ACCELERATED SULFATE RESISTANCE TEST FOR CONCRETE -

CHEMICAL AND MICROSTRUCTURAL ASPECTS

Andreas Leemann, Roman Loser

Empa - Swiss Federal Laboratories for Materials Science and Technology, Dbendorf,
Switzerland

Abstract
The sulfate resistance of concrete was tested with an accelerated method using drying-
immersion cycles in Na2SO4 solution. The measured expansion corresponds with the sulfur
ingress in the test specimens. The microstructural analysis indicates that the phase conversion
from monosulfate/monocarbonate to ettringite is related to the observed expansion. However,
the C-S-H of the slag cement system seems to adsorb more sulfur than the C-S-H of the OPC-
system possibly reducing the amount of ettringite formed. The sulfur content in the specimens
and the mineral assemblage present are similar to the ones found in on-site concrete and
specimens used for long-term tests with relatively low concentrated sulfate solution.
Therefore, the test method seems to be applicable for assessing the sulfate resistance of
concrete.

1. INTRODUCTION
External sulfate attack can be defined as the interaction between concrete and sulfate-
bearing groundwater usually leading to a degradation of the cementitious building material. It
is a widely studied reaction in cement and concrete research [e.g. 1-3]. The majority of studies
about sulfate attack on concrete concentrates on laboratory experiments. There are relatively
few studies characterizing sulfate attack on real structures [4-7]. External sulfate attack is a
common phenomenon in Swiss tunnels [7-9]. It mainly occurs at weak areas of the concrete
lining like cracks, cold joints, etc. At these locations, the sulfate reacts with the hydrates
forming ettringite. This reaction leads to expansion and a reduction in the strength of the
concrete eventually causing cracks and spalling. It must be noticed that the failure of the
concrete is always the failure of a system and not the failure of one of its specific components.
Testing the sulfate resistance of concrete usually involves the immersion of specimens in
sulfate solution allowing its ingress by diffusion. The disadvantage of such an approach is a
typical test durations of several months. The determined parameters are generally length and
mass change complemented with a visual assessment and, in the case of research, with
microstructural analysis. These tests are mainly suited to study the mechanisms of sulfate

The 2nd International Conference on Microstructural-related Durability of Cementitious Composites

Amsterdam, The Netherlands, April 11-13, 2012
attack and the cement specific sulfate resistance. However, the construction industry needs a
fast method to test the sulfate resistance of specific concrete mixtures. Based on the results
mix designs are developed to decrease the probability of damages to a given structure in the
future. In addition, such a test has to be used to control concrete production. In connection
with the two Alptransit tunnel projects in Switzerland an accelerated test using drying-
immersion cycles to accelerate sulfate ingress was developed (Swiss standard SN 505262/1).
Currently, a revised method is under development and an extensive testing program is in
progress: the expansion of concrete with various mix designs including different cement types
exposed to sulfate solutions of different composition is measured: The length measurements
are complemented by the determination of concrete properties and microstructural analysis.
This paper focuses on the chemical and microstructural aspects of concrete tested with this
revised method. Concrete mixtures produced with two different water-to-cement ratios (w/c)
and two different cement types are investigated. The sulfate distribution within the tested
specimens and the present hydrate assemblages are analysed using electron microscopy in
combination with EDX.

2. MATERIALS AND METHODS

One cement used was an ordinary Portland cement (OPC / CEM I according to EN 197-1 /
Table 1). The other was an industrially-mixed slag cement containing 20-34% OPC and 66-
80% blast furnace slag, sold as cement with high sulfate resistance (CEM III/B according to
EN 197-1). Two concrete mixtures with a water-to-cement ratio (w/c) of 0.45 and 0.60 and
constant volume of paste were produced with each cement (Table 2). The maximum grain size
of the alluvial gravel aggregates was 22 mm. Concrete flow was measured according to EN
12350-5.

Table 1: Composition of the two cements used.

type abbrev. CaO SiO2 Al2O3 Fe2O3 MgO K2O Na2O SO3 Blaine LOI density
2
[-] [%] [%] [%] [%] [%] [%] [%] [%] [cm /g] [%] [g/cm3]
CEM I 32.5 R PC 63.4 20.3 5.2 3.1 2.5 0.9 0.2 2.4 2840 1.0 3.17
CEM III/B 32.5 N SL 47.6 29.9 9.4 1.6 4.3 0.7 0.1 4.5 5080 0.7 2.94

Table 2: Composition and workability of the concrete mixtures (agg: aggregate, s/g:
sand/gravel-ratio, SP: superplasticizer, VOP: volume of paste).
mixture agg. s/g CEM I CEM III/B water w/b SP VOP flow
3 3 3 3
[-] [kg/m ] [-] [kg/m ] [kg/m ] [kg/m ] [-] [kg/m ] [l/m3] [cm]
3

PC-45 1927 0.54 335 - 150 0.45 1.3 260 47

PC-60 1929 0.54 280 - 168 0.60 - 263 57
SL-45 1928 0.54 - 325 145 0.45 1.3 262 49
SL-60 1923 0.54 - 275 164 0.60 - 264 43

After production, the specimens (cubes 150 x 150 x 150 mm3) were stored at 20C and
90% relative humidity for 24 hours. Afterwards, they were demolded and stored again in the
same climate. At the age of 26 days, seven cores with a diameter of 28 mm und a length of
148 mm were taken from a cube of each mixture. A plug gauge for strain measurements was

The 2nd International Conference on Microstructural-related Durability of Cementitious Composites

Amsterdam, The Netherlands, April 11-13, 2012
glued at their ends. Sulfate resistance of the different mixtures was then determined with a
revised version of the test method described in Swiss standard SN 505262/1 starting at an age
of 28 days. In this revised test, the specimens were first dried in an oven at 50 C for 120 2
hours, followed by storage in a 5% sodium sulfate solution for 48 2 hours (note: duration of
drying and immersion exchanged in relation to the original version of SN 505262/1). This
cycle was repeated another three times (four cycles in total). Afterwards, the cores were
stored in 5% sodium sulfate solution for 8 weeks (no additional immersion in the original
version). During this additional immersion, the length change was recorded weekly.
After the drying-immersion cycles and after the final immersion period, cores were
prepared for the microstructural analysis. A disc was cut from the middle part of the cores,
dried in an oven at 50C for three days, impregnated with epoxy resin, polished and coated
with carbon. The analysis was conducted with an environmental scanning electron
microscope (ESEM-FEG XL30). The samples were studied in the high vacuum mode (2.0-6.0
10-6 Torr) with an accelerating voltage of 15 kV and a beam current of 170-190 A. The
sulfur concentration was determined with energy dispersive X-ray spectroscopy (EDX). An
EDAX 194 UTW detector, a Philips digital controller and Genesis Spectrum Software
(Version 4.6.1) with ZAF corrections was used. At each depth analysed (0.2 mm, 1.0 mm, 2.2
mm, 3.5 mm, 7.0 mm, 10.5 mm, 14 mm), two or three line scans were made, totalling 80
point measurements per depth.

3. RESULTS

3.1 Expansion
While concrete PC45, PC60 and SL45 show little expansion during the drying-immersion
cycles (0.21-0.27 ), concrete SL60 expands considerably (0.89 / Figure 1). However, its
length increase during the additional immersion is in the range of concrete PC45 and SL45
(0.56 compared to 0.27 and 0.77 , respectively). Concrete PC60 expands rapidly in this
period, leading to the failure (breaking apart) of single cores after an additional immersion of
three weeks.
3.0
PC45
2.5 PC60
SL45
2.0 SL60
expansion []

1.5

1.0

0.5

0.0
0 2 4 6 8 10 12
cycles weeks
(additional immersion)
Figure 1: Expansion of the concrete mixtures PC45, PC60, SL45 and SL60.

3.2 Profiles
The differences in the sulfur profile after four drying-immersion cycles and after the
additional immersion are small for all investigated samples (Figures 2a-d). Concrete PC60

The 2nd International Conference on Microstructural-related Durability of Cementitious Composites

Amsterdam, The Netherlands, April 11-13, 2012
shows a higher sulfur content than concrete PC45 at a depth > 1.0 mm. Sodium content is
generally at the level of 2 mass-% or lower except at the edge, where it reaches values up to 4
mass-%. In concrete PC45 and PC60, the content is somewhat lower after the additional
immersion than before. The Ca/Si profile shows some scatter but there is a general trend with
a slight increase in the Ca/Si-ratio at the edge from 2.6 to 2.9 (Figure 3a).
Sulfur content in concrete SL60 is higher at a depth > 1.0 mm than in concrete SL45
similar to the PC-system. However, the highest values in concrete SL60 are not reached at the
edge but in a depth of 1.0-3.5 mm. The sodium content is higher in concrete SL60 than in
SL45. However, contrary to the OPC-systems, the maximum values are reached at a depth of
3.5 mm. Generally, this maximum does not correspond to the maximum in sulfur content. The
scatter in the Ca/Si profile does not permit to clearly identify a trend (Figure 3b). However,
the Ca/Si-ratio seems to drop at the very edge of concrete SL60. With a mean value of 1.9 the
Ca/Si-ratio in the slag cement system is significantly lower than in the OPC-system
displaying a mean value of 2.7.
PC 45 2a PC 60 2b
10 10
S (4cy) S (4cy)
9 9
Na (4cy) Na (4cy)
8 8
content [mass-%]

S (4cy+im) S (4cy+im)
7 7 Na (4cy+im)
content [mass-%]

Na (4cy+im)
6 6
5 5
4 4
3 3
2 2
1 1
0 0
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14
depth [mm] depth [mm]

2c 2d
SL45 SL60
10 10
S (4cy) S (4cy)
9 9
Na (4Cy) Na (4Cy)
8 S (4cy+im) 8 S (4cy+im)
content [mass-%]

content [mass-%]

7 Na (4cy+im) 7 Na (4cy+im)
6 6
5 5
4 4
3 3
2 2
1 1
0 0
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14
depth [mm] depth [mm]

Figures 2a-d: Sulfur (S) and sodium (Na) profiles in the concrete mixtures PC 45, PC 60, SL
45 and SL 60 after 4 drying-immersion cycles (cy) and after the additional immersion of 8
weeks (4cy+im).

The 2nd International Conference on Microstructural-related Durability of Cementitious Composites

Amsterdam, The Netherlands, April 11-13, 2012
 PC 3a 3b
SL
3.5 3
S (4cy) SL45 (4cy+im)
SL60 (4cy) SL60 (4cy+im)
molar Ca/Si-ratio [-]

molar Ca/Si-ratio [-]

3.0
2.5
2.5

2.0
2
1.5 PC 45 (4cy) PC 45 (4cy+im)
PC 60 (4cy) PC 60 (4cy+im)
1.0 1.5
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14
depth [mm] depth [mm]

Figures 3a-b: Molar Ca/Si-ratio versus depth of the concrete mixtures PC45, PC60, SL 45 and
SL 60 after 4 drying-immersion cycles (cy) and after the additional immersion of 8 weeks
(4cy+im).

3.3 Mineral assemblages

The mineral assemblages present in the concrete produced with w/c 0.45 and 0.60 are
principally the same but are present at a different depth in agreement with the sulfur profiles.
As a simplification, only the mineral assemblage of the concrete PC60 and SL60 are
described here (Figures 4a-b).
In the core of sample PC60, monosulfate and ettringite are present beside some portlandite
and the main hydrate phase calcium-silicate-hydrate (C-S-H). In a depth of 10.5, 7.0, 3.5 mm
the same mineral assemblage is found but with an ongoing increase towards the surface of the
sample in the number of points indicating ettringite. Moving even further towards the surface
three things happen: the amount of monosulfate is decreasing, the amount of ettringite is
increasing and the S/Ca-ratio of C-S-H is increasing. Additionally, there are some points at a
depth of 0.2 mm indicating the presence of gypsum. In this area, the Ca/Si-ratio is slightly
decreased.
PC60 (4cy+im) 4a SL60 (4cy+im) 4b
0.6 0.6
Ett 0.2 mm 0.2 mm
Ett
0.5 2.2 mm
0.5 2.2 mm
14.0 mm
14.0 mm
0.4 0.4
T T
S/Ca

S/Ca

0.3 0.3
MS MS
0.2 0.2

0.1 0.1 C-S-H

C-S-H MC MC
0 0
0 0.1 0.2 0.3 0.4 0.5 0 0.1 0.2 0.3 0.4 0.5
Al/Ca Al/Ca
Figures 4a-b: S/Ca-ratio versus Al/Ca-ratio in concrete mixtures PC 60 and SL 60 after the
additional immersion at a depth of 0.2, 2.2 and 14.0 mm.

In the centre of concrete SL60 monocarbonate, monosulfate and C-S-H are present. At a
depth of 10.5 and 7.0, monocarbonate starts to decrease and the S/Ca-ratio of the C-S-H starts

The 2nd International Conference on Microstructural-related Durability of Cementitious Composites

Amsterdam, The Netherlands, April 11-13, 2012
to increase. This increase keeps on to a depth of 1.0 mm. At 3.5 mm from the surface
ettringite appears with increasing occurrence up to a depth of 1.0 mm. At 0.2 mm ettringite is
nearly absent, no monosulfate is present and the Al/Ca-ratio of the C-S-H increases
significantly, while its Si/Ca-ratio decreases.
As described, an increase in the S/Ca-ratio of the C-S-H is observed with increasing sulfur
content of the cement paste both in PC60 and SL60. However, the increase in the slag system
is more pronounced than in the OPC-system, indicating that more sulfur can be bound in the
C-S-H of the former. The S/Ca-ratio of points attributable to C-S-H (Si/Ca-ratio between
0.45-0.60) increases from 0.07 in the centre of the tested cores (concrete PC60) to 0.11 in a
depth of 2.2 mm. The Si/Ca-ratio of C-S-H in the slag cement is slightly higher [10].
Therefore, points with a Si/Ca-ratio between 0.50 and 0.65 are chosen for this comparison; the
S/Ca-ratios in the centre of the specimen (SL60) and at a depth of 2.2 mm are 0.07 and 0.15
respectively.

4. DISCUSSION
As concrete PC60 has a higher porosity and a higher permeability than concrete PC45 it
desiccates more in the drying step [11]. Consequently, it takes up more sulfate during the
immersion step resulting in a higher sulfur content of the paste. The same in regard to
desiccation and sulfate uptake applies to the concrete mixtures SL45 and SL60. Calculating
the sulfate uptake per volume, the concrete with w/c 0.60 takes up about 60% more sulfur
than the concrete with w/c 0.45 and the concrete produced with OPC about 120% more than
the concrete produced with slag cement. These differences are reflected in the measured
expansion after the additional immersion; the concrete with w/c 0.45 expands less than the
concrete with w/c 0.60 and the system with OPC shows more expansion than the system with
slag cement. However, it has to be pointed out that concrete SL60 already shows a relatively
high expansion during the drying-immersion cycles while its expansion during the additional
immersion is relatively low. The opposite applies to concrete PC60; after showing little
expansion during the drying-immersion cycles, it expands rapidly during the additional
immersion. Obviously, there already is a reaction between the hydrate phases and the sulfate
during the drying-immersion cycles leading to expansion. But the kinetics of the process are
too slow to allow a complete reaction. This completion is approached during the additional
immersion. As the amount of available aluminium is higher in the OPC-system it shows a
higher expansion during the additional immersion.
Based on the identification of the mineral assemblages in different depths of the cores the
reactions of the hydrates with the sulfates are comparable in the OPC and the slag cement
systems; monocarbonate and monosulfate are converted to ettringite. This reaction consumes
some portlandite [12]. In both systems the increasing occurrence of points indicating ettringite
goes together with an increase in the sulfur content. However, the higher capacity of the C-S-
H in the slag cement system to adsorb sulfur could have an effect on expansion [13]; due to
this relatively high adsorbtion, less sulfur might be available for the formation of ettringite
resulting in less expansion.
Gypsum is only found at the edge of the samples produced with OPC. However, its
formation is not likely to have a significant effect on expansion in the tested samples due to
its rarety. Based on thermodynamic modelling, gypsum starts to form at a sulfur content of
about 20 mass-% [14]. This value is not reached on average in these samples. Due to an

The 2nd International Conference on Microstructural-related Durability of Cementitious Composites

Amsterdam, The Netherlands, April 11-13, 2012
inhomogeneous sulfur distribution, occasional presence of gypsum seems still possible
locally.
The Ca/Si-ratio at the edge of the samples indicates a minor amount of Ca-leaching in the
OPC, while this process is more pronounced in concrete SL60.
Porous materials can be seriously damaged during drying-immersion cycles in Na2SO4
solution due to the phase transition from thenardite to mirabilite, as tests on sandstone have
shown [4, 15]. Therefore, thenardite/mirabilite formation has to be taken into consideration
when testing concrete with drying-immersion cycles. Thenardite would form during the
drying stage and mirabilite at the beginning of the immersion stage. The sodium levels of all
samples are increased when compared to the composition of the cements. Obviously, sodium
is able to penetrate the entire sample during the test. In spite of this increase, the sodium
concentration in the OPC-system seems to be fairly low, making thenardite/mirabilite
formation unlikely. The sodium concentration in the slag-system is higher. However, the
maximum concentration of sodium does not go together with the maximum of sulfur
concentration. As sodium has to be bound to another counter-ion than sulfate, the probability
of thenardite formation decreases. However, in contrast to the other mixtures, concrete SL60
shows a relatively high expansion during the drying-immersion cycles, where the formation
of thenardite/mirabilite would take place. The reason for this behaviour is not clear but
thenardite/mirabilite formation cannot be excluded entirely. During the additional immersion
sodium concentration is decreasing as it is highly soluble and therefore diffuses into the
sulphate solution to reach equilibrium.
The sequence of the identified phase assemblages in relation to the sulfur concentration in
the concrete is comparable to the one found in structures exposed to sulfate attack [5, 7, 9]
and to the one present in mortar used for long-term tests [12, 16, 17]. Moreover, they agree
with thermodynamic modelling [12, 18]. As such this accelerated test seems to be an
applicable approach to determine the sulfate resistance of concrete.

5. CONCLUSIONS
An accelerated test to assess the sulfate resistance was applied on concrete produced with
OPC and slag cement. In addition to expansion measurements the microstructure of the
concrete and the composition of the mineral assemblages were investigated. The following
conclusion can be drawn:
Expansion increases with increasing w/c.
Concrete with slag cement may expand more than concrete with OPC during the
drying-immersion cycles but expands less after the additional immersion.
The expansion in the OPC and slag cement systems can be attributed to the phase
conversion from monocarbonate/monosulfate to ettrigite.
The C-S-H formed in concrete with slag cement shows a higher capability to
adsorb sulfur than C-S-H formed in the OPC-system, possibly reducing ettringite
formation.
The test specimens produced with slag cement are more prone to leaching during
the test procedure than their OPC counterparts.
The sulfur content in the paste and the formed mineral assemblages are comparable
with the ones in on-site concrete exposed to sulfate attack and mortar used in long-
term test with relatively low concentrations of sulfate solution.

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Amsterdam, The Netherlands, April 11-13, 2012
 Based on the results of this study the test method seems to be applicable to assess
the sulfate resistance of concrete. Due to its relatively short duration it is suited to
survey the production of sulfate resistant concrete.

ACKNOWLEDGEMENTS
The federal road authorities are acknowledged for financing this study, B. Lothenbach and
P. Lura for critically reviewing the manuscript.

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Amsterdam, The Netherlands, April 11-13, 2012