Construction and Building Materials 229 (2019) 117100

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Construction and Building Materials

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Durability study of AAMs: Sulfate attack resistance

Josep Aliques-Granero a, Monique Tohoue Tognonvi a,b,⇑, Arezki Tagnit-Hamou a
a
Department of Civil Engineering, University of Sherbrooke, 2500, boul. de l’Université, Sherbrooke (Québec) J1K 2R1, Canada
b
Department of Biology Sciences, University of Peleforo Gon Coulibaly, BP 1328 Korhogo, Cote d’Ivoire

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 High curing temperature of OPC

mortar foster expansion due to
sulfate attack.
 AAM systems better withstand
sulfate attack than the ones of OPC.
 Curing temperature required before
sulfate attack depends on the
material source.
 Dimension and mass changes not
suitable to assess degree of sulfate
attack for AAM.
 Microstructural characterization used
to identify attack product.

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

Article history: This paper is a part of works intended to determine more appropriate durability test methods for alkali
Received 4 May 2019 activated materials (AAMs). Indeed, the current methods used to characterize durability of AAMs are
Received in revised form 23 September those initially developed for ordinary Portland cement (OPC) and blended OPC. As the chemistry that gov-
2019
erns both AAMs and OPC systems is completely different, using OPC durability methods for AAMs could
Accepted 26 September 2019
induce inaccurate results. This work aims to study sulfate resistance of alkali activated slag (AAS), alkali
activated fly ash (AAFA) and OPC (used as reference) to propose appropriate sulfate resistance test for
AAMs by using ASTM C1012 as a basis. Both temperature of curing and sodium sulfate concentration
Keywords:
Alkali activated materials
were studied. Expansion of samples was evaluated over time. Results showed that all the OPC bars
Sulfate resistance exceeded the limit compliance with less expansion for those precured at 35 °C. The expansion was attrib-
Ordinary Portland cement uted in all cases to gypsum and ettringite formation. AAS samples underwent expansion that remains
Water absorption below the limit compliance. At high curing temperature, an initial high expansion attributed to water
Cross-sectional dimension absorption by the formed porosity was observed. For AAFA systems, no expansion was detected whatever
the curing regime and the sulfate concentration, showing a great resistance of such systems to sodium
sulfate attack.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction

⇑ Corresponding author at: Department of Biology Sciences, University of Peleforo Although AAMs appear to be the best alternative binder for OPC
Gon Coulibaly, BP 1328 Korhogo, Cote d’Ivoire. in construction field, there is still misinterpretation of their
E-mail address: t.tognonvi@usherbrooke.ca (M.T. Tognonvi).

https://doi.org/10.1016/j.conbuildmat.2019.117100
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
2 J. Aliques-Granero et al. / Construction and Building Materials 229 (2019) 117100
behavior in real service. The lack of long-term data is one of the
facts that hinders the use of AAMs by the construction industry.
As all the constructions are designed for a service life of decades,
it would be valuable to have available long-term data of the perfor-
mance of the materials. Most of the existing investigations have
been done for OPC because it was traditionally the construction
material par excellence. Thus, construction industry has a histori-
cal base in order to design an OPC-based concrete for future struc-
tures. On the contrary, AAMs data is relatively low compared to
those of OPC. Consequently, there is a mistrust on how these mate-
rials will behave some decades later. To solve this problem, efforts
in the development of new standards that could predict in a more
realistic manner the long-term properties of the material, and con-
sequently accelerate the industrial scale implementation of new
materials need to be developed. There is currently RILEM technical
committee, namely the TC 247-DTA ‘‘Durability testing of alkali
activated materials”, dealing with regulation of such materials
[1–3].
Due to the difference between OPC and AAMs chemistry, the
use of durability standards of OPC-based concrete to characterize
AAMs could induce incorrect results. In addition, owing to the large
variety of raw materials susceptible to be activated, the properties
of resulting AAMs vary. This makes difficult the standardization of
the durability methods for such materials.
Moreover, previous study on sulfuric acid resistance (5 wt%) of
AAMs revealed different behavior as a function of the AAM type
[4]. It has been demonstrated that gypsum was the main corrosion
product in both AAS and OPC samples with different deterioration
processes. Indeed, AAS specimens exhibited expansion with mass
and dimension gains resulting in internal cracks and ultimately
splitting of specimens into pyramid-like pieces. While OPC sam-
ples showed both mass and dimension loss resulting in their com-
plete disintegration. The difference observed could be due to the
nature of the hydration product, C-S-H in OPC system and C-(A)-
S-H for AAS system. AAFA, in the same conditions, showed no mass
and no dimensional change. However, their compressive strength
values were affected, as they decreased after acid exposure due
to progressive dealumination and dealkalization of N–A–S–H gel
during acid penetration [4].
Another important durability aspect in concretes of AAMs that
needs to be studied is the external sulfate attack. Several service
applications can subject concrete to external sulfate attack that
may lead to its deterioration. Thus, it has been a classic point
to study in OPC-based binders. The major part of the test meth-
ods used to evaluate chemical resistance to sulfate ions are con-
ducted under accelerated conditions to reduce the testing time.
Therefore, sulfate ions penetration in the samples is accelerated
by immersing the samples in a high concentrated sulfate solu-
tion. The sulfate concentration in the solution is usually ten
times higher than that accepted in practice [5]. ASTM C 452
and ASTM C1012 standards are often used for this test. ASTM
C452 standard is very prescriptive and is only applicable to
OPC. However, ASTM C1012 standard can also be applied to
blends of OPC with pozzolans or slags, and blended hydraulic
cements. None of them considers the possibility of using other
materials than those above-mentioned. Several other methods
can be found in literature [5]. Some works have been done to
characterize AAMs depending on the aluminosilicate precursor
used [6–9]. From the different findings, we can notice a great
variability of procedures in terms of curing conditions, time
and conditions of exposure, type of samples used (paste, mortar
or concrete) and indicator used (expansion, compressive and
flexural strength, mass change or analytical characterization).
Therefore, there is an evident necessity to establish standardized
procedures to better compare the results of different works.
However, the new procedures should have some flexibility in
the mix design and curing conditions. Actually, AAMs perfor-
mances highly depend on the formulation and sometimes
requires a short special curing at elevated temperatures. More-
over, there are few works focusing on concretes, as no standard
test method for evaluating the sulfate resistance of concrete is
available. Gu et al. [10] studied the influence of sulfuric acid
attack test methodologies including non-accelerated test, brush-
ing, wetting and drying cycling and increased acid concentration
on both conventional and AAFA concretes. Degradation of speci-
mens were evaluated considering changes in physical, mechani-
cal and microstructural properties. According to these authors,
the rate of change of the simple measures was significantly
mix dependent and unsuitable for the comparison of the degra-
dation performance of the different materials. They also stated
that owing to the continued hydration of the materials, compres-
sive strength could not be an appropriate indicator of degrada-
tion. As solution, they proposed a heat curing of the material
before testing. Moreover, the same authors demonstrated in
another study [11] that despite the relatively high strength
showed by alkali-activated concrete after sulfuric acid attack,
the coarse aggregates appeared to be more subject degradation
than those in OPC concrete. The concentration of the acid solu-
tion was found to significantly affect specimens as increasing
the concentration accelerated the degradation process.
This work aims to study the effect of the test conditions and the
indicator of the degree of attack to analyze AAMs sulfate resis-
tance. The parameters studied were sulfate concentration and cur-
ing regime before exposing the mortars to sulfate solution. Mass
and cross-sectional dimension changes and microstructural evalu-
ation such as SEM-EDX and XRD were used as indicators of the
degree of attack. Finally, the applicability of these typical indica-
tors of the degree of attack for AAMs according to the deterioration
mechanism was highlighted.
2. Materials and methods
2.1. Materials
Class F fly ash (FFA) and blast furnace slag (BFA) provided by
Holcim (Montreal, QC, Canada) and Grancem Holcim (Everett,
MA, USA) respectively were used as aluminosilicate sources.
General-use Portland cement (OPC) from Holcim was used for
comparative purposes in order to establish a direct relationship
between test methods and results. Physical properties and chemi-
cal composition of studied materials are shown in Table 1 and their
XRD patterns are displayed in Fig. 1. The cement is composed of
crystal phases of alite (A), ferrite (F) and aluminate (C). The Bogue
composition of this cement has been found to be: 65.9% C3S, 6.3%
C2S, 7.4% C3A and 7.1% C4AF. Its density and fineness are 3.15 kg/
m3 and 3820 cm2/g respectively. The slag is mostly composed of
CaO (42%) and SiO2 (35.1%), with an important content in Al2O3
(10.8%) and is amorphous with the presence of mullite as impurity
(Fig. 1b). BFS presents the highest fineness of 6422 cm2/g with a
density of 2.97 kg/m3 almost similar to the one of OPC.
2.1.1. LOI: lost on ignition
The chemical composition of the fly ash with sum of
SiO2 + Al2O3 + Fe2O3 of 85.9% higher than 70% according to ASTM
C618, is effectively class F fly ash. Its mineralogical composition
provided in Fig. 1c, shows the presence of a broad halo between
15 and 35° (2h) characteristic of an amorphous phase as well as
the typical crystalline products of class F fly ashes, such as mullite
(M), magnetite (N) and quartz (Q). Its density and fineness are
2.59 kg/m3 and 3723 cm2/g respectively. The mean diameter of
particles of all studied materials is in the same range, as it is of
11.21, 10.3 and 12.63 lm for OPC, BFS and FFA respectively.
 J. Aliques-Granero et al. / Construction and Building Materials 229 (2019) 117100 3

Table 1
Physical properties and chemical composition of the raw materials.

Physical properties
Density (kg/m3) Blaine surface (cm2/g) Particle size, D50 (lm)
OPC 3.15 ± 0.00 3820 ± 15 11.21
BFS 2.97 ± 0.01 6422 ± 56 10.03
FFA 2.59 ± 0.00 3723 ± 39 12.63
Chemical composition (wt%)
1
SiO2 Al2O3 Fe2O3 CaO Na2O K2O MgO SO3 LOI
OPC 19.5 4.6 2.3 62.5 0.2 0.8 2.0 3.0 5.2
BFS 35.1 10.8 0.4 42.0 0.2 0.3 7.9 1.1 1.7
FFA 45.9 23.2 16.9 4.5 1.3 1.9 1.0 0.1 4.2

Fig. 1. Mineralogical composition of: (A) General use Portland cement. A: C3S, C: C3A, F: C4AF, (B) blast furnace slag and (C) fly ash. M: mullite, N: Magnetite, Q: quartz.

Both FFA and BFS were activated using an industrial sodium sil-
icate solution (SS) and a sodium hydroxide pellets (SH) supplied by
Brenntag Canada. SS chemical composition was: 29.3 wt% of SiO2,
9.1 wt% of Na2O and 61.6 wt% of H2O with the silica modulus in
molar of 3.3. As previously described [4], a 50 wt% SH solution
was prepared and used to modify the silica modulus of the SS. In
the case of the BFS, as setting time was detected only 5 min after
casting the mortar, a 2 wt% hydrated-lime slurry (HL) was added
to the activator prior to addition to the mix. This action induces
an increase in the setting time from 5 min to 62 min of mortars,
measured according to the ASTM C807 standard.
The silica sand used to produce mortars meets the specifica-
tions of the ASTM C778 standard. This sand was supplied by
‘‘GENEQ Inc” (Ottawa, Illinois (EE.UU)). The particle size of this
sand ranges from 600 mm (sieve No. 30) to 150 mm (sieve No. 100).
2.2. Mortar preparation
25  25  285 mm mortar bars and 50  50 cm mortar cubes
were prepared using the procedure previously described [4]. The
mix design of the mortars is provided in Table 2. As, AAS mortar pre-
sented a fast setting (below 5 min), 2 wt% hydrated lime (HL) was
required to delay the setting to 62 min according to ASTM C807. A
modified ASTM C305 was used to produce AAFA mortars. The detail
of the procedure was described in previous work [4]. OPC mortars
were prepared in accordance with ASTM C305 without any
4 J. Aliques-Granero et al. / Construction and Building Materials 229 (2019) 117100
Table 2
Mix proportions of OPC, AAS and AAFA mortars (g).
Mortar (g) OPC AAS
Binder 400 400
w/s 0.49 0.45
SS – 93.8
SH – 29.6
HL – 8
Sand 1100 1100
modification. After mixing, the mortars were cast in molds. Then,
samples were covered with a plastic film before subjecting to three
different curing regimes: (1) 23 °C and 100% relative humidity; (2)
35 °C during the first 24 h followed by normal curing at 23 °C; (3)
24 h at 80 °C and storage at 23 °C. To prevent water evaporation
for the curing temperature at 35 and 80 °C the first 24 h, mortars
covered with a plastic film were sealed in plastic bags containing
water [4]. After 24 h at the different studied temperatures, the spec-
imens were removed from the molds and stored under normal con-
ditions (23 °C and 100% RH) until the different tests.
2.3. Testing procedure
Both the stability in water and the sulfate resistance of
25  25  285 mm mortar bars were studied. The goal of the water
stability test was to assess the behavior of mortars in tap water.
The water immersion test was performed following the procedure
described in the ASTM C1038 standard. The expansion and mass of
bars were measured as a function of time up to 1 week. Tests were
performed on mortar bars cured at 35 °C (according to conditions
applied for sulfate resistance test (ASTM C1012)) and 80 °C (in line
with AAFA curing conditions) for 24 h.
Sulfate resistance tests were carried out by using the ASTM
C1012 standard as basis. The standard recommends to use sodium
sulfate as a source of sulfates, at a concentration of 5 wt%. And test
is performed on samples cured at 35 °C. However, it allows to use
other sources of sulfates and other concentrations depending on
the real service conditions that has to be reproduced. As the aim
of this work is to evaluate the procedure rather than a real service
conditions, sodium sulfate was used as the sulfate source with dif-
ferent concentrations of 2, 5 and 8 wt%. Also, the influence of cur-
ing regime was evaluated. Three different curing temperatures
during the first 24 h have been studied: 23 °C (normal curing),
35 °C (according to ASTM C1012), and 80 °C (special curing tem-
perature for AAFA) followed by normal curing (23 °C and 100% of
RH) until the required strength. Indeed, according to ASTM
C1012 standard, the compressive strength required for samples
before submitting them to sulfate attack test must be equal to or
higher than 20 MPa. Therefore, compressive strength test was per-
formed on 50  50 cm mortar cubes according the ASTM C109
standard. And samples that did not achieve 20 MPa the first day,
were stored in a controlled humidity and temperature chamber
(23 °C and 100% of RH) until the required strength was reached.
Specimens were then placed in the different sodium sulfate solu-
tion (2, 5 and 8 wt%). Once the test has started, the expansion of
specimens was measured as a function of time up to 12 months
for cross-sectional tests. After each measurement, the sulfate solu-
tion was renewed by a fresh sulfate solution. For mass measure-
ment, only 12 month attacked samples were considered.
Scanning electron microscopy, combined with energy
dispersive X-ray spectroscopy (SEM-EDX) and X-ray diffraction
(XRD) were used to identify the resulting attack products after
one year of exposure. XRD characterization were realized with an
X’pert Pro MPD diffractometer in CuKa configuration. Data were
obtained by scanning at 0.1° (2 h) with a divergence slit of 1/4°.
A Hitachi S-3400 N scanning electron microscope in backscattering
AAFA mode (BSE) was used to perform SEM observations on polished
465 surfaces.
0.25
133.2 3. Results and discussion
40.7
–
1279
3.1. Compressive strength results
Fig. 2 displays the variation of the compressive strength of OPC,
AAS, and AAFA mortar cubes according to curing temperature for 1,
7 and 28 days of curing. The mechanical behavior strongly depends
on the nature of the mortar.
In the case of OPC mortars (Fig. 2a), the best compressive
strength after 28 days is obtained with a normal curing at 23 °C,
with 40 MPa. Heating the specimens from 23 to 35 °C for the first
day induces an increase in the compressive strength from
15 MPa to 21 MPa. However, the increase of the compressive
strength over time of mortars cured at 35 °C is no significant as
for the normal curing mortars. Since the compressive strength at
7 and 28 days is of 30 and 35 MPa for 35 °C while it is about 33
and 40 MPa respectively in the case of 23 °C. The same behavior
is observed when the specimens are heated at 80 °C during the first
day. Indeed, precuring the specimens at 80 °C results in a signifi-
cant early strength development of 33 MPa which seems to
decrease by 3 MPa (i.e. 30 MPa) at 7 days followed by a slight raise
of 2 MPa (i.e. 32 MPa) after 28 days of curing. The low compressive
strength of the OPC mortar cubes at later ages when they are cured
at elevated temperatures is related to the total porosity which is
higher [12–14]. According to Al-Dulaijan et al [15] and Elkhadiri
et al. [16], when OPC mortars are subjected to elevated tempera-
tures, specifically above 55 °C, the compressive strength continu-
ously decreases because of an increase of the porosity. When
elevated temperatures are stopped applying, the hydration is sup-
posed to continue but with a low reaction rate. This could explain
the slight increase of the compressive strength observed from
7 days to 28 days in this work.
The variation of the compressive strength of AAS mortars as a
function of the curing temperature is shown in Fig. 2b. One can
observe that AAS mortars behave like OPC mortars. The best com-
pressive strength of 59 MPa is obtained with a normal curing at
23 °C after 28 days. As for OPC, heating mortars during the first
day from 23 °C to 35 or 80 °C leads to enhance the compressive
strength from 25 MPa to 44 and 56 MPa respectively. Although,
the compressive strength of AAS mortar cubes precured at 35 °C
continue to increase over time, this increase is lower than the
one observed with mortars of 23 °C-curing especially for 28 days
of curing. Since for 35 °C of preheating, the 28-day compressive
strength is of 52 MPa while it is about 59 MPa at 23 °C. In the case
of 80 °C of preheating, the highest compressive strength of 56 MPa
is obtained the first days. Afterward, it decreases by 11% (50 MPa)
and 9% (51 MPa) for 7 days and 28 days respectively. Due to the
low difference between the compressive strength at 7 days and
the one obtained at 28 days, it can be considered as constant for
these two ages. Similar results were reported by Bakharev et al.
[17] and Chi et al. [18], where they obtained better final resistance
for the AAS cured at 23 °C than those cured at elevated
temperatures.
The reaction mechanism that governs the formation of mortars
in AAS system is comparable to that of OPC system. Actually,
applying thermal curing to AAS system induces the increase of
the porosity resulting in the decrease in the compressive strength
as-above observed. These results are also in accordance with those
obtained by Fernández-Jiménez et al. [19]. Indeed, these authors
showed that when AAS were heated at 45 °C during the first 24 h
before a normal curing, they first suffered a loss of compressive
 J. Aliques-Granero et al. / Construction and Building Materials 229 (2019) 117100
Fig. 2. Compressive strength for OPC (a), AAS (b) and AAFA (c) mortars at 1, 7 and 28 days for different curing temperatures during the first 24 h: 23, 35 and 80 °C, followed
with a normal temperature of 23 °C until test.
strength at 7 days. However, the compressive strength slightly
increased with a normal tendency afterwards.
For AAFA system (Fig. 2c), as expected, the compressive
strength for mortar cubes cured at normal temperature (23 °C)
did not achieve a high compressive strength (less than 5 MPa). This
is due to the particularity of these systems that need a thermal cur-
ing in order to accelerate the hardening process [20]. The highest
strength obtained in this curing condition is 14 MPa at 28 days.
Even preheating AAFA mortars at 35 °C during the first 24 h does
not significantly improve the compressive strength. Nevertheless,
this action induces a slight strength gain as the compressive which
was less than 5 MPa the first day for normal curing, becomes 7 MPa
when mortars were thermally treated at 35 °C and reaches 17 MPa
at 28 days instead of 14 MPa. Thermal treatment of AAFA mortar
cubes the first 24 h at 80 °C results in a significant improvement
of the compressive strength. Unlike the progressive strength devel-
opment in the case of 23 °C and 35 °C, mortar cubes precured at
80 °C develop their best performance the first day (34 MPa) fol-
lowed by a slight decrease the 7 days before remaining constant
up to 28 days. The mechanism processes occurred in the case FA
is used as a precursor of AAM is of different nature from those that
took place in both OPC and AAS systems. In AAFA systems, thermal
curing at elevated temperatures is sometimes required (depending
on composition and physical properties of FA) for a good dissolu-
tion of FFA particles. In fact, a bad dissolution of FFA lowers the
reaction rate as well as the hydration degree. This leads to the pres-
ence of a significant anhydrous particles and more porous
microstructure [21]. This is perfectly highlighted in obtained
5
results that show lesser strength development when mortar cubes
are cured at 23 °C and 35 °C than those preheated at 80 °C. These
results are in line with those obtained by Bakharev [22] even if
there is a difference in the curing regime. Actually, in his study,
thermal treatment was applied on fly ash-based geopolymer after
24 h of normal curing (at 23 °C). An increase in the compressive
strength was only observed after thermal curing at elevated tem-
peratures (75 and 95 °C) followed by either a constant evolution
or a slight decrease of the strength. Such a behavior was also
observed by other researchers in the case of metakaolin-based
geopolymers [21,23]. In fact, both metakaolin and fly ash have
been proved to undergo the same reaction process during their
activation. According to these authors, the strength behavior of
AAFA or metakaolin-based AAM significantly depended on curing
conditions confirming results obtained in this study.
3.2. Dimensional stability in water
Fig. 3 and Table 3 show respectively, the length and the mass
change of the OPC, AAS and AAFA mortar bars stored in water dur-
ing 7 days after subjecting them to thermal curing at 35 and 80 °C
the first 24 h. As it can be observed, the dimensions of the OPC bars
heated at 35 °C (Fig. 3a) remain practically constant until 7 days,
showing a negligible shrinkage with a mass gain of 1.1% (Table 3)
probability due to water absorption. The AAS bars exhibit an
expansion up to 0.02% from 180 min to 3 days before keeping con-
stant. These mortars show a very low mass gain of 0.32%. Contrary
to the others, the AAFA bars undergo a rapid expansion of 0.05%
6 J. Aliques-Granero et al. / Construction and Building Materials 229 (2019) 117100

Fig. 3. Dimensional stability of OPC, AAS and AAFA mortar bars submerged in water during time: a) Curing procedure 35 °C (24 h) + 23 °C, b) 80 °C (24 h) + 23 °C, c)
Comparison of OPC and AAS cured at 35 °C with AAFA cured at 80 °C.

Table 3
Evolution of the mass change of specimens exposed to water as a function of the preheating temperature.

Time (days) Mass change (%)

35 °C (24 h) + 23 °C 80 °C(24 h) + 23 °C
OPC AAS AAFA OPC AAS AAFA
0 0 0 0 0 0 0
0.01 (15 min) 0.40 0.15 0.23 2.00 1.01 1.29
0.125 (3 h) 0.52 0.17 0.65 3.93 1.20 2.89
2 0.52 0.25 1.24 4.05 1.28 2.86
4 0.92 0.31 1.12 4.05 1.36 2.83
6 1.06 0.32 1.05 4.17 1.39 2.67
7 1.06 0.32 1.02 4.26 1.74 2.81

from 15 min to about one hour where their size becomes progres-
sively constant with a mass gain of 1% at the end of the 7-day
experiment. Although the difference observed the first moments
of the test, the dimensions of all the studied specimens are almost
stabilized before the 7 days of testing. The result of mass change
indicates that AAS samples at this temperature (35 °C) exhibit finer
microstructure than the others (OPC and AAFA), as they show the
less mass gain in water.
At 80 °C (Fig. 3b), OPC bars show an expansion of 0.01% the first
day before remaining practically constant until 7 days. A signifi-
cant mass gain of 4.3% was observed suggesting the presence of
high porosity (Table 3). The AAS bars experiment a significant
expansion of 0.045% the first day followed by a slight increase
reaching 0.05% up to 7 days with a mass gain of 1.7%. The AAFA
bars behave like OPC bars with a constant expansion of 0.01% from
the first day up to the 7 days of testing. However, AAFA specimens
present a mass gain of 2.8% lower than the one of OPC bars. As
observed with the 35 °C heat curing, the dimensions of all the stud-
ied specimens are stabilized before the 7 days of testing suggesting
that expansion occurs the first times of water exposition.
OPC bars precured at 80 °C and AAS bars precured at 35 °C and
80 °C exhibit an expansion after 3 days of testing. This behavior can
be related to the total porosity of the microstructure, as explained
in SECTION 3.1. When the mortar bars are cured at elevated tem-
perature, the total porosity is higher and thus the water uptake
is higher, resulting in higher expansion. This is confirmed by the
 J. Aliques-Granero et al. / Construction and Building Materials 229 (2019) 117100
mass change of specimens (Table 3). Since increasing the preheat-
ing temperature induces a raise in the mass gain. This shows that
the curing temperature has a significant effect on specimen poros-
ity. Therefore, this expansion is attributed to the water absorption
by the total porosity. And the stabilization of bar dimensions
before the 7-day experiment could be due to the saturation of
pores with water.
In AAFA system, two behaviors can be observed depending on
the preheating temperature. When the bars are heated at 35 °C, a
strong expansion occurred early after only 15 min of exposition
in water with a total expansion of 0.05%. While at 80 °C of preheat-
ing, the bars underwent slight expansion of 0.01% during the whole
experiment. This result suggests that the optimum curing temper-
ature of AAFA system is 80 °C. This explains the special thermal
curing of the AAFA that requires energy in order to accelerate the
hydration rate and thus improving microstructure properties of
the studied material. As previously explained (Section 3.1), at
35 °C anhydrous FA content is higher than the one at 80 °C. This
results in higher expansion due to water absorption. However,
AAFA mortars precured at 80 °C showed higher mass gain of 2.8%
while those preheated at 35 °C exhibit only 1% mass gain. This
could indicate that, although at 80 °C, the total porosity was lower,
the geopolymer product obtained would be more susceptible to
adsorb water on its surface and then formed more hydrated
product.
When comparing each system with its best curing temperature
(Fig. 3c) (35 °C for OPC and AAS and 80 °C for AAFA), one can note
that all specimens have similar behavior despite minor differences.
Indeed, in the OPC system, there is no expansion and for both AAS
Fig. 4. Sulfate resistance for OPC bars (ASTM C1012) at 2, 5 and 8% of sulfate concentrations with curing temperature for first 24 h of: a) 23 °C, b) 35 °C, c) 80 °C, followed by a
normal temperature conditioning at 23 °C.
7
and AAFA systems, there is only 0.01% of expansion which can be
neglected. Thus, it can be concluded that each system needs its
own specific curing conditions in order to have comparable
behaviors.
3.3. Sulfate resistance
3.3.1. Expansion results
Sulfate expansion results for the OPC, AAS and AAFA mortar
bars are shown in Figs. 4, 5 and 6 respectively. The influence of
both the sodium sulfate concentration (2, 5 and 8 wt%) and the cur-
ing regime on the results was reported up to 1 year. It is important
to note that after the special curing temperature during the first
24 h at 35 °C and 80 °C, the test was conducted at 23 °C until the
end.
Fig. 4a presents the expansion curves of all the OPC bars pre-
pared and stored at 23 °C. As the 1-day compressive strength of
14.5 MPa was lower than the 20 MPa required by the ASTM
C1012 standard, the bars were put in the sulfate solutions after
2 days with 22.2 MPa of strength. Whatever the sulfate concentra-
tion, all the bars exceeded the limit compliance specified in the ACI
201.2R (Guide to durable concrete) for Class 2 exposure, of 0.05% at
6 months and 0.10% at one year. The expansion was strongly
related to the sulfate solution since it was higher and faster with
increasing sulfate concentration. The values of the expansion are
reported in the Table 4 according to the sulfate concentration
and the time of exposure.
Fig. 4b shows the OPC bars expansion when the curing temper-
ature was 35 °C during the first 24 h in accordance with the ASTM
8 J. Aliques-Granero et al. / Construction and Building Materials 229 (2019) 117100
Fig. 5. Sulfate resistance for AAS bars (ASTM C1012) at 2, 5 and 8% of sulfate concentrations with curing temperature for the first 24 h of: a) 23 °C, b) 35 °C, c) 80 °C.
C1012 standard. As previously observed for normal curing samples,
all the bars exceeded the limit compliance at 6 months and 1 year,
except the bars exposed in the lowest sulfate concentration
(2 wt%), that passed the test at 6 months, but failed it at 1 year.
However, even if the test failed too, results were better compared
to the bars exposed all the time at 23 °C (Fig. 4a). In addition, there
was a correlation between the sulfate concentration and the
expansion. Actually, expansion increased with increasing the
sulfate concentration.
Fig. 4c shows expansion results for the OPC bars precured at
80 °C during the first 24 h. In this case, with an unusual curing con-
ditions for this system, the bars experimented a fast and high
expansion after only 50 days. This expansion was almost the same
for all the sulfate concentrations up to 150 days. From these days,
expansion became sulfate concentration dependent as it increased
with the concentration. All the bars exceeded the limit compliance
of 0.01% (at 1 year) after 50 days.
All these results were in accordance with the mass gain of OPC
specimens after 12 months of exposure reported in Table 5. Indeed,
the mass gain directly related to the expansion increases with
increasing both sulfate concentration and curing temperature. If
samples cured at normal temperature (23 °C) or at 35 °C showed
moderate mass gain (2–3%), those precured at the highest temper-
ature (80 °C) exhibits the greatest mass gain that varied from 6 to
8% according to the solution concentration. Since the mass gain in
the case of sulfate attack was higher than the one observed with
water exposition, the excess in mass would result from the forma-
tion of more expansive products due to sulfate attack.
Fig. 5a shows the sulfate expansion results for the AAS mortar
bars cured at 23 °C. As it can be observed, there were no expansion
whatever the sulfate concentration. Therefore, the sulfate concen-
tration had no influence on the results.
Fig. 5b shows the sulfate expansion results for the AAS mortar
bars precured at 35 °C during the first 24 h. A rapid expansion of
0.05% was observed after the first week of immersion and became
constant afterwards with the same tendency as the bars exposed
all the time at 23 °C (Fig. 5a). This behavior correlates well with
the results of dimensional stability test. The bars exposed only to
tap water gained a similar expansion at 7 days like those exposed
to sulfates. Therefore, the expansion observed in this case is attrib-
uted to the water absorption of the bars but not to sulfate attack.
This was confirmed by the constancy of the mass gain of about
0.3% in both water and sulfate solution (Tables 3 and 5). Fig. 5c
shows the sulfate expansion results for the AAS mortar bars heated
at 80 °C during the first 24 h. As observed with the bars cured at
35 °C, a rapid expansion occurred after the first week of immersion
followed thereafter by a constant value. In this case, a slight gain in
the mass (0.5–0.6%) that apparently did not affect the integrity of
samples was observed (Table 5). This expansion correlates well
also with the results of dimensional stability test, and it is attribu-
ted as well to the water absorption. According to these results, AAS
appears to well withstand the sulfate attack.
Fig. 6 gathers the sulfate expansion results for the AAFA mortar
bars cured at 23 °C (Fig. 6a), 35 °C (Fig. 6b) and 80 °C (Fig. 6c)
respectively. For the bars cured at 23 and 35 °C, the test was
started after 28 days of curing, even if the compressive strength
did not achieve the 20 MPa required by ASTM C1012 standard.
The compressive strength was 14 MPa and 18 MPa at 28 days
for curing temperature of 23 and 35 °C respectively (Fig. 2c).
And, due to the slow hardening reactions of AAFA at low curing
 J. Aliques-Granero et al. / Construction and Building Materials 229 (2019) 117100 9

Fig. 6. Sulfate resistance for AAFA bars (ASTM C1012) at 2, 5 and 8% of sulfate concentrations according to curing temperature for first 24 h of: a) 23 °C. b) 35 °C. c) 80 °C.

Table 4
Expansion of OPC mortar bars at 6 and 12 months

6 months 12 months
Na2SO4 wt% 2 5 8 2 5 8
23 °C 0.07 0.09 0.16 0.20 0.32 0.42
35 °C (24 h) + 23 °C 0.04 0.06 0.07 0.12 0.16 0.20
80 °C (24 h) + 23 °C 1.14 1.13 1.22 1.68 2.04 2.36
Limit compliance* <0.05% <0.10%
*
According ACI 201.2R for Class 2.

Table 5
Mass change of specimens as a function of the preheating temperature after 12 months of exposure to sulfate solution.

Mass change (wt%)

OPC AAS AAFA
Na2SO4 wt% 2 5 8 2 5 8 2 5 8
23 °C 1.58 2.27 2.90 0.29 0.31 0.32 1.68 2.06 2.42
35 °C (24 h) + 23 °C 2.46 2.71 3.05 0.28 0.31 0.39 1.77 2.06 2.11
80 °C (24 h) + 23 °C 5.81 7.10 8.08 0.54 0.50 0.56 2.84 2.78 2.75

temperatures, it would take too long time to achieve the 20 MPa
required before staring the test. Accordingly, it was decided to start
the test after 28 days. Since the goal of this test was rather to study
the influence of the test parameters, it was thought interesting to
evaluate the influence of the compressive strength. As it can be
observed, there was not any expansion for all the studied condi-
tions. It was found that the sulfate concentration had no influence
on the results. Instead, a little shrinkage during time was observed
for all the bars in all the conditions. In addition, the mass gain of
2.8% (for T = 80 °C) is similar to the one observed in the water sta-
bility test indicating that this gain is only due to water absorption.
Therefore, AAFA shows a good resistance to sulfate attack.
According to results, unlike OPC mortars which do not well
resist to sulfate attack, AAS and AAFA mortars better withstand a
sulfate attack whatever the solution concentration. This difference
is probably due to the chemical nature of the reaction products
10 J. Aliques-Granero et al. / Construction and Building Materials 229 (2019) 117100
formed during each mortar. Mineralogical and microstructural
characterizations were therefore required to identify the different
reaction products.
4. Mineralogical characterization by means of X-ray diffraction
XRD experiments were performed on attacked samples after
1 year of sulfate exposition (2, 5, and 8 wt%). For each system, a
piece of sample collected from a bar according to the sulfate con-
centration and the curing regime, was analyzed. XRD patterns for
the OPC specimens are provided in Fig. 7 according to the three
studied curing temperatures, 23 °C (Fig. 7a), 35 °C (Fig. 7b) and
80 °C (Fig. 7c). In all cases, similar peaks, characteristics of quartz
(Q), C-S-H gel (X), portlandite (P), ettringite (E) and gypsum (G),
were observed with different intensity depending on the curing
temperature.
For curing temperature of 23 °C (Fig. 7a), the intensity of the
main peak of portlandite (2h = 18.0°) slightly decreased when the
sulfate concentration in the solution was higher, meanwhile the
intensity of other portlandite peaks remained almost constant. At
the same time, the intensity of the main peak of the ettringite
(2h = 9.1°) slightly increased with the sulfate concentration. The
intensity of the main peak of gypsum observed at 2h = 11.6° also
increased when the sulfate concentration raised, while remaining
very similar for both 5 and 8 wt%. These results are in line with
the fact that when more sulfates are available in the solution, most
of them react with the portlandite present in the OPC mortar,
Fig. 7. XRD patterns for OPC mortar bars exposed at different sodium sulfate solutions (2, 5, and 8 wt%) after 1 year of exposition. Curing temperature during the first 24 h of:
a) 23 °C; b) 35 °C; c) 80 °C. Peaks: E, ettringite; G, gypsum; P, portlandite; Q, quartz; X, C-S-H gel.
evidenced by a decrease in the intensity of the portlandite peaks.
Therefore, the portlandite reacts with the sulfates to form in a first
step gypsum and thereafter converts to ettringite [24]. Both gyp-
sum and ettringite were found to increase with the sulfate concen-
tration resulting in the decrease in the portlandite. The ettringite
and gypsum were thus responsible for the expansion observed in
Fig. 4a. The region attributed to the C-S-H gel (2h = 29.0°) was
almost the same in the 3 studied cases, indicating the stability of
the gel in these conditions. The huge peaks of quartz observed in
all the conditions were due to the sand used for the confection of
the mortar specimens. These peaks of quartz were not illustrated
completely because of rescaling the figure to better differentiate
the important peaks. This rescaling is applied in all the XRD
patterns.
For curing regime of 35 °C (during the first 24 h) – 23 °C
(Fig. 7b), there was not a clear evolution of the peak intensity with
the sulfate concentration. Regarding the peaks of gypsum and
ettringite, they seemed to keep constant with the sulfate concen-
tration. For the portlandite, the main peak intensity increased with
5% of sulfates, but decreased at 8% to the minimum value. With a
normal behavior, when more sulfates were present in the solution,
they would be able to react with the portlandite. For this reason,
the peak intensity of portlandite expected at 5% should be lower
than that of 2%. The ettringite and gypsum were therefore respon-
sible for the expansion observed in Fig. 4b. In the case of the C-S-H
gel (X), the intensity of the peak was constant in all cases. When
comparing these results with those of the bars cured at 23 °C all
 J. Aliques-Granero et al. / Construction and Building Materials 229 (2019) 117100
Fig. 8. XRD patterns for AAS mortar bars exposed at different sulfates dissolutions (2, 5, and 8 wt%) after 1 year of exposition. a) curing temperature during the first 24 h:
23 °C; b) 35 °C; c) 80 °C. Peaks: Q, quartz; X, C-(A)-S-H gel; HT, hydrotalcite; C, calcite.
the time, the peaks of the portlandite, gypsum and ettringite, in
this case of 35 °C, appeared to have lower intensity. Lower quantity
of the gypsum and ettringite will result in lower expansion. This is
corroborated by the expansion results shown in Fig. 4a and b,
where the bars cured at 35 °C the first 24 h exhibited lower expan-
sion than those cured the whole time at 23 °C in each sulfate
concentration.
At 80 °C (during the first 24 h) – 23 °C regime curing (Fig. 7c), as
for 35 °C (Fig. 7b), there was not a clear evolution of the peak inten-
sity with the sulfate concentration. The intensities of the main
peak of portlandite, gypsum and ettringite were almost similar
for 2% and 8% of sulfate concentration, while for 5% the intensity
was lower. Concerning the expansion (Fig. 4c), there was a clear
difference according to the sulfate concentration, with more
expansion for the highest sulfate concentration. Compared to the
bars cured at 23 °C and 35 °C, the main peak of the portlandite
showed lower intensity in this case, while the main peak of gyp-
sum and ettringite were higher. This is in line with the expansion
results (Fig. 4a, b and c), where the bars cured at 80 °C during the
first 24 h suffered a much higher expansion and mass gain than
those cured at 23 °C and 35 °C, attributed to a significant formation
of gypsum and delayed ettringite.
Fig. 8 provides the XRD spectra for the AAS specimens when
curing temperature was 23 °C (Fig. 8a), 35 °C (Fig. 8b) and 80 °C
(Fig. 8c).
The peaks found were quartz (Q), C-(A)-S-H gel (X) and hydro-
talcite (HT). These compounds are in accordance with the findings
of other studies for AAS at normal curing conditions [25,26]. No
other peaks of crystalline products due to sulfate attack were
found, in accordance with the expansion results shown in
11
Fig. 5a, b and c. The intensities of the main peak of C-(A)-S-H gel
(2h = 29.3°) and hydrotalcite (2h = 11.3°) were practically the same
in all the cases, indicating the stability of AAS to sodium sulfate
attack. The peaks of quartz varied depending on the sampling pro-
cess, and it was due to the sand used in the confection of the mor-
tars. Similar results were obtained by other authors in similar
attack conditions [27].
Fig. 9 provides the XRD patterns in the case of the AAFA speci-
mens for curing temperature of 23 °C (Fig. 9a), 35 °C (Fig. 9b) and
80 °C (Fig. 9c). In this case, as observed with the AAS specimens,
no peaks of the presence of new crystalline products due to the sul-
fate attack was found. The peaks found were mostly the crystalline
phases of the unhydrated FA (M, mullite; N, magnetite) displayed
on Fig. 1 plus the quartz due to the sand used for the confection
of the mortars.
The absence of expansion products such as ettringite and gyp-
sum highlighted by XRD experiments in the case of alkali activated
materials (AAS and AAFA) explains well the ability of such a mate-
rial to withstand sulfate attack.
5. Microstructural analysis by means of SEM-BSE coupled with
EDX
SEM-BSE experiments were performed on attacked samples
after 1 year of exposition to sulfate solutions. For each system, a
piece of one bar exposed only to 5% of sulfate concentration for
each curing regime was collected to analysis.
Results of OPC specimens are displayed in Fig. 10 for the curing
temperature of 23 °C (Fig. 10A), 35 °C (Fig. 10B) and 80 °C
(Fig. 10C). SEM images show the presence of ettringite crystals
12 J. Aliques-Granero et al. / Construction and Building Materials 229 (2019) 117100
Fig. 9. XRD patterns for AAFA mortar bars exposed at different sulfates dissolutions (2, 5, and 8 wt%) after 1 year of exposition. Curing temperature during the first 24 h: a)
23 °C; b) 35 °C; c) 80 °C. Peaks: Q, quartz; M, mullite; N, magnetite.
responsible for the expansion. For the bars cured at 23 °C and 35 °C
(Fig. 10A and B), the presence of fine crystals and deposits of ettrin-
gite in the regions near the aggregates, are observed. At curing
temperature of 80 °C (Fig. 10C), significant deposits of ettringite
can be observed. In this case, all the region is practically covered
by delayed ettringite evidenced by EDX analysis. Therefore, these
bars exhibit higher expansion than those cured at 23 °C and
35 °C. The formation of significant amount of delayed ettringite is
related to the elevated temperature used in this case, 80 °C.
It is well known that the external sulfates react with some com-
ponents of the hydrated OPC paste [24,28]. XRD analysis per-
formed after 12 months of exposure to sulfates confirmed the
presence of gypsum and ettringite. Precipitation of ettringite near
the aggregates evidenced in SEM observations, could be the conse-
quence of a higher concentration of portlandite in these regions
[29]. Portlandite may react with sulfates to form gypsum, and then
with calcium aluminate compounds to form ettringite. Gypsum
crystals were revealed by XRD analysis but difficult to detect by
SEM. Moreover, samples precured at 80 °C present similar fast
expansion regardless of the sulfate concentration until 150 days.
However, at later ages (above 150 days), the expansion increases
with the sulfate concentration, showing a direct influence of the
sulfate concentration. Accordingly, there seems to be two different
effects. In a first stage, at early ages, an expansion due to an
internal sulfate attack (ISA) could occur. This type of attack is
favored in OPC systems when they have been subjected to high
temperatures over 60–70 °C [30,31]. At these conditions, primary
ettringite normally produced during hydration and beneficial for
the concrete is not formed or, if it is already formed, it decomposes
to monosulfoaluminate. As a consequence, more of the sulfates, no
stabilized by the primary ettringite, may be either in the pore solu-
tion or incorporated in the C-S-H gel. In presence of high humidity
and microcracks (also produced by the thermal curing), the sul-
fates normally adsorbed in the C-S-H gel can be released and pro-
duce again ettringite (thus called delayed-ettringite: DEF) with a
subsequent expansion [30–32]. This stage which would be less
affected by the external sulfate concentration, is therefore respon-
sible for the fast expansion experienced by OPC bars. In a second
stage, at later ages, the influence of an external sulfate source is
manifested (external sulfate attack: ESA) and thus the reaction of
external sulfates with the calcium and aluminum compounds of
the cement paste will produce again ettringite, causing further
expansion. In this second stage, the concentration of the external
sulfates will have an important role, with more expansion when
the sulfate concentration is higher.
SEM images along wit EDX analysis of AAS specimens are pro-
vided in Fig. 11 for curing temperature of 23 °C (Fig. 11A), 35 °C
(Fig. 11B) and 80 °C (Fig. 11C). In all the studied cases, as already
observed with XRD results (Fig. 8a, b and c), no anomalous com-
pound was found. The presence of anhydrous slag particles indi-
cates a partial hydration of the material. Fine cracks observed on
some particles could be due to the shrinkage that can undergo such
systems [33–36]. Unlike the good continuity between the paste
and aggregates for specimens cured at 23 °C, a disconnection is
observed for specimens precured at 35 °C and 80 °C. This porosity
could probably be due to a desiccation during the heat treatment.
This could be responsible for the expansion related to water
absorption observed in the water immersion test (Section 3.2).
 J. Aliques-Granero et al. / Construction and Building Materials 229 (2019) 117100
Fig. 10. SEM-EDX images for OPC mortar bars exposed to 5% of sulfate concentration after 1 year of exposition. Curing temperature during the first 24 h: A) 23 °C; B) 35 °C; C)
80 °C.
EDX analysis reveals the presence of Si, Ca, Al, Mg and Na elements
which are typical compounds of hydration products such as C-A-S-
H gel and hydrotalcite (HT) (Mg6Al2CO3(OH)16
4(H2O)) often
obtained in alkali activated slag [25,26]. These products result from
the hydration of the anhydrous slag with the activator, in this case,
sodium silicate (Ms = 1.45). XRD analysis also confirmed the pres-
ence of these hydration products. As, both compounds (C-A-S-H
and HT) are intermixed, it is difficult to differentiate them by
SEM-EDX analysis. Si, Ca and Al are present in the main hydration
product, the C-A-S-H gel. Al, otherwise, is also present in the
hydrotalcite together with Mg. The extent to which the Al is pre-
sent on the hydrotalcite or in the C-A-S-H gel is influenced by
the Mg content [37,38]. Therefore, the excess of Al that is not incor-
porated to the hydrotalcite will be further incorporated in the C-S-
H gel. The presence of Na in the matrix is still controversial, but it is
believed to be adsorbed on the C-A-S-H gel rather than incorpo-
rated in the gel structure [39]. Moreover, EDX spectra reveal the
presence of S, probably present in the pore solution due to the
ingress of sulfates. According to the results obtained in this part
of the work, it is evident that AAS system is resistant to the sodium
sulfate attack. These results are in accordance with other works
found in literature [8,9,27,40].
Although no attack product was found after exposing to the
sodium sulfate, this does not mean that AAS are always sulfate
13
C
resistant. As shown in other works [9,41], sulfate attack on AAS
pastes depends also on the nature of the cations. Therefore, AAS
binders has been found to be deteriorated by sulfate attack when
they were exposed to magnesium sulfate. In this case, decalcifica-
tion of the binder, gypsum formation, loss of mechanical perfor-
mance and dimensional changes were found as a result of the
magnesium sulfate attack of AAS. The degradation of the C-A-S-H
gel was mainly attributed to the low solubility of magnesium
hydroxide compounds (formed during the interaction of the mag-
nesium sulfate with the gel) and the resulting low pH value
[24,41].
Fig. 12 provides SEM images for the AAFA specimens with cur-
ing temperature of 23 °C (Fig. 12A), 35 °C (Fig. 12B) and 80 °C
(Fig. 12C). No attack products resulting from the sodium sulfate
exposure is found in the micrographs. In all cases, the EDX spectra
obtained show the presence of elements of the sodium aluminosil-
icate gel (N-A-S-H), typical hydration product of such systems: Si,
Al and Na [20,42]. Anhydrous FA particles (plenospheres, spheres)
and white particles related to mullite/magnetite present in the
original FA are also observed. Observing these images, it can also
be deduced a relative hydration degree in terms of anhydrous FA
particles (spheres). For the curing temperature of 23 °C and 35 °C
(Fig. 12A and B), the quantity of anhydrous FA particles is higher
than in the case of curing at 80 °C. Thus, in this particular system,
14 J. Aliques-Granero et al. / Construction and Building Materials 229 (2019) 117100
Fig. 11. SEM-EDX images for AAS mortar bars exposed to 5% of sulfate concentration after 1 year of exposition. Curing temperature during the first 24 h: A) 23 °C; B) 35 °C; C)
80 °C.
it is demonstrated that curing at elevated temperatures dissolves
all the necessary elements present in the FA [42]. Table 6 shows
the atomic ratios of the paste regions for each image. The atomic
ratios are an average of a minimum of 5 points of the image
(1.00 k of scale). It can be observed that the Si/Al ratio decreases
with increasing the curing temperature during the first 24 h. This
means that more aluminum elements are dissolved and thus fixed
on the structure of the N-A-S-H gel. It is also observed that the
Na/Al ratio is constant when curing temperature is 23 °C and
35 °C, and then decreases for 80 °C. This is also an evidence of
the increase of the aluminum content in the structure at elevated
temperatures. Therefore, the atomic ratios corroborate the high
solubility of the elements at elevated curing temperatures.
AAFA samples showed no expansion regardless of the curing
regime and the sulfate concentration. Although curing temperature
showed to be an important aspect on the mechanical performance of
these systems (Fig. 2c), it seems that mechanical properties are not
the most important aspect regarding the sulfate resistance but the
chemical composition of the AAM precursor. The low Ca-content
of the class F fly ash could be the reason that AAFA is highly resistant
to sodium sulfate attack. XRD analysis performed on samples after
12 months of sulfate exposure did not show the presence of new
crystalline products other than those present initially in the FA (mul-
lite and magnetite). SEM-BSE images neither revealed the formation
C
of any crystalline product nor a degradation of the matrix. EDX anal-
ysis (for the three curing regimes) showed typical spectra of AAFA
(when sodium silicate is used as activator) [42], with Na, Al and Si
as the main elements attributed to the formation of the N-A-S-H
gel. Therefore, the results showed very good resistance of AAFA to
sodium sulfate attack, independently of the curing regime and sul-
fate concentration. These results are in accordance with those found
in literature [7,43,44]. However, Bakharev [45] found different
results depending on the nature of the activator and the type of
the sulfate. Even though no visual deterioration signs were detected
on AAFA samples after 5 months in 5% sodium or 5% magnesium sul-
fate solution, a slight mass gain and a compressive strength loss
were observed with traces of ettringite. Mg sulfate appeared to be
more aggressive than Na sulfate. However, in both cases, AAFA bet-
ter resisted to sulfate attack than OPC samples [45]. It is important to
note that the AAFA composition and the curing regime used by
Bakharev were different from those used in this study. This can
explain the difference observed in results, as, no trace of ettringite
that is the main deterioration product and no expansion were
observed in this work (Figs. 6, 9 and 12), unlike the one observed
by Bakharev. This clearly demonstrates that AAFA is more resistant
to sulfate than OPC. However, AAFA can somewhat be vulnerable to
sulfate attack depending on several parameters which need to be
appropriately defined according to required usage.
 J. Aliques-Granero et al. / Construction and Building Materials 229 (2019) 117100 15

C
Fig. 12. SEM-EDX images for AAFA mortar bars exposed to 5% of sulfate concentration after 1 year of exposition. Curing temperature during the first 24 h: A) 23 °C; B) 35 °C;
C) 80 °C.

Table 6
Atomic ratios obtained by the EDX analysis of the AAFA mortars exposed during probably be due to a higher porosity of the bars cured at 35 °C
12 months to 5 wt% sodium sulfate solution for curing temperature during the first which could buffer the effect of the stress caused by ettringite crys-
24 h of 23 °C, 35 °C and 80 °C. tals growth inhibiting expansion. Preheating OPC bars at 80 °C
Curing temperature Si SiO2 Na Na2 O induced a fast expansion from the beginning, exceeding the limit
Al Al2 O3 Al Al2 O3
compliance at 1 year (0.1%) after 50 days of exposure. This has
23 °C 5.22 10.44 0.54 0.54
been attributed to a double effect: internal sulfate attack and
35 °C 4.07 8.15 0.53 0.53
80 °C 3.56 7.12 0.38 0.38 external sulfate attack. The ISA would be the result of the curing
temperature at 80 °C.
In AAS system, the expansion of the bars was quite below the
6. Conclusion limit compliance whatever the curing temperature and the sulfate
concentration. However, a slight curing temperature dependence
The resistance of OPC, AAS and AAFA systems to sodium sulfate was noticed. Indeed, higher curing temperatures resulted in higher
attack was assessed using ASTM C1012 as basis. The effect of cur- initial expansion (after 7 days) before remaining constant during
ing temperature and sulfate concentration was studied. Cross- time. This was attributed to a water absorption rather than a sul-
sectional dimension and mass changes were used as main indica- fate attack. Since large porosity surrounding the aggregates was
tors of the degree of attack. SEM-EDX and XRD experiments were detected for samples precured at 35 and 80 °C. And no presence
performed to identify the corrosion products. Different behaviors of crystalline products other than the normal hydration products
were observed depending on the nature of the mortar. (C-A-S-H gel and hydrotalcite) was found. Therefore, AAS appear
All the OPC bars exceeded the limit compliance established in to better resist to sodium sulfate attack.
the ACI201.2R for class 2 of exposure to sulfates. The only excep- AAFA specimens did not show any expansion regardless of
tion was the bars cured at 35 °C and exposed in 2 wt% sulfate solu- attack conditions, suggesting a great resistance to sodium sulfate
tion, which passed the test at 6 months but failed at 1 year. The attack. Instead, slight shrinkage during time was found. In addition,
expansion was attributed in all cases to a gypsum and ettringite microstructural characterizations showed no presence of crys-
formation. OPC bars precured at 35 °C (as required in the standard) talline products associated to sulfate attack, but a sodium alumi-
showed lower expansion than those cured at 23 °C. This could nosilicate hydrate gel typical of these systems was observed.
16 J. Aliques-Granero et al. / Construction and Building Materials 229 (2019) 117100
This study clearly showed that curing regime (temperature and
time) should not be a prescriptive parameter but selected accord-
ing to the AAM precursor used. As curing temperature is an impor-
tant parameter in the development of AAM performance, it should
be considered to improve the resistance of such a system against
sulfate attack. The sulfate concentration, as in the ASTM C1012,
should also be selected depending on the real conditions simu-
lated. Moreover, the expansion, caused by the calcium-sulfate-
based products, seemed to be a suitable indicator for measuring
the degree of sodium sulfate attack in OPC systems. But, for AAM
systems which contain low amount of calcium, other indicators
of the degree of attack should be considered, e.g. the compressive
strength loss and the change in the corrosion depth through car-
bonation test. Microstructural characterization of samples after
sulfate exposure should be performed to confirm the stability of
the binder. And due to the great variability of AAM sources, the
20 MPa required in the ASTM C1012 standard prior to start the test
should not be a requirement.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
The authors gratefully acknowledge the financial support of the
Industrial Chair on the Valorization of Glass in Materials provided
by the Société des Alcools du Quebec (SAQ).
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