by the tempera-
ture, at 60 °C the concentration of Na had a high variability and
the average chemical composition (in at.%) of the condensed gel
was 7% Ca, 27% Na, 15% Al and 52% Si, evidencing the formation
of phases with high content of Si and Na and lower concentration
of Ca and Al, being more favorable the curing at 20 °C for the
advance of the reactions and development of compressive
strength.
The results are useful to understand and compare the behavior
of different alkali-activated binders exposed to different curing
temperatures, and will help as a basis to select the most adequate
binder as a function of the environment and work conditions.
Acknowledgements
This research was funded by Conacyt Mexico project 53563.
Burciaga-Díaz also acknowledges the scholarship from Conacyt
(203549).
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