Cement and Concrete Research 116 (2019) 134–145

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Cement and Concrete Research

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Durability of cement pastes exposed to external sulfate attack and leaching: T

Physical and chemical aspects
⁎
Rim Ragouga, Othman Omikrine Metalssib, , Fabien Barberonc, Jean-Michel Torrentid,
Nicolas Roussele, Loïc Divetf, Jean-Baptiste d'Espinose de Lacaillerieg
a
CESI,93 Boulevard de la Seine, 92000 Nanterre, France
b
Civil Engineering at the Research Unit: Experimental and Numerical Analysis of Structures, IFSTTAR-Paris-Est University, IFSTTAR, 14-20 Bd Newton, 77447, Champs/
Marne, MLV Cedex 2, France
c
EQIOM, 49 Avenue Georges Pompidou, 92300 Levallois-Perret, France
d
Materials & Structures Department, MASTat IFSTTAR-PARIS/Paris-Est University, IFSTTAR, 14-20 Boulevard Newton, Cité Descartes Champs sur Marne, F-77447
Marne la Vallée, Cedex 2, France
e
Civil Engineering at the Research Unit: NAVIER, IFSTTAR, IFSTTAR, 14-20 Boulevard Newton, Cité Descartes Champs sur Marne, F-77447 Marne la Vallée, Cedex 2,
France
f
Physical-Chemical Behaviour and Durability of Materials Laboratory, IFSTTAR, 14-20 Boulevard Newton, Cité Descartes Champs sur Marne, F-77447 Marne la Vallée,
Cedex 2, France
g
ESPCI-CNRS, École Supérieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), PSL Research University, Soft Matter Sciences and Engineering
Laboratory, CNRS UMR 7615, 10 rue Vauquelin, F-75005 Paris, France

A R T I C LE I N FO A B S T R A C T

Keywords: Sulfate ions in seawater or underground can attack the cement paste leading to expansion and strength loss. This
External sulfate attack expansion is usually related to ettringite and gypsum precipitation. This study aims to characterize the possible
Structure durability altered zone and to identify the mechanisms of degradation under such conditions. For this study, cement pastes
Sulfate ingress manufactured using CEM I with two w/c ratios (0.45 and 0.60) were exposed to sodium sulfate solutions (semi-
Microstructure
immersion at a controlled pH = 8.0 ± 0.1) after one year of curing in water. The analysis of the physical aspect
Leaching
of this phenomenon shows that two modes of transfer occur: transfer of sulfate ions to the cement matrix and
leaching of calcium ions to the external solution. The analysis of the chemical composition of the affected
material highlights the progressive consumption of portlandite at the surface, the decalcification of C-S-H and
the formation of AFt from both Afm and aluminium incorporated in C-S-H.

1. Introduction
The durability of concrete structures can be significantly improved
if the effects of the surrounding environment are taken into account
upstream of the material formulation and of the structure di-
mensioning. Despite numerous studies and expertise, some degradation
mechanisms remain unclear and controversial. This is the case for ex-
ample of external sulfate attack (ESA) [1–7] which can be defined as a
chemical reaction between the sulfate ions, having penetrated into the
concrete by a transfer mechanism, and the mineral components of the
hardened cement paste, mainly tricalcium aluminate [8–10]. It can
cause a macroscopic swelling of the material with an appearance of
cracks inducing a loss of the mechanical resistance [11,12]. Indeed, the
processes associated with ESA and their consequences have been ex-
tensively studied in different laboratories; however they are often
presented as being complex and dependent on several variables in-
trinsic to the material or to its surrounding environment [1,13–15].
Moreover, most previous studies have investigated the mechanisms of
ESA and its macroscopic consequences by studying the effect of this
phenomenon on loss of mass, loss of mechanical resistance and possible
expansions [13,16,17]. Recent works are increasingly interested in the
transfer aspect in ESA and the coupled chemistry-transport aspect
[10,18]. Despite differences in the literature, all studies conclude on the
severity of this type of attack on the durability of the concrete structures
since it can induce very high damage after a short period (10 to
15 years).

⁎
Corresponding author.
E-mail addresses: rragoug@cesi.fr (R. Ragoug), othman.omikrine-metalssi@ifsttar.fr (O.O. Metalssi), fabien.barberon@eqiom.com (F. Barberon),
jean-michel.torrenti@ifsttar.fr (J.-M. Torrenti), nicolas.roussel@ifsttar.fr (N. Roussel), loic.divet@ifsttar.fr (L. Divet),
jean-baptiste.despinose@espci.fr (J.-B. d'Espinose de Lacaillerie).

https://doi.org/10.1016/j.cemconres.2018.11.006
Received 15 May 2018; Received in revised form 7 November 2018; Accepted 8 November 2018
Available online 24 November 2018
0008-8846/ © 2018 Published by Elsevier Ltd.
R. Ragoug et al.
It seems that two main processes are responsible for ESA: a physical
process of transfer of the outer solution to the porous media of the
cement matrix [19–23] and a chemical interaction between sulfate ions
having penetrated into the pore solution and the hydrates of the cement
paste [24]. The first process obviously depends on the transfer para-
meters and the second one on the initial chemical composition of the
material. As a consequence of the transfer of sulfate ions through the
interconnected capillary porosity, supersaturation conditions can be
achieved and the mineralogy of the cement paste drastically affected.
As known in the hydration mechanisms of the cement paste, some hy-
drates are sensitive to the presence of sulfate ions in solution [1,8].
Essentially, the balance of the calcium mono-sulfoaluminate (Afm) can
be very disturbed and can cause the re-precipitation of ettringite (Aft).
However, the molar volume of AFt is about twice as large as that of
AFm (707 cm3·mol−1 for 309 cm3·mol−1) [25,26]. Therefore, the pre-
cipitation of secondary ettringite in a hardened cement paste can im-
pose a significant internal pressure on the microstructure [26].
On the other hand, leaching phenomenon in neutral solution (e.g.
seawater) is accelerated at the surfaces [27,28] and can affect the in-
gress of aggressive ions into the material. This phenomenon leads to
dissolution of hydrated products particularly portlandite out of the
material causing consequently a change in the microstructure allowing
an increase of the porosity and inevitably the transport properties in the
porous media [29–31]. It leads also to the formation of a layer of de-
posits at some micros of the sample surface. Therefore, it is necessary to
take this phenomenon into account for the structures exposed to the
ESA.
This work aims to describe the results of the exposition of a mature
cement pastes with two w/c ratios (0.45 and 0.60), assumed to be to-
tally hydrated, to a sodium sulfate solution of constant pH 8.0 ± 0.1
automatically controlled and under semi-immersion conditions. The
objective of this work is, by mimicking in the laboratory exposure to
seawater, to characterize the possible altered zone and to identify the
physical and chemical mechanisms of degradation under such condi-
tions (case of bridge piers partially immersed in seawater). Here, the
results concerning ion transport, namely the transfer of sulfate ions into
the cement matrix and calcium ions leaching in the surrounding solu-
tion are presented. Then, the samples altered or not, are characterized
along the sulfate profile by a variety of investigation techniques such as
XRD, ICP, NMR (27Al and 29Si), TGA and DTA.
2. Experimental study
2.1. Materials and exposure conditions
Cement paste samples were obtained by hydration of CEM I (CEM I
52.5 N CE CP2), which satisfied the requirements of the European
Standard EN 197-1 [32], where the composition of the clinker is given
in Table 1. This composition was determined using TGA and ICP
techniques. The clinker phase contents are calculated according to
Bogue's approach and shown in Table 2. This calculation highlights the
high quantity of aluminates in C3A and C4AF favouring the formation of
secondary ettringite after reaction with a high quantity of sulfate ions.
For the laboratory specimen's fabrication, cylindrical samples of
10 cm diameter and 14 cm initial length were cast from cement pastes
prepared with two water-to-cement ratios (w/c equal to 0.45 and 0.6).
Cement paste mixtures were cast into moulds maintained in rotation
Table 1
Chemical composition of CEM I cement by using ICP-AES and TGA.
Constituents (%)
CaO SiO2 Al2O3 Fe2 O3 CaO (free)
62.81 20.22 4.85 2.92 1.58
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Cement and Concrete Research 116 (2019) 134–145
Table 2
The main cement clinker phases according to Bogue's analysis.
Cement Anhydrous phases (%)
C3S C2S C3A C4AF
CEM I 65.2 8.8 7.9 8.9
during 24 h by using a slow rotation device shown in Fig. 1-a. This
device limits bleeding and segregation during setting and produce
homogenous samples especially for higher w/c ratios. After 24 h, all
specimens were removed from their moulds and cut into 5 cm thick
cylinders. Then, they were cured in 200 L of non-renewed tap water for
one year (matured case). After this long curing period (a total hydration
of cement is then assumed to be reached), samples were placed in the
sulfate solution tanks. Beforehand, an epoxy resin was applied on the
peripheral surface of the samples in order to insure unidirectional dif-
fusion of sulfate ions (Fig. 1-b). Only one side of the specimens was in
contact with the test solution (semi-immersion), which was prepared
with 15 g/L of sodium sulfate in deionized water (10 g/L of sulfate). The
surface area of samples to the solution volume ratio was 25. The pH of
the sulfate solution was adjusted to 8.0 ± 0.1, as explained later using
the pH regulator. Finally, some samples were kept in 200 L of tap water
as reference cases.
2.2. Accelerated test for ESA
As described above, the constant pH value of 8.0 ± 0.1 (pH lower
than the one of the pore solution) of the cementitious materials appears
to be a desirable feature of testing for ESA resistance, since it permits
simulation of field exposure conditions (e.g. seawater) and it allows
accelerating the sulfate degradation process [19]. Thus, the experi-
mental conditions provided in our proposed accelerated test method are
more representative of field conditions because the sulfate concentra-
tion and the pH of the solution remain constant and similar to field
conditions. A schematic and a photo of the test apparatus are given in
Fig. 2.
The device consists of one big tank containing approximately 60 L of
sulfate solution with a concentration of 15 g/L and acting as a reservoir.
A pump with a maximum flow rate of 750 L/h was immersed in this
tank in order to circulate the sulfate solution towards a series of smaller
specimens' tanks containing 10 L each (Fig. 2-a and -b). At the output of
these tanks, the solution crosses a cylindrical tube (process 1) where the
pH of the solution is constantly monitored and regulated to 8.0 ± 0.1
by means of a continuous titration with sulfuric acid H2SO4 (0.05%)
before it flows back into the reservoir tank (process 2). The added
sulfuric acid is well mixed in the sulfate solution as this one is con-
tinuously moving between the sulfate reservoir and the specimens tanks
(process 3).
In the small tanks, semi-immersed samples (1 cm thickness was
immersed in the sulfate solution) of similar chemistry are arranged on a
mesh. The volume ratio of the specimens to the sulfate solution in each
tank is adjusted to disturb as little as possible the variation of the cir-
culating sulfate concentration. This parameter remains approximately
constant because of the weekly renewing of the solution. Moreover, the
use of sulfuric acid instead of another acid in the titration ensures that
the sulfate concentration of the solution remains almost constant over
MgO SO3 S K2O Na2O Ignition loss
0.84 2.88 0 0.77 0.34 2.59
R. Ragoug et al. Cement and Concrete Research 116 (2019) 134–145

Fig. 1. Specimens used for the study (a) and a slow rotation device used during the setting (b).

time. ettringite, from those expanding in free volumes and well-crystallized

that causes no damage at the microstructure scale.
Furthermore, the X-ray diffraction (XRD) test was performed on
2.3. Experimental techniques for investigation
some samples exposed to the ESA. The X-ray patterns were obtained on
a D8 advance diffractometer from Bruker operating at 35 kV and
Several test methods were used in this study to characterize the
40 mA, using CoK (1.79 A) radiation at an angular step of 0.01 °C per
sound materials and to investigate the kinetics of sulfate ingress in the
second between 3.0° and 80° [2θ] angles. This technique is a reliable
porous media of the cement pastes and its consequences on their mi-
method for the identification of cement paste hydrates and especially
crostructures. Indeed, Inductively Coupled Plasma, ICP-AES was used to
crystallographic phases as portlandite and ettringite. At each mea-
quantify sulfate content and/or sulfate ingress into the samples. The
surement time, powders, previously drawn from exposed samples, are
output from this experimental method is the total sulfur concentration,
manually ground and sieved to obtain a uniform particle size less than
from which sulfate concentration is computed. In this study, specimens
80 μm. These powders are then analysed to draw the mineralogical
were grinded starting from the exposed surface. The obtained amount
profile and to identify the evolution of different mineralogical phases
of powder corresponding to a 1 mm thick sample displayed an average
depending on the type of exposure. Another method, also added in this
particle size of 315 μm. All sulfates present in this powder were ionized
investigation to confirm the results given by XRD is Nuclear Magnetic
by an acid attack. The resulting solution was then tested using ICP-AES.
Resonance (NMR) of 27Al and of 29Si. This technique aims at de-
Otherwise, thermogravimetric analysis (TGA) coupled to differ-
termining the quantity of aluminate and the change in C-S-H structure
ential thermal analysis (DTA) tests were performed by using a
in the cementitious materials and then, to deduce the quantity of dif-
METTLER TOLEDO TGA/DSC1 with a balance accuracy of 0.1 μg. These
ferent phases (AFm and Aft) in the cement after the spectra decom-
methods were used as techniques for quantitative characterization of
position.
cement pastes during the ESA. In this work, these techniques could
Finally, some visual observations of swelling, cracks or material loss
explain the mechanism of the AFt formation from other hydrates of
were carried out on samples after different exposure durations to the
cement.
sulfate solution.
Moreover, Environmental Scanning Electron Microscopy (Env. SEM,
Quanta 400 from FEI company) (SEM) was also used as a technique for
qualitative characterization of cement pastes to obtain information on
the spatial distribution of different cement paste phases. Even though
this technique provided only qualitative information, the SEM images
can distinguish the phases crystallizing in confined pores as compressed

Fig. 2. Schematic of pH-control for ESA accelerated test (a), Photo of the device (b).

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R. Ragoug et al.
Fig. 3. Sulfate profiles measured using ICP-AES, for different exposure duration to the sulfate solution.
3. Results and discussion
3.1. Physical aspects of degradation
3.1.1. Sulfate profiles
Fig. 3 illustrates the effect of the w/c ratio on the sulfate ion
transport profiles obtained using ICP-AES. Two clearly distinct areas are
highlighted. The first is characterized by a penetration front of sulfate
ions corresponding to an affected zone of depth of about 4.5 mm. The
second one is the zone beyond this front (sound zone) where the sulfate
concentration corresponds to the amount of sulfate present in the re-
ference cement paste (of the order of 3% in g/g of anhydrous cement).
The initiation of ESA occurred therefore by a transfer process of sulfate
ions into the cement matrix. In addition, the average sulfate content,
from the surface (of the order of 14% in g/g of anhydrous cement) is
well above that of what one would expect from a simple equilibrium
between the internal pore solution and the external sodium sulfate
solution (of the order of 0.4% in g/g of anhydrous cement). Thus, the
measured sulfate content does not reflect the sulfate in the pore solu-
tion, but rather represents the solid phase content containing sulfate in
the matrix (CS H2; C6AS 3H32; C3AS H12), as highlighted in previous stu-
dies [31]. In other words, the content of physically or chemically bound
sulfates is higher than the free sulfates in the interstitial solution [33].
Consequently, the energy involved in the fixation process is extremely
high. On the other hand, the limiting parameter of adsorption is the C/S
ratio more than the free sulfate content. This C/S ratio is directly af-
fected by the leaching phenomenon that could have a significant effect
on the ESA mechanisms.
Furthermore, the sulfate profiles are similar near the surface after
one and two months of exposure. Thus, the important part of the
transfer of sulfate ions to the cement matrix occurs during the first
month of exposure. Therefore, this observation suggests that the sulfate
fixation kinetics is faster than the one of the ion transfer in the porous
network. Even if a diffusion process due to a concentration gradient is
initially responsible for the penetration of sulfate ions into the ce-
mentitious matrix, the physicochemical interaction with the hydrates
seems to have higher kinetics. Consequently, ESA is characterized by
the coexistence of diffusion and physicochemical fixation of sulfate ions
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Cement and Concrete Research 116 (2019) 134–145
in the cement matrix. In this coupled chemistry-transport process, dif-
fusion acts as a limiting phenomenon.
On the other hand, the transfer profiles are almost similar in terms
of penetration depth for cement pastes with the two w/c ratios. Indeed,
as reported earlier, the penetration front is about 4.5 mm (affected
zone) and only the amount of accumulated sulfate ions in the subsur-
face zone [0–2 mm] differs between the two cement pastes. The pene-
tration front kinetics of the sulfate ions is rapidly slowed down after
1 month of exposure to the surrounding solution for both cement pastes
due to self-deceleration. Indeed, the chemical interaction with the hy-
drates can induce the formation of sulfated products in the available
porosity of the cement paste. This could slow the diffusion of ions into
the interstitial solution as long as chemical fixation is possible [33,34].
This interaction occurs as long as the concentrations of calcium, alu-
minium and sulfate in the porosity allow it. Once these elements are
exhausted, the sulfates can penetrate to the following depths.
Fig. 4 compares the measured amounts of sulfates in the case of w/
c = 0.60 to the theoretical one assuming that all C3A and C4AF react
with sulfate to form ettringite (the reaction with dissolved calcium to
form gypsum is neglected in this simulation) and considering the sulfate
ions in the pore solution. In Fig. 4-a, only C3A is assumed to be totally
consumed to form Aft. In this case, a maximum of 6% of sulfate in g/g
of cement paste could be chemically bound to form AFt. Since about 9%
was actually measured, this means that the amount of physically ad-
sorbed sulfate is about 3% in g/g of cement paste or that the sulfate can
be fixed in gypsum. Another explanation is that aluminium can come
from the C4AF phase and allow a chemical fixation of additional sulfate
ions, up to about 9.5% g/g of cement paste (Fig. 4-b). This amount
corresponds to the maximum value measured by ICP on the surface.
However, this approximation depends on the local equilibrium and the
thermodynamics of the system. In areas very close to the surface, the pH
is low favouring the dissolution of the AFt and the likely formation of
the gypsum if the concentrations of calcium and sulfate ions allow it
[9,35,36]. As already mentioned in this study, the pH is 8.0 ± 0.1 and
the ettringite could then decompose to form gypsum. Once the alumi-
nate source is exhausted, ettringite formation stops, so sulfates may
react with calcium ions to form gypsum.
R. Ragoug et al. Cement and Concrete Research 116 (2019) 134–145

Fig. 4. Different sulfate contents of cement paste with w/c = 0.60 after 1 month of exposure to ESA: (a) reaction of only C3A (b) reaction of both C3A and C4AF.

3.1.2. Calcium leaching

In order to quantify the leached calcium in the solution before its
renewal (each week), ICP measurements of calcium concentration in
the baths were performed (Fig. 5-a). The calcium leaching is almost
similar for the two cases of cement pastes. The shape of the curves
reflects a diffusive phenomenon as the concentration of leached calcium
is a function of the square root of time ([Ca2 +] = a· t + b ) as found in
[31]. However, there are two diffusive regimes with different kinetics
for the case of cement pastes with w/c = 0.60: slower and then higher
kinetics. This increase of leaching kinetics can be explained by the high
quantity of calcium ions coming from the CH, the decalcification of C-S-
H or possibly dissolved gypsum. Therefore, the increase of calcium
leaching is favoured by the low value of pH of the exposure solution.
Indeed, this value is lower than that of the interstitial solution equili-
brium which causes dissolution of CH leading to the increase of Ca2+
and OH− ions in the surrounding solution.
On the other hand, Fig. 5-b presents the amount of leached calcium
Fig. 6. CaO content for different depths after 2 months of sulfate exposure.
in solution as a function of the total measured sulfate content for the
case of w/c = 0.60. The curve shows that the value measured at the
surface of about 9% in g/g of cement paste (14% in g/g of anhydrous after 2 months of exposure to the sodium sulfate solution, is measured
cement) corresponds to a saturation value of sulfate ions. Indeed, at this for the first 6 mm of depth. The results presented in Fig. 6 show a de-
value, only the calcium leaching increases without additional fixation crease of the CaO content for the first 4 mm. This result is in line with
process of sulfate. the sulfate front shown in Fig. 3. However, the CaO content for the first
Furthermore, CaO content of the cement paste with 0.60 w/c ratio, depth (0–1 mm), although lower than the core content of the sample,
stays higher than the content for the other “affected” depths. This

Fig. 5. Variation of leached calcium vs. (a) time and (b) sulfate concentration at the surface.

138
R. Ragoug et al.
Fig. 7. Degradation of cement paste with w/c = 0.60 by ESA: (a) after 2 months, (b–c) after 3 months of exposure to sulfate solution.
finding may be explained by the possible interaction between the cal-
cium and sulfate ions at the surface to form gypsum and AFt, which
leads to an overconcentration of calcium ions necessary for these re-
actions. This may also explain the increase in leaching at this time,
since an additional concentration of calcium ions is needed to interact
with the surplus sulfate ions at the surface.
3.1.3. Macroscopic degradation
Fig. 7 illustrates the degradation observed in the case of cement
paste with w/c = 0.60. Longitudinal and transverse cracks appeared
after just two months of exposure to the sodium sulfate solution (Fig. 7-
a). Then after three months of testing, the cement paste has lost all
cohesion and the damage is total (Fig. 7-b and -c). Degradation oc-
curred at the periphery of the cement paste cylinder while the core
remained unaffected. The appearance of transverse cracks is caused by
significant tensile stresses that are rather at the origin of this de-
gradation.
Otherwise, some visual monitoring were carried out on cement
paste with w/c = 0.45 (Fig. 8). Degradation is also observed but is
delayed in time. Indeed, the beginning of the degradation is observed
with the appearance of some cracks and swelling at the edge of the
sample after 6 months of testing. Then, the cracking is followed by a
chipping causing a significant and rapid loss of material. After 8 months
of exposure, the cement paste is totally damaged (Fig. 8-c and -d). Thus,
the degradation is faster in the case of cement paste with a higher w/c
ratio. What is more striking in these observations is the different me-
chanical behaviour of the two cement pastes. This difference suggests
that the mechanical response of the material occurs differently de-
pending on the porosity of the material. The behaviour is possibly
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Cement and Concrete Research 116 (2019) 134–145
related to the process of interaction of the microstructure with sulfate
ions. Here, the pressure exerted by AFt and/or gypsum would be dif-
ferent, depending on where the crystal exerting this pressure is formed
(in which range of porosity).
To explain the mechanisms of the degradations of cementitious
materials by ESA illustrated in Figs. 7 and 8, different theories exist: (i)
the molar volumes of any precipitates (gypsum and AFt) forming in a
hardened paste are about twice as large as the molar volumes of the
initial phases (portlandite and AFm). This simplistic theory implies that
a material with low porosity should degrade more quickly (less space
available to contain the extra volume of hydrates). A comparison of the
observed degradations on the two cases of cement paste in our study
eliminates this hypothesis. (ii) The second theory is based on the
principle of crystallization pressure [37]. According to this theory, two
conditions are necessary to induce mechanisms of expansion within the
hardened material. The first is that the crystal develops from a super-
saturated solution resulting in sufficient energy to induce expansion.
The second condition obeying the mechanics of porous media is that the
crystal develops in a confined space (small enough pore size), and that
it exerts an expansive strength in a pore size range fine enough to in-
duce higher stresses than ultimate tensile strength.
Therefore, the precipitated ettringite or gypsum content resulting
from the sulfate ion supply is not the only cause of the degradation
observed on cement pastes. This seems to be related to the range of pore
and the energy released by the development of the precipitated mineral
to explain the observed cracks.
R. Ragoug et al.
Fig. 8. Degradation of cement paste with w/c = 0.45 by ESA: (a) after 2 months, (b) after 6 months, (c–d) after 8 months of exposure to sulfate solution.
3.2. Chemical aspects of degradation
3.2.1. Characterization of sound materials
As previously described, some investigation techniques were used to
determine the effect of the long curing in water on the reference ma-
terial. TGA was used to quantify the possible surface leaching while the
29
Si NMR was performed to determine the degree of hydration and
structure of the C-S-H chains. Moreover, XRD and 27Al NMR tests are
also carried out for a more complete monitoring of the chemical com-
position of the material.
Fig. 9 presents the results given by XRD analysis for cement paste
with 0.60 w/c ratio after one month and one year of curing in water.
Investigations using this technique were performed on three depths:
0–1 mm, 2–3 mm and 4–5 mm. The main crystallized phase is the por-
tlandite whose peaks become more intense with depth. Traces of et-
tringite are also detected with an additional presence of peaks after
1 year of curing in water. Moreover, some traces of calcite are high-
lighted for all the analysed depths, resulting from low carbonation of
the samples despite the precautions taken to avoid it. Finally, a poorly
defined peak appeared for all the powders tested, corresponding to the
presence of C-S-H.
On the other hand, TGA-DTA curves obtained for the sound cement
paste after one month and one year of curing in water are plotted in
Fig. 10. These techniques give water losses for C-S-H + AFt, AFm, CH
and CC for cementitious materials. The results show a slight difference
in the thermal losses (about 0.76%) between the two curing times.
Thus, dissolution of portlandite occurs between 1 month and 1 year of
curing. However, this dissolution is negligible and can be explained by
the long duration of the curing in water. On the other hand, in the case
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Cement and Concrete Research 116 (2019) 134–145
of water loss for CSH and AFt (maximum respective endothermic peaks
of DTA, at 144.7 °C and 140.7 °C), an important difference is measured
between the two curing times. Indeed, about 8% increase in this loss of
water is measured after 1 year of curing. This increase may be caused by
both a decalcification of the C-S-H and an increase in the AFt content at
the surface. Otherwise, the mass losses relative to the AFm phases
(maximum endothermic peaks of DTA, respectively 199.1 °C and
198.7 °C) seem to have a slight difference of 0.17%, which might sug-
gest that the large increase in water loss corresponding to (CSH + AFt)
is rather driven by decalcification of C-S-H. Finally, no change in the
mass loss related to the calcite (endothermic peaks of 807.8 °C and
814.5 °C respectively). Indeed, this mass loss is about 2.61% and 2.64%
between 1 month and 1 year of curing in water.
Furthermore, low pH and sulfate ingress could affect C-S-H by
changing the C/S ratios and chain lengths [38]. It is therefore necessary
to quantify the C-S-H in order to observe the evolution of the cement
matrix before and after contamination by the aggressive solution. The
results of TGA/DTA exposed above, provide qualitative information on
this evolution of the C-S-H. However, it is necessary to know before-
hand the quantities of ettringite that can be formed by the calcium of
the C-S-H for a quantitative synthesis. It is for this reason that the 29Si
NMR is particularly suitable in this case of study for characterizing and
quantifying the C-S-H phase [39]. Indeed, this technique makes it
possible to determine the chain length change in the C-S-H, their
quantity and the degree of hydration of the anhydrous phases. In ad-
dition, the proportion of aluminium incorporated into the C-S-H can be
also detected by 27Al NMR [39]. Then, by combining these techniques,
it will be possible to calculate the mass percentage of C-S-H in cement
paste.
R. Ragoug et al.
Fig. 9. XRD analysis for cement paste with 0.60 w/c ratio: (a) one month of curing, (b) one year of curing.
The hydration rate of the anhydrous phases concerns only the
progress of the formation of CSH (represented by Q1 and Q2 in 29Si
NMR tests) resulting from the anhydrous phases (represented by Q0).
The 29Si NMR results, shown in Fig. 11-a and concern only the first
depth of the sample (0–1 mm) taken from the surface. The evolution of
the CSH structure (Q1 + Q2) after 24 h of setting, after 3 months and
after 1 year of curing is presented by the various 29Si NMR spectra. The
hydration of the cement paste is almost complete after 1 year of curing
in water (at 3 months a peak relative to anhydrous Q0 is no longer
present). The structure of the C-S-H shows an increase in the peak of the
Q2 chains (long chains) due to a condensation of these hydrates after
curing in water. This result confirms a decalcification of C-S-H by a long
curing in water, which is in line with the results of TGA/DTA observed
previously. This increase in long chains is reflected in the chemical
equilibrium by a decrease in the C/S ratio in the stoichiometry of C-S-H
[38].
The results of DRX and TGA/DTA exposed above provide informa-
tion on the presence of aluminate phases. However, these techniques do
not make it possible to quantify the distribution of these phases. That is
why the 27Al NMR was used.
The evolution of the proportions of the aluminate phases is de-
scribed in Fig. 11-b. In general, the hydration of the CEM I gives a
majority of AFm phases. The AFt rate decreases with curing time in
favour of AFm formation and therefore the AFt/AFm ratio decreases
over time. Silicon-substituted aluminium in C-S-H (Al (IV)) and cal-
cium-substituted aluminium in C-S-H are rebalanced over the course of
the water curing with a slight increase after 1 year of curing. This
Fig. 10. TGA-DTA analysis for cement paste with 0.60 w/c ratio: (a) one month of curing, (b) one year of curing.
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Cement and Concrete Research 116 (2019) 134–145
increase suggests a change in the structure and chemical balance of C-S-
H. This is consistent with the observations of the 29Si NMR results.
Indeed, the decalcification of C-S-H causes an increase in the level of
calcium in solution. Therefore, the C/S ratio and the C/Al ratio are
modified as well as the C-S-H structure.
3.2.2. Chemical fixation of sulfate ions
XRD analysis was coupled with 27Al NMR to follow the evolution of
the aluminate phases after 2 months of exposure to the sodium sulfate
solution (Fig. 12). The results show a change in the mineralogical
composition of the cement matrix. In comparison with the sound ma-
terial, an increase in the intensities of the AFt peaks is highlighted.
Ettringite is thus the main crystallized phase. On the other hand, the
peaks corresponding to the portlandite have their intensity greatly re-
duced. This suggests its dissolution in the interstitial solution leading to
the formation of AFt. In addition, a peak corresponding to gypsum
appeared confirming the coexistence of gypsum and ettringite in the
first zone of the material from the exposed surface. These results are
confirmed by 27Al NMR where the spectrum shows the disappearance of
the AFm peak and the appearance of the AFt one. This confirms that
ettringite is formed after dissolution of AFm given the availability of
calcium and sulfate with adequate concentrations in the solution
(Fig. 13).
Fig. 14 shows the comparison of the microstructure between a
sound and affected cement paste by ESA given by SEM technique. The
application of this investigation method confirms the coexistence of
gypsum and ettringite in the affected samples as detected by other
R. Ragoug et al. Cement and Concrete Research 116 (2019) 134–145

29 27
Fig. 11. NMR spectra for cement paste with 0.60 w/c ratio: (a) Si NMR, (b) Al NMR.

Fig. 12. Determination of phases newly formed by NMR (a) and XRD (b) after exposure of cement paste samples to the sulfate solution.

27
Fig. 13. Al NMR spectrum of the AFm and Aft content during water curing and sulfate exposure.

methods. Moreover, the observations confirm the precipitation of the
pre-stressed AFt in the pores leading to the expansion of the material
and the creation of some micro-cracks in the cement matrix (see Fig. 14-
b).
3.2.3. Dissolution of CH in presence of sulfate ions
The leaching of calcium ions from the cement paste to the sur-
rounding solution, due to the calcium concentration gradient and the
low pH of the surrounding solution, is an important process in the ESA
study. Indeed, this leaching contributes to changes in the local ther-
modynamic equilibrium of the cement matrix. These solid phase
changes are also observed according to the XRD analysis for the sound
cement paste. Fig. 15-a presents the DTA curves for reference and af-
fected samples at the surface zone. Portlandite disappears after
2 months of sodium sulfate exposure (Fig. 15-b). On the other hand, the
endothermic peak corresponding to the chemically bound water of C-S-

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R. Ragoug et al. Cement and Concrete Research 116 (2019) 134–145

Fig. 14. SEM images: (a) sound cement matrix; (b) ESA-affected cement matrix [(1): Pre-stressed Aft, (2): Micro-cracks].

Fig. 15. Quantification of hydrates during ESA: (a) DTA characterization, (b) CH content.

Fig. 16. Changes of C-S-H structure investigated by NMR: (a) spectrum, (b) average lengths of C-S-H chains.

H and AFt increases, highlighting the decalcification of C-S-H and also
the increase of the AFt content. In addition, the DTA curve has a
shoulder around 200 °C confirming the presence of AFm in the case of
sample cured in water. This shoulder disappears after 2 months of
contact with the sodium sulfate solution, which confirms the XRD and
NMR analysis (Figs. 12 and 13). This finding also asserts that AFt's
formation mechanism is carried out in part from AFm. As illustrated in
Fig. 15-b, a progressive consumption of calcium ions from the dis-
solution of the CH over the depth of the sulfate ingress is highlighted.
3.2.4. Change of C-S-H structure during ESA
The 29Si NMR spectra are shown in Fig. 16-a for both cases: the
reference and the exposed samples to the sodium sulfate solution. A
decrease of the peak of short chains Q1 and an increase of that of the
long chains Q2 are highlighted. This change therefore highlights a
modification of the C-S-H structures. The average length of the C-S-H
chains increases to about the value of 10 leading to polycondensation in
the C-S-H structure (Fig. 16-b). This fact is also characteristic of acid
attacks on cement pastes, as shown in [34,40]. Indeed, the dec-
alcification causes a decrease of the C/S ratio and therefore an increase
in the length of the C-S-H chains. This effect is not observed in the case
of exposure to sodium chloride solution [41].
Furthermore, the solid phase's distribution is given in Fig. 17. As
clearly highlighted, the AFt dominates the aluminates phases (total

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Fig. 17. Solid phase's distribution before and after sulfate exposure.
disappearance of AFm). Indeed, the mass content of ettringite is
therefore three times higher after 2 months of samples exposure to the
sodium sulfate solution. On the other hand, the CH content becomes
zero with a 12% increase in the “other” phases that would correspond
to the transformation of portlandite to form gypsum.
4. Conclusions
- The analysis of the physical aspect of ESA shows that two modes of
transfer occur. Sulfate ion transfer to the cement matrix and
leaching of calcium ions to the outer solution which deposits on the
surface. Moreover, this phenomenon is characterized by the coex-
istence of diffusion and physicochemical fixation of sulfate ions in
the cement matrix. In this coupled chemistry-transport process,
diffusion acts as a pilot phenomenon. Indeed, a concentration gra-
dient transfer occurs initially. Then, the sulfate ion transfer is ra-
pidly stabilized and only surface accumulation of sulfate ions is
observed, suggesting that fixation occurs causing self-deceleration of
the ingress as long as the sulfates can react with the cement hy-
drates.
- On the other hand, the analysis of the chemical composition made it
possible to highlight the consumption of the surface portlandite,
until a total consumption after 2 months of exposure to the sulfate
solution. In addition, the decalcification of C-S-H with highly sig-
nificant chain extension is confirmed by the 29Si NMR results. As for
ettringite, it is formed from both AFm and aluminium incorporated
in C-S-H.
- Finally, in the case of low pH exposure, the simultaneous formation
of gypsum and ettringite can be highlighted. The relative propor-
tions of those hydrates are a function of both the free sulfate con-
centration in the pore solution and aluminates and calcium contents.
Acknowledgements
The authors would like to thank the members of Bouygues Society
for its financial and technical support.
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