ACI MATERIALS JOURNAL
Title No. 113-M44
Preconditioning Method for Accelerated Testing of
Concrete under Sulfate Attack
by Hocine Siad, Mohamed Lachemi, Mustafa Sahmaran,
¸ and Khandaker M. Anwar Hossain
This paper aims to recommend a new supplementary precondi-
tioning procedure that can accelerate the degradation process of
concrete specimens when exposed to sulfate attack. Several spec-
imens obtained from 30 and 60 MPa (4.4 and 8.7 ksi) strength
concretes were tested. Expansion, mass change, and ultrasonic
pulse velocity measurements were conducted for specimens
subjected to two primary methods of presaturation using sulfate
solution and desiccators, then immersed in sulfate solution. A
complementary microstructural analysis was also carried out to
define the degradation mechanism. When compared to the control
method, which had the same immersion conditions without primary
presaturation, test results showed an important acceleration of the
degradation process with the use of supplementary preconditioning
in desiccators. In addition to the remarkable acceleration in the
degradation process, the microstructure study confirmed that the
degradation mechanism of concrete specimens subjected to supple-
mentary preconditioning by desiccators reflected the field observa-
tions in sulfate attack environments.
Keywords: concrete degradation; expansion; microstructure; sulfate attack;
test method.
INTRODUCTION
Sulfate attack can be classified as an aggressive natural
threat to concrete structures due to the large presence of sulfate
in soil, groundwater, seawater, and industrial effluents.1-3 It is
classified as a “very severe attack” in the ACI 318-99 building
code,4 and research shows that concrete is susceptible to
ingress by sulfate ions from the environment. The interaction
between concrete and sulfate ions usually produces gypsum
and ettringite. The rapid precipitation of ettringite in concrete
can cause volume change, cracking, disintegration, and
strength loss, which can lead to structural failure.
Degradation of concrete due to external sulfate attack
progresses slowly in the field, occurring over decades.5 The
main challenges in assessing concrete performance are simu-
lating natural environmental conditions in the laboratory,
and limiting testing time to the minimum. The absence of
standard accelerated procedures for testing the vulnerability
of concrete samples to sulfate attack has been observed in
the literature. Most traditional accelerated methods, based
on the ASTM C10126 standard, evaluate external sulfate
attack on cementitious materials using mortar or paste spec-
imens. Regardless of the criticisms of this method made
by researchers,7-10 tests involving cement paste or mortar
samples are not necessarily good indicators on concrete
behavior. According to Crumbie11 and Chabrelie,5 both
the interface between aggregates and cement paste (the
so-called ITZ), and the nature and content of the aggregate,
ACI Materials Journal/July-August 2016
TECHNICAL PAPER
play important roles in any transport process in concrete.
Additionally, varying types of concrete require that sulfate
resistance testing be performed on concrete specimens, not
the equivalent mortar or paste specimens. Although concrete
deterioration due to sulfate ions has been widely studied, the
mechanism of degradation by sulfate attack and the long-
term duration of laboratory tests remain real obstacles to
emphasizing the difference in concrete composition. The
ASTM C1012 test, performed on mortar specimens with
dimensions of 25.4 x 25.4 x 285 mm (1 x 1 x 11.22 in.),
takes 12 to 18 months of immersion in 5% sodium sulfate
solution, which means that testing on concrete samples may
require a very long period of time (in regards to minimum
dimensions required for concrete samples).
There are examples (not exhaustive) of proposed methods
that attempt to deal with the problem of testing time in sulfate
attack by accelerating the degradation process of concrete.
Based on ASTM procedures, Mehta12 proposed automati-
cally controlling the PH of the solution rather than renewing it
weekly. However, the complexity of the test setup has inhib-
ited its use as a standard method.13 Several subsequent accel-
erated test methods rely on: 1) a high sulfate concentration14
(instead of the 5% suggested in ASTM C1012); 2) dry/wet
cycles15 or partial immersion16 as a replacement for full
immersion; or 3) storage at high temperatures17 instead of
25oC (77°F), as proposed by ASTM International. Due to the
change in the degradation mechanism that does not reflect
the field observations, these test methods have all undergone
numerous criticisms and have been deemed inadequate for
assessing concrete resistance to sulfate. According to Bell-
mann et al.9 and De Belie,18 in high sulfate concentrations,
gypsum is the main product, whereas under realistic field
conditions, the primary product is ettringite or a combina-
tion of gypsum and ettringite. For wet/dry cycles or partial
immersion methods, Clifton et al.19 showed that concrete
degradation has a physical process due to the concentra-
tion of sulfate salts on outer concrete surfaces. Assaad et
al.16 observed that the partial immersion test can be better
used to determine resistance against corrosion due to sulfate
attack. For the method that employs storage at high tempera-
tures, Damidot and Glasser20 showed that, at 25°C (77°F),
ettringite and gypsum are stable, and monosulfoaluminate is
ACI Materials Journal, V. 113, No. 4, July-August 2016.
MS No. M-2015-298.R1, doi: 10.14359/51688705, received September 1, 2015, and
reviewed under Institute publication policies. Copyright © 2016, American Concrete
Institute. All rights reserved, including the making of copies unless permission is
obtained from the copyright proprietors. Pertinent discussion including author’s
closure, if any, will be published ten months from this journal’s date if the discussion
is received within four months of the paper’s print publication.
493
a metastable phase. Increased temperature drastically influ-
ences the CaO-A12O3-CaSO4-H2O system; at temperatures
above 45°C (113°F), monosulfoaluminate becomes increas-
ingly stable at the expense of ettringite. Other examples of
proposed methods of accelerating sulfate attack can be also
cited,21-23 however, the minimum recommended time may
exceed 2 years for conservation and monitoring.
A new testing procedure needs to be developed to accel-
erate testing of the resistance of concrete samples against
sulfate attack. This may be achieved by accelerating the
degradation of concrete samples. The objective of this study
is to suggest a faster and more realistic procedure to accel-
erate the rate of degradation and, therefore, test duration, to
limit testing time to a few months while depicting long-term
influence. To develop a realistic test procedure, the test setup
must be simple and the required equipment must be econom-
ical and accessible to most material laboratories. The experi-
mental study conducted in this work was based on the accel-
eration of the diffusion of sulfate ions into concrete. Two
new methods of pre-conditioning were proposed and tested
based on preliminary saturation by sulfate solution. Using
desiccators and under vacuum, sulfate ions were forced
to migrate through the concrete specimens. The reliability
of the proposed methods was evaluated by monitoring the
expansion, mass change, and ultrasonic pulse velocity of
normal and high-strength concretes (30 and 60 MPa [4.4 and
8.7 ksi] compressive strength). Mineralogical, chemical,
and microstructural studies were also carried out on several
layers of degraded samples using X-ray diffraction (XRD)
and scanning electronic microscopy (SEM) coupled with
Table 1—Chemical composition and physical
properties of cementitious materials
Chemical component, % GU
SiO2 19.2
Fe2O3 3.13
Al2O3 4.9
CaO 62.3
MgO 2.7
SO3 3.73
K 2O 0.54
Na2O 0.24
Physical properties
Specific gravity 3.15
Blaine fineness, m /kg2
411
energy-dispersive X-ray spectroscopy (EDS) and micro­
analyses on polished surfaces.
RESEARCH SIGNIFICANCE
Most laboratory methods aimed at studying the sulfate
attack mechanism are based on accelerated mortar tests.
However, using these tests to evaluate concrete perfor-
mance is impractical because deterioration will not occur in
concrete within a reasonable period of time, as in the mortar
sample. The aim of the new test method is to develop an
accelerated and reproducible procedure for monitoring the
resistance of different types of concrete to external sulfate
attack. The test results showed that an important acceleration
of the degradation process of concrete exposed to external
sulfate attack occurred with supplementary pre-conditioning
in desiccators under vacuum.
EXPERIMENTAL PROGRAM
Materials, mixture characteristics, and specimen
preparation
General-use (GU) portland cement complying with ASTM
C150 Type I cement24 and Type High Early (HE) cement
conforming with Canadian Standards in CSA A3000-0825
were used to produce normal and high-strength concrete
(30  and 60 MPa [4.4 and 8.7 ksi] compressive strength),
respectively. Siliceous natural sand with a maximum grain
size of 5 mm (0.2 in.) and silico-calcareous crushed gravel
with 15 mm (0.59 in.) maximum size were used as fine and
coarse aggregates. Specific gravity and water absorption
properties were 2.65% and 0.8%, and 2.7 and 0.5%, respec-
tively. Silica fume (SF) was used as a mineral admixture
in the production of the 60 MPa (8.7 ksi) concrete. Table 1
describes the physical and chemical characteristics of
HE Silica fume cements and silica fume, and Table 2 provides the mixture
21.2 95.6 proportions of the two concretes used in this study.
For each mixture (Mix 1 and Mix 2), Ø100 x 200 mm
3.4 0.07
(3.94 x 7.87 in) (diameter x length) cylindrical specimens
5.6 0.14 were used to determine compressive strength. Prismatic
64.6 0.38 75 x 75 x 285 mm (2.95 x 2.95 x 11.22 in.) specimens were
2.1 0.29 prepared to measure expansion, mass change, and ultrasonic
pulse velocity before and after exposure to sulfate attack,
1.20 0.26
and the average values from three identical specimens were
2.51 0.53 used. All specimens were demolded after 24 hours and cured
0.5 0.15 at 21°C (69.8°F) and 95% relative humidity. After 28 days,
the initial compressive strength, mass, length, and ultrasonic
pulse velocity of the specimens were determined before
3.15 2.35
exposure to sulfate attack.
490 620

Note: 1 m /kg = 0.54 yd /lb.

2 2

Table 2—Mixture proportions of investigated concretes

Composition, kg/m3 Cement Silica fume Sand Gravel Water HRWRA* w/b† 28-day compressive strength, MPa
Mixture ID
Mix 1 285 — 930 930 172 — 0.60 31.1
Mix 2 415 25 890 810 171 5 0.39 60.4
*
High-range water-reducing admixture.
†
Water-binder (cement + silica fume) ratio.
Notes: 1 kg/m3 = 1.685 lb/yd3; 1 MPa = 0.145 ksi.

494 ACI Materials Journal/July-August 2016

Fig. 1—Vacuum desiccator used for Method A and Method B preconditioning.
Proposed accelerated preconditioning methods
Degradation of concrete by external sulfate ions involves
both physical and chemical aspects. The physical aspect is
related to the ingress of sulfate ions into concrete pores,
especially by diffusion. The influence of the chemical aspect
depends on the profile of penetration of sulfate ions.26
Based on the acceleration of the diffusion process of sulfate
ions into concrete, two methods of preconditioning were
proposed and tested, and sulfate ions were forced to migrate
through the concrete specimens via preliminary saturation
by vacuum desiccators. After applying the new methods
of supplementary preconditioning, all concrete specimens
were immersed in sulfate solution for the duration of the
test. To facilitate the presentation and discussion of results,
preconditioning procedures were divided into Method A,
Method B, and the control method.
In Methods A and B, concrete prisms were dried in an
oven after 28 days of curing. To avoid pore structure damage
that can be caused by the drying procedure,27 a 50°C (122°F)
drying temperature was used up to a constant weight, usually
between 1 and 3 weeks.28 After the oven drying time, the
concrete prisms were placed vertically in the desiccator
(described by ASTM C120229 as one requiring two hose
connections). The prisms were kept under vacuum for
24  hours to remove the maximum amount of air, and a
5% sodium sulfate solution (by weight) was prepared. The
difference between Methods A and B can be observed in the
procedure of presaturation by sulfate solution.
In Method A, after 24 hours of dried vacuuming with
the desiccator with vacuum pump and pressure main-
tained between –635 mm Hg and –760 mm Hg (0.084 and
0.1 MPa), the sulfate solution was drained slowly into the
desiccator container to cover the entire surface and length
of specimens. Draining stopped after levels reached 10 to
20 mm (039 to 0.79 in.) above the tops of the samples. The
vacuum pump was kept running for another 72 hours, with
full immersion of specimens.
In Method B (Fig. 1), after 24 hours of dried vacu-
uming with the desiccator (Fig. 1(a)) with the running
vacuum pump and pressure running between –635 and
–760 mm  Hg (0.084  and 0.1 MPa), the sulfate solution
was drained slowly into the desiccator container to cover
approximately one-third of the specimen’s length (approx-
ACI Materials Journal/July-August 2016
imately 90 mm [3.54 in.]) in the first stage (Fig. 1(b)). The
vacuum pump was kept running for an additional 24 hours.
The sulfate solution was then drained slowly into the desic-
cator container for the second time to cover two-thirds of the
length (around 180 mm [7.09 in.]), and the vacuum was kept
running for another 24 hours (Fig. 1(c)). The sulfate solution
was drained into the desiccator for the third time to cover the
specimens’ length completely (Fig. 1(d)). The vacuum pump
was run for an additional 24 hours for maximum penetration
of sulfate solution into the concrete prisms.
In the control method, no special preconditioning was
applied to the concrete specimens. After 28 days of curing,
the samples were immersed directly in the 5% sodium
sulfate solution.
After supplementary preconditioning using the control
method, Method A, and Method B, testing was followed by
immersing concrete prisms in tanks containing 5% sodium
sulfate solution at a temperature of 23 to 27°C (73.4 to
80.6°F). The volume of solution used was calculated as
five times the concrete prisms’ volume for all concretes.
According to ASTM C1012-04,6 the solution must be
renewed each week, which requires large amounts of sodium
sulfate. Mehta12 recommended controlling the pH within a
range of 6.0 to 8.0 by adding a suitable amount of sulfuric
acid solution (0.1 N H2SO4); this study combined the two
methods. The pH of the sulfate solution was corrected daily
(between 6 and 7) during immersion time, and the aggres-
sive solution was completely renewed every 6 weeks.
The efficiency of supplementary preconditioning via
Methods A and B was tested by assessing the expansion,
mass, and ultrasonic pulse velocity changes of concrete
samples. The results were compared with the control
method (which had no preliminary saturation) using the
same immersion conditions. Thirty and 60 MPa [4.4 and
8.7 ksi] medium and high sulfate-resistant) concretes were
tested. To investigate the most effective method for accel-
erating degradation by sulfate attack, the control method,
Method A, and Method B results were compared. Miner-
alogical (XRD) investigations were performed to clearly
understand the mechanism of attack using the new method
of preconditioning, and chemical and microstructural
studies were carried out using SEM coupled to EDS and
microanalyses of polished surfaces.
495
Fig. 2—Expansion of concrete specimens in 5% Na2SO4 solution after being subjected to different preconditioning methods.
RESULTS AND DISCUSSION
Expansion measurements
Figure 2 shows the 1-year expansion of concrete speci-
mens exposed to sulfate attack after being subjected to
the control and new methods of supplementary precondi-
tioning. The length changes of the 30 MPa (4.4 ksi) class
concrete samples presented in Fig. 2(a) show a difference in
expansion trend between test methods. Unlike the 120-day
dormant period in the case of the control method, expan-
sion increased systematically for specimens preconditioned
via Methods A and B, which may prove the efficiency of
presaturation using desiccators. The specimens subjected to
supplementary preconditioning using Method B showed the
highest degree of expansion from the first week of immer-
sion in sodium sulfate solution. The difference in expansion
appears to have been more pronounced with time, especially
when comparing Method B and the control method. Speci-
mens subjected to Method A consistently exhibited higher
expansions than those subjected to the control method;
however, they showed a lower rate of expansion evolution
compared to those exposed to Method B. At 1 year, expan-
sions of 0.11%, 0.31%, and 0.82% were measured using the
control, A, and B preconditioning procedures, respectively.
Method B provided expansion 7.5 times higher than the
control method, and 2.6 times higher than Method A. As
cited in the literature, ettringite formation is believed to be
496
the first cause of expansion and damage of concrete under
sulfate attack.30 According to Perruchot et al.,31 ettringite
crystals formed by the reaction between sulfate ions and
aluminates (sulfoaluminate or carboaluminates) may cause
crystallization pressure related to super-saturation and pore
size, which generate significant expansive pressure. The
high expansion in specimens subjected to preconditioning
via Method B can be explained by the accelerated diffu-
sion of sulfate ions throughout the core of concrete spec-
imens up to super-saturation. Early super-saturation and
ettringite formation caused early expansion that increased
dramatically with time. The continuous increase of expan-
sion for 60 MPa (8.7 ksi) class specimens subjected to
Method A and Method B can be observed from the results
in Fig. 2(b). Negligible (0.004%) expansion was recorded
for specimens subjected to the control method. At the end
of 1 year, expansions of 0.18% and 0.08% were recorded
for Methods  B and A, respectively. In previous studies of
high-strength concretes (high-sulfate-resistant concrete),
first expansion started after at least 2 years of exposure to
sulfate attack.26 Using desiccators to presaturate the speci-
mens using Method A or B resulted in expansion, starting
from the first weeks of immersion in sulfate solution. This
result explains the importance of supplementary precondi-
tioning by presaturation on the acceleration of expansion in
sulfate attack environments.
ACI Materials Journal/July-August 2016
Fig. 3—Mass change of concrete specimens in 5% Na2SO4 solution after being subjected to different preconditioning.
Mass measurements
Mass change results for specimens subjected to supple-
mentary preconditioning using control, A, and B methods
and immersed in 5% sulfate solution are shown in Fig. 3.
The effects of preconditioning methods can be observed
from the trends in mass change (Fig. 3(a)). Starting with the
first week of immersion, specimens subjected to Method B
gained greater mass than their counterparts subjected to
Method A or the control method, and Method A speci-
mens gained greater mass than those exposed to the control
method. Unlike the systematic gain of mass evident with
the control method, specimens exposed to Methods A and
B showed three stages of change: a rapid increase of mass,
a short stabilization period, and finally a decrease in mass.
Concrete specimens subjected to preconditioning using
Method B had the shortest mass-gain time and earlier and
greater mass decrease. The greater mass gain with Method B
specimens can be related to the higher expansion from the
first week of exposure to sulfate attack. In addition, the use
of presaturation, especially with Method B, may accelerate
ettringite formation, and, consequently, water absorption.
Indeed, mass gain in sulfate attack is usually attributed to
the hydration of anhydrous cement, and to the formation of
gypsum and secondary ettringite due to reactivity between
hydrates and sodium sulfate.26 In addition, according to
ACI Materials Journal/July-August 2016
Khelifa et al.,32 the mass gain may be due to water filling
cracks and to the mass of water used to precipitate the
hydrated phase as ettringite. Mass decrease occurred due
to degradation by sulfate attack, starting by spalling and
cracking at corners and edges.
Figure 3(b) shows that for the 60 MPa (8.7 ksi) strength
class, at 360 days of exposure to sulfate attack, mass change
showed an increasing trend for specimens subjected to
preconditioning using the control method or Method A.
Specimens preconditioned using Method B presented
greater mass gain starting from the first week of immer-
sion. As in the 30 MPa (4.4 ksi) class, this trend in mass
gain can be attributed to the higher expansion in Method B
results, and also to accelerated ettringite precipitation and
gypsum formation from sulfate reaction, which need more
solution absorption. The superiority of Method B (as accel-
erated test) compared to Method A and the control method,
can be explained by the fact that, in Method B, the trend of
decrease in mass change (which can be considered as initi-
ation of deterioration due to sulfate attack) was observed
within 360 days.
Ultrasonic pulse velocity measurements
Figure 4 shows the variation of ultrasonic pulse velocity
(UPV) with time for different concrete samples subjected to
497
Fig. 4—Ultrasonic pulse velocity change of concrete in 5% Na2SO4 solution after being subjected to different precondi-
tioning methods.
preconditioning using the control method and Methods A
and B, and immersed in 5% Na2SO4 solution. Figure 4(a)
shows that in the first 120 days of exposure to sulfate attack,
using new Method A or B preconditioning procedures led to
higher velocity gain than using the control method, with the
pre-conditioning method showing a significant influence
on velocity variation over time. Starting from 135 days
of immersion, the pulse velocity of samples subjected to
Method B dropped with time. Those subjected to Method A
showed a decrement in pulse velocity after roughly
240 days of immersion, and the control method showed a
systematic increment of velocity with time. At 360 days of
exposure to sulfate attack, pulse velocities of 8%, –2.1%,
and –10.6% were recorded for specimens subjected to
Control, A, and B methods, respectively. In terms of reduc-
tion in pulse velocity (which exhibits the concrete deterio-
ration), the results demonstrate that preconditioning using
Method B is much more dominant than Method A and the
control method. Because all samples of 30 MPa (4.4 ksi)
class concrete were taken from the same mixture and had
the same initial properties, and because the pulse velocity
test offers information about the internal microcracking and
the soundness of the materials microstructure,33 the reason
for pulse velocity differences is likely due to the accel-
498
eration of damage process stemming from presaturation
according to Method A or B. However, it is evident that
Method B speeds up the damage process of concrete speci-
mens more significantly.
Fig. 4(b) shows that the UPV results of 60 MPa (8.7 ksi)
class concrete specimens were not severely affected by the
preconditioning method used. However, after 220 days of
immersion in sulfate solution, the UPV values of specimens
subjected to Method B decreased slowly with immersion
time. These results provide information about changes in
microstructure and the beginning of internal deteriora-
tion due to accelerated sulfate ingress with presaturation
according to Method B. Method A preconditioning showed
a small decrease of velocity after 320 days of immersion,
while UPV values of specimens subjected to the control
method showed no decrements up to 360 days of exposure.
This illustrates the inability of the control method to initiate
sulfate deterioration within 360 days, and confirms the
acceptability of Method B as an accelerated test. The dense
microstructure of the 60 MPa (8.7 ksi) concrete prevented
initiation and spread of deterioration. However, a compar-
ison of UPV curves confirms that the supplementary precon-
ditioning methods can significantly affect sulfate vulnera-
bility testing.
ACI Materials Journal/July-August 2016
Fig. 5—X-ray diffraction spectra at different layers after 1-year immersion in sulfate solution (Note: C is calcite; D is dolomite;
E is ettringite; G is gypsum; P is portlandite; Q is quartz; 1 mm = 0.0394 in.)
Microstructural observations is in agreement with the realistic degradation in sulfate envi-
To better understand the effects of different precondi- ronments shown in literature. Indeed, according to Bellmann
tioning methods on degradation levels of concrete, 30 MPa et al.,9 in field conditions where sulfate attack is present,
(4.4 ksi) class specimens subjected to preconditioning using ettringite or both gypsum and ettringite can be observed as
the Control, A, and B methods were examined by XRD after results of concrete damage. A relatively higher quantity and
1 year of immersion in sodium sulfate solution. Measurements strong peaks of ettringite can be noted in the surface layer of
were performed starting from the surface layer (0 to 2 mm samples subjected to preconditioning by Methods A and B
[0 to 0.079 in.]), moving toward the core (8 to 10, 18 to 20, than those exposed to the control method, especially at around
28 to 30 mm [0.31 to 0.39, 0.71 to 0.79, 1.1 to 1.2 in.]). Figure 5 22.04 deg 2θ and 45.15 deg 2θ. Furthermore, an ettringite
presents the XRD spectra at different layers for concretes peak of around 30.55 deg 2θ was present only in the surfaces
subjected to each type of preconditioning. Patterns were of the Method B samples. Important peaks of gypsum can be
obtained using an X-ray diffractometer with Cu Ka radiation seen on all surfaces; however, at around 11.6 deg 2θ, they
and 2θ scanning, ranging between 5 and 80 degrees of 2θ. were more significant in the Method B results. There was no
The superposition of the XRD patterns of different layers detectable trace of portlandite on all surfaces, which indi-
shows dominant peaks of ettringite and gypsum on all cates total leaching of this phase in the surfaces that were in
surfaces exposed to the sodium sulfate solution. This finding permanent content with the sulfate solution.

ACI Materials Journal/July-August 2016 499

Fig. 6—Sulfate profile of concrete samples exposed to sulfate attack after preconditioning. (Note: 1 mm = 0.0394 in.)
Greater differences between the data of each layer were
observed by moving into the specimen cores. In spite of
the presence of ettringite, gypsum, and portlandite, in all
8 to 10 mm (0.31 to 0.39 in.) layers, XRD results showed
higher intensity of ettringite peaks in specimens subjected
to Method B, especially in the principal calcite peaks,
located at around 22.04 deg 2θ, 35.5 deg 2θ, 36.84 deg 2θ,
and 45.15 deg 2θ. Starting from a 18 mm (0.71 in.) depth,
strong ettringite peaks were noted only in concrete samples
subjected to Method B, though with fewer peaks in the inner
layer (28 to 30 mm [1.1 to 1.2 in.]). For specimens subjected
to preconditioning by Method A, ettringite patterns were
also detected; however, the amount and intensity were lower
than for those subjected to Method B. Very weak peaks of
ettringite were seen in the 18 to 20 mm (0.71 to 0.79 in.) and
28 to 30 mm (1.1 to 1.2 in.) layers of samples preconditioned
using the control method.
Better-defined portlandite peaks were seen, starting from
the 8 to 10 mm (0.31 to 0.39 in.) layer of the control speci-
mens, than in the Method A samples. There was a detectable
trace of portlandite, starting only from 18 mm (0.71 in.) of
the samples preconditioned by Method B, indicating signif-
icant leaching of calcium hydroxide before this phase. It is
well known that CH reacts with sulfate to create more expan-
sive secondary ettringite and gypsum,26 which is also in
agreement with the higher ettringite peaks in the Method B
results. In comparing the gypsum content of each layer,
unlike the important peaks showing in the exterior layer of
all the specimens, only a few gypsum patterns were notice-
able in the 8 to 10 mm (0.31 to 0.39 in.) layer, with a slightly
better defined peak at around 11.65 deg 2θ in Method B spec-
imens. Gypsum peaks were totally absent in the 18 to 20 mm
(0.71 to 0.79 in.) layer of concretes preconditioned by the
control method or Method A; however, a trace of gypsum
was seen in those preconditioned by Method B. Regardless
of preconditioning method, the presence of gypsum within
a few millimeters of the surface of specimens immersed in
sulfate solution has been noted in literature. According to
Santhanam et al.,34 in concrete damaged by sulfate attack,
gypsum is primarily detected close to the surface, especially
in cracks and voids. The trace of gypsum, which appeared
even in inner (18 to 20 mm [0.71 to 0.79 in.]) layers of spec-
imens from Method B, can be attributed to the penetration of
500
sulfate ions up to this layer, which can lead to the formation
of gypsum or ettringite.
According to Siad et al.,26,35 looking at the sulfate profile
on polished surfaces is a reliable method of determining the
level of degradation by sulfate attack. To better understand
the role of the preconditioning method on the acceleration
of degradation, sulfur variation was investigated from the
surface toward the core of specimens. The concretes inves-
tigated by SEM were examined using EDS analysis on
polished surfaces. Line profiles avoided maximum aggre-
gates. Figure 6 presents the sulfate profile of the samples
subjected to different methods of preconditioning and
immersed for 1 year in sodium sulfate solution.
As seen from the figure, the sulfur was not uniformly
dispersed in the concrete pastes. Profiles presented in
Fig. 6 follow three stages: a maximum density within a few
millimeters of the exterior layer; a gradual increase; and
a different extent of the stable amount. A small difference
in sulfur content was seen in the exterior surface exposed
directly to sulfate attack. Within 1 mm (0.04 in.) of depth,
maximum amounts of sulfur of approximately 13.1, 13.5,
and 14.6% were recorded for the control method, Method A,
and Method B specimens, respectively. Starting from 1 mm
(0.4 in.) toward the core, an important difference was notice-
able. When compared to the control results, the amount of
sulfur seemed to stabilize at approximately 2% density.
Using this value to characterize the unaffected zone, the
depth of degradation was found to be equal to 7.8, 13.8,
and 25 mm (0.31, 0.54, and 0.98 in.), for the control, A, and
B specimens, respectively. Moreover, the density of sulfur
in concrete specimens subjected to Method B showed a
minimum amount of roughly 8% (up to 23 mm [0.91 in.] in
depth), which is four times the density found in the control
specimens. These results are consistent with XRD patterns,
which show strong ettringite peaks starting from the surface
and reaching the 18 to 20 mm (0.71 to 0.79 in.) layer of
Method B specimens. The presence of high amounts of
ettringite can explain the high expansion and damage shown
above in the Method B results.
To detect and quantify the form of sulfur (ettringite,
gypsum, or monosulfoaluminate) shown in the sulfate profiles
section, a complementary analysis of the microstructure was
performed according to the Scrivener correlation.36 Figure 7
presents the changes in the phase assemblage from the surface
ACI Materials Journal/July-August 2016
toward the core (0 to 8 mm [0 to 0.31 in.] and 18 to 26 mm
[0.71 to 1.02 in.] zones) of the element ratios S/Ca as a func-
tion of Al/Ca. The plots of S/Ca versus Al/Ca suggest that
the ettringite phase has S/Ca = 0.5 and Al/Ca = 0.33, and
the S/Ca and Al/Ca ratios of 1 and 0 correspond respec-
tively to gypsum and monosulfoaluminate, with S/Ca =
0.25 and Al/Ca = 0.5.
Fig. 7—Phase assemblages of concrete specimens exposed
to sulfate attack after preconditioning (Atom ratio plot of
S/Ca versus Al/Ca for surface zone and core.) (Note: G is
gypsum; Ett is ettringite; Ms is monosulfoaluminate; CH is
portlandite; 1 mm = 0.0394 in.)
Fig. 8—SEM and EDS data for concrete specimens subjected to preconditioning using control method.
ACI Materials Journal/July-August 2016
Microanalysis of the external zone (0 to 8 mm [0 to
0.31 in.]) showed the presence of ettringite partly intermixed
with C-S-H in all specimens. High amounts of ettringite
were noticed in specimens subjected to Method B, with less
in Method A specimens and an even smaller amount in the
control specimens. Gypsum was also identified in all the
external zones exposed to sulfate attack, with higher content
in Method B specimens. Greater amounts of monosulfoalu-
minate intermixed with the C-S-H phase were detected in
the control specimens. Furthermore, portlandite was clearly
absent among the external zone of Method B specimens, but
was present in the Method A and control samples.
The phase assemblage across the cores of concrete
samples revealed the presence of high amounts of ettringite
in Method B specimens, partly intermixed with C-S-H,
even between 18 and 26 mm (0.71 and 1.02 in.) of depth. A
slight quantity of ettringite was detected in Method A speci-
mens, and even less was observed in the control specimens.
Portlandite was detected in Method B specimens, however,
with lower amounts compared to the Method A and control
samples. An insignificant difference was noted for monosul-
foaluminate intermixed with the C-S-H phase of different
specimen cores.
SEM-EDS analyses were also conducted to investigate the
form of ettringite and gypsum produced by sulfate reaction.
Figures 8 through 10 show SEM micrographs and EDS
analysis of concrete samples subjected to different methods
of preconditioning. The gypsum micrographs (Fig. 8(a), 9(a),
and 10(a)) are taken from areas close to the surface layer,
while ettringite micrographs (Fig. 8(b), 9(b), and 10(b)) are
taken from 10 to 15 mm (0.39 to 0.59 in.) inside the core.
SEM micrographs confirmed the presence of significant
amounts of compressed (Fig. 10(b)(1)), massive (Fig. 10(b)
(2)), and needle (Fig. 10(b)(3)) forms of ettringite dispersed
along cement paste/aggregate interfaces and in the cavities
501
Fig. 9—SEM and EDS data for concrete specimens subjected to preconditioning using Method A.

Fig. 10—SEM and EDS data for concrete specimens subjected to preconditioning using Method B.
left by disintegrated aggregates of samples subjected to
preconditioning by Method B. This type of ettringite has
been noted in literature as an expansive form.37,38 According
to Divet and Pavoine,38 the abundance of the massive form
of ettringite at the cement paste/aggregate interface gives
the impression that its formation will have generated suffi-
ciently large internal stresses to cause deformation and
cracking within the material. In addition to the large quan-
tity of ettringite throughout the cores of samples subjected
to preconditioning by Method B, they also had higher
sulfate profiles and phase assemblage sections; the quality
of ettringite generated from the reaction with sulfate attack
confirmed to be expansive. These results can explain the
acceleration method of degradation by using part-by-part
saturation in primary preconditioning of concrete speci-
mens. Indeed, the use of desiccators to saturate specimens
under vacuum forced the sulfate ions to migrate through
their cores.
Ettringite detected in the cores of samples subjected to
Method A (Fig. 9) also showed massive (Fig. 9(b)(1)) and
needle (Fig. 9(b)(3)) forms, mainly present around cavi-
ties left by the disintegration of aggregates during prepa-
ration. However, although saturation by complete immer-
sion (Method A) accelerated sulfate penetration inside the

502 ACI Materials Journal/July-August 2016

specimens, preconditioning using part-by-part saturation
(Method B) caused maximum diffusion. This can lead to
super-saturation by sulfate ions and accelerate the formation
and precipitation of ettringite needles, which generate local-
ized high pressure and consequently lead to early expansion.
For the control specimens, it was difficult to identify the
ettringite phase in the sample cores (Fig. 8(b)). However,
some agglomerations (massive [Fig. 8(b)(2)] and needle
[Fig. 8(b)(3)] forms of ettringite) were noticed randomly
scattered in the paste around aggregates. Although the expan-
sive ettringite was present inside the control specimens, its
abundance prevented the generation of high pressure and,
therefore, expansion occurred later than in Method A speci-
mens and especially in Method B specimens.
Gypsum from the control (Fig. 8(a), A (Fig. 8(b)), and B
(Fig. 8(c)) specimens was also detected at the inner surface,
close to regions where maximum ettringite was observed.
However, it was more pronounced and denser for Method B
and A specimens. Despite the debate over the expansivity
of gypsum caused by sulfate attack,34,39,40 the clearly high
quantity of this product related to the high expansion and
damage in specimens preconditioned by Methods B and A
offers information about the possible role of gypsum forma-
tion in the acceleration of damage caused by sulfate attack.
CONCLUSIONS
This paper presents the results of a study aimed to recom-
mend a new method of accelerating the degradation of
concrete specimens exposed to external sulfate attack. The
study is important, considering the absence of a standard
accelerated test to inspect concrete sulfate resistance. The
goal was to reduce testing time while simulating degrada-
tion mechanisms that reflect field conditions. The reliability
and performance of methods based on immersion in sulfate
solution coupled with primary preconditioning were inves-
tigated. The study compared two new methods involving
presaturation (A and B) with a control method using no
special preconditioning. In Method A, preconditioning
involved a one-time complete immersion inside the desic-
cator under vacuum, while in Method B, presaturation was
performed with part-by-part presaturation under vacuum.
The efficiency of the newly proposed methods was studied
by assessing the expansion evolution, mass change, and UPV
of the concrete specimens during the immersion period. The
following conclusions were drawn from the study:
1. Higher expansion was observed in specimens subjected
to preconditioning by Method B than by Method A and the
control method. For the 30 MPa (4.4 ksi) strength concrete,
Method B provided 7.5 and 2.5 times more expansion than
the control method and Method A, respectively, at the end
of a 1-year exposure period. For the high-strength concrete
(60 MPa [8.7 ksi]), negligible (0.004%), 0.08%, and 0.18%
expansion was recorded for specimens made with the
control, A, and B methods, respectively.
2. Although no mass loss was measured during immersion,
differences in mass change influenced by preconditioning
method were noted. Method B samples showed higher mass
gain, and early and higher mass decrements than the control
and A methods.
ACI Materials Journal/July-August 2016
3. Preconditioning methods had a significant influence
on UPV variation, with early and higher variations noted
in Method B specimens. For instance, the 30 MPa (4.4 ksi)
concrete specimens showed UPV decrements after 135 and
240 days for B and A preconditioning methods, respec-
tively. The control method showed a systematic increment
of velocity with time. It is evident that Method B sped up the
damage process and is therefore more effective as an accel-
erated test.
4. Microstructural analysis showed that sulfate profiles
and phase assemblages were consistent with expansion
results. Significant amounts of ettringite throughout the
surfaces and cores of Method B specimens were observed.
The depth of sulfur was equal to 7.8, 13.8, and 25 mm (0.31,
0.54, and 0.98 in.), for the control, B, and A method spec-
imens, respectively. Density of sulfur in specimen cores
subjected to Method B preconditioning was four times that
of the control specimens. SEM micrographs and EDS anal-
yses confirmed the expansive quality of ettringite found in
the cores of Method B specimens. The mechanism of degra-
dation of Method B specimens confirmed those observed in
field conditions.
AUTHOR BIOS
Hocine Siad is a Postdoctoral Researcher in the Department of Civil Engi-
neering at Ryerson University, Toronto, ON, Canada. His research interests
include the development and assessment of new materials and methods for
concrete durability.
Mohamed Lachemi is a Professor in the Department of Civil Engineering
at Ryerson University. His research interests include the use of high-
performance materials and self-consolidating concrete, including the
development and use of reactive powder in concretes.
Mustafa Şahmaran is an Associate Professor in the Department of Civil
Engineering at Gazi University, Ankara, Turkey. His research interests
include advanced materials technology and composite materials develop-
ment for sustainable infrastructure.
Khandaker M. Anwar Hossain is a Professor in the Department of Civil
Engineering at Ryerson University. His research interests include the devel-
opment of construction materials with volcanic materials/industrial wastes
and composite materials for structural applications.
REFERENCES
1. Sahmaran, M.; Erdem, T. K.; and Yaman, I. O., “Sulfate Resistance
of Plain and Blended Cements Exposed to Wetting-Drying and Heating-
Cooling Environments,” Construction and Building Materials, V. 21, No. 8,
2007, pp. 1771-1778. doi: 10.1016/j.conbuildmat.2006.05.012
2. Sahmaran, M.; Kasap, O.; Duru, K.; and Yaman, I. O., “Effects of
Mix Composition and Water-Cement Ratio on the Sulfate Resistance of
Blended Cements,” Cement and Concrete Composites, V. 29, No. 3, 2007,
pp. 159-167. doi: 10.1016/j.cemconcomp.2006.11.007
3. Girardi, F.; Vaona, W.; and Di Maggio, R., “Resistance of Different
Types of Concretes to Cyclic Sulfuric Acid and Sodium Sulfate Attack,”
Cement and Concrete Composites, V. 32, No. 8, 2010, pp. 595-602. doi:
10.1016/j.cemconcomp.2010.07.002
4. ACI Committee 318, “Building Code Requirements for Structural
Concrete (ACI 318-99) and Commentary,” American Concrete Institute,
Farmington Hills, MI, 1999, 353 pp.
5. Chabrelie, A., “Mechanisms of Degradation of Concrete by External
Sulfate Ions under Laboratory and Field Conditions,” PhD thesis, Ecole
Polytechnique Fédérale de Lausanne, Lausanne, Switzerland, 2010, 186 pp.
6. ASTM C1012-95a, “Standard Test Method for Length Change of
Hydraulic-Cement Mortars Exposed to a Sulfate Solution,” ASTM Interna-
tional, West Conshohocken, PA, 1995, 5 pp.
7. Hooton, R. D., and Brown, P. W., “Development of Test Methods
to Address the Various Mechanisms of Sulphate Attack,” Proceedings of
Concrete in Aggressive Aqueous Environments, Performance, Testing and
Modeling, Toulouse, France, 2009, pp. 280-297.
503
 8. Aleksic, M., “Development and Standardization of the NIST Rapid
Sulphate Resistance Test,” master’s thesis, Department of Civil Engi-
neering, University of Toronto, Toronto, ON, Canada, 2010, 178 pp.
9. Bellmann, F.; Moser, B.; and Stark, J., “Influence of Sulfate Solution
Concentration on the Formation of Gypsum in Sulfate Resistance Test Spec-
imen,” Cement and Concrete Research, V. 36, No. 2, 2006, pp. 358-363.
doi: 10.1016/j.cemconres.2005.04.006
10. Suleiman, A. R., “Physical Sulphate Attack on Concrete,” master’s
thesis, Department of Civil and Environmental Engineering, The University
of Western Ontario, London, ON, Canada, 2014, 127 pp.
11. Crumbie, A. K., “Characterization of the Microstructure of Concrete,”
PhD thesis, University of London, Imperial College, London, UK, 1994,
pp. 253-258.
12. Mehta, P. K., “Evaluation of Sulfate Resisting Cements by a New Test
Method,” ACI Journal Proceedings, V. 72, No. 10, Oct. 1975, pp. 573-575.
13. Drimalas, T., “Laboratory and Field Evaluations of External Sulfate
Attack,” PhD thesis, University of Texas at Austin, Austin, TX, 2007, 187 pp.
14. Cohen, M. D., and Mather, B., “Sulfate Attack on Concrete—
Research Needs,” ACI Materials Journal, V. 88, No. 1, Jan.-Feb. 1991,
pp. 62-69.
15. Almeida, I. R., “Resistance of High-Strength Concrete to Sulfate
Attack: Soaking and Drying Test,” Durability of Concrete, SP-100,
J. M. Scanlon, ed., American Concrete Institute, Farmington Hills, MI,
1991, pp. 1073-1092.
16. Assaad, V. F.; Jofriet, J. C.; Negi, S. C.; and Hayward, G. L., “Labo-
ratory Tests of Sulphide and Sulphate Corrosion of Reinforced Concrete,”
Proceedings of the Vth International Symposium on Concrete for a Sustain-
able Agriculture, El Escorial, Spain, 2005, pp. 179-190.
17. Damidot, D., and Glasser, F. P., “Thermodynamic Investi-
gation of the CaO-Al2O3-CaSO4-H2O System at 50°C and 85°C,”
Cement and Concrete Research, V. 22, No. 6, 1992, pp. 1179-1191. doi:
10.1016/0008-8846(92)90047-Y
18. De Belie, N., “Evaluation of Methods for Testing Concrete Degra-
dation in Aggressive Solutions,” Workshop on Performance of Cement-
Based Materials in Aggressive Aqueous Environments—Characterization,
Modeling, Test Methods and Engineering Aspects, N. De Belie, ed., Ghent,
Belgium, 2007, pp. 63-74.
19. Clifton, J. R.; Frohnsdorff, G.; and Ferraris, C., “Standards for Eval-
uating the Susceptibility of Cement-Based Materials to External Sulfate
Attack,” Materials Science of Concrete, Sulfate Attack Mechanisms,
Special Volume, 1999, pp. 337-355.
20. Damidot, D., and Glasser, F. P., “Thermodynamic Investiga-
tion of the CaO-Al2O3-CaSO4-K2O-H2O System at 25°C,” Cement
and Concrete Research, V. 23, No. 5, 1993, pp. 1195-1204. doi:
10.1016/0008-8846(93)90180-H
21. Higgins, D. D., “Increased Sulfate Resistance of GGBS Concrete
in the Presence of Carbonate,” Cement and Concrete Composites, V. 25,
No. 8, 2003, pp. 913-919. doi: 10.1016/S0958-9465(03)00148-3
22. Osborne, G. J., “Durability of Portland Blast-Furnace Slag Cement
Concrete,” Cement and Concrete Composites, V. 21, No. 1, 1999, pp. 11-21.
doi: 10.1016/S0958-9465(98)00032-8
23. Neville, A., “The Confused World of Sulfate Attack on Concrete,”
Cement and Concrete Research, V. 34, No. 8, 2004, pp. 1275-1296. doi:
10.1016/j.cemconres.2004.04.004
24. ASTM C150/C150M-12, “Standard Specification for Portland
Cement,” ASTM International, West Conshohocken, PA, 2012, 9 pp.
504
25. CAN/CSA A3000-08, “Cementitious Materials Compendium,”
Canadian Standards Association, Rexdale, ON, Canada, 2008, 282 pp.
26. Siad, H.; Kamali-Bernard, S.; Mesbah, H. A.; Escadeillas, G.;
Mouli, M.; and Khelafi, H., “Characterization of the Degradation of
Self-Compacting Concretes in Sodium Sulfate Environment: Influence
of Different Mineral Admixtures,” Construction and Building Materials,
V. 47, Oct. 2013, pp. 1188-1200. doi: 10.1016/j.conbuildmat.2013.05.086
27. Neville, A. M., Properties of Concrete, third edition, Longman
Scientific and Technical, Essex, UK, 1981, pp. 338-344.
28. Sanjuán, M. A., and Muñoz-Martialay, R., “Oven-Drying as a Precon-
ditioning Method for Air Permeability Test on Concrete,” Materials Letters,
V. 27, No. 4-5, 1996, pp. 263-268. doi: 10.1016/0167-577X(95)00283-9
29. ASTM C1202-12, “Standard Test Method for Electrical Indication
of Concrete’s Ability to Resist Chloride Ion Penetration,” ASTM Interna-
tional, West Conshohocken, PA, 2012, 7 pp.
30. ACI Committee 201, “Guide to Durable Concrete (ACI 201.2R-92),”
American Concrete Institute, Farmington Hills, MI, 1992, 41 pp.
31. Perruchot, C.; Chehimi, M. M.; Vaulay, M. J.; and Benzarti, K.,
“Characterization of the Surface Thermodynamic Properties of Cement
Components by Inverse Gas Chromatography at Infinite Dilution,” Cement
and Concrete Research, V. 36, No. 2, 2006, pp. 305-319. doi: 10.1016/j.
cemconres.2005.02.005
32. Khelifa, R.; Brunetaud, X.; Chabil, H.; and Al-Mukhtar, M.,
“Conséquences Mécaniques de L’attaque Sulfatique Externe sur les BAP,”
SciTechnol Journal, V. 28, 2008, pp. 23-28.
33. Skaropoulou, A.; Kakali, G.; and Tsivilis, S., “Thaumasite Form
of Sulfate Attack in Limestone Cement Concrete: The Effect of Cement
Composition, Sand Type and Exposure Temperature,” Construction
and Building Materials, V. 36, Nov. 2012, pp. 527-533. doi: 10.1016/j.
conbuildmat.2012.06.048
34. Santhanam, M.; Cohen, M. D.; and Olek, J., “Effects of Gypsum
Formation on the Performance of Cement Mortars during External Sulfate
Attack,” Cement and Concrete Research, V. 33, No. 3, 2003, pp. 325-332.
doi: 10.1016/S0008-8846(02)00955-9
35. Siad, H.; Lachemi, M.; Bernard, S. K.; Sahmaran, M.; and Hossain,
A., “Assessment of the Long-Term Performance of SCC Incorporating
Different Mineral Admixtures in a Magnesium Sulphate Environment,”
Construction and Building Materials, V. 80, Apr., 2015, pp. 141-154. doi:
10.1016/j.conbuildmat.2015.01.067
36. Scrivener, K. L., “Backscattered Electron Imaging of Cementi-
tious Microstructures Understanding and Quantification,” Cement and
Concrete Composites, V. 26, No. 8, 2004, pp. 935-945. doi: 10.1016/j.
cemconcomp.2004.02.029
37. Cohen, M. D., “Modeling of Expansive Cements,” Cement
and Concrete Research, V. 13, No. 4, 1983, pp. 519-528. doi:
10.1016/0008-8846(83)90011-X
38. Divet, L., and Pavoine, A., “Delayed Ettringite Formation in Massive
Concrete Structures: An Account of Some Studies of Degraded Bridges,”
International RILEM TC-186 ISA, Switzerland, 2002, pp. 98-126.
39. Tian, B., and Cohen, M. D., “Does Gypsum Formation during Sulfate
Attack on Concrete Lead to Expansion,” Cement and Concrete Research,
V. 30, No. 1, 2000, pp. 117-123. doi: 10.1016/S0008-8846(99)00211-2
40. Mather, B., “Discussion of the Process of Sulfate Attack on
Cement Mortars,” Advanced Cement Based Materials, V. 5, No. 3, 1996,
pp. 109-110.
ACI Materials Journal/July-August 2016