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Cement & Concrete Composites 55 (2015) 364373

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Cement & Concrete Composites


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

Sulfate resistance of cement-reduced eco-friendly concretes


Florian Mittermayr a,,1, Moien Rezvani b,1, Andre Baldermann c, Stefan Hainer b, Peter Breitenbcher d,
Joachim Juhart a, Carl-Alexander Graubner b, Tilo Proske b
a

Graz University of Technology, Institute of Technology and Testing of Building Materials, Inffeldgasse 24, 8010 GRAZ, Austria
Technische Universitt Darmstadt, Fachgebiet Massivbau, Franziska-Braun-Strae 3, 64287 DARMSTADT, Germany
c
Graz University of Technology, Institute of Applied Geosciences, Rechbauerstrae 12, 8010 GRAZ, Austria
d
OBERMEYER Planen + Beraten GmbH, Niederlassung Wiesbaden, Biebricher Allee 36, 65187 Wiesbaden, Germany
b

a r t i c l e

i n f o

Article history:
Received 6 March 2014
Received in revised form 24 September 2014
Accepted 28 September 2014
Available online 13 October 2014
Keywords:
Durability
Degradation
Sulfate attack
Thaumasite
Supplementary cementitious material
Superplasticizer

a b s t r a c t
Two newly developed cement-reduced eco-friendly concretes with high limestone powder content and
low water/powder ratio were tested for sulfate resistance. Mortar samples with a paste composition of
eco- as well as conventional concretes were immersed in 30 g l 1 Na2SO4 and saturated Ca(OH)2 reference solutions for 200 days at 8 C. To evaluate the reaction mechanisms of progressing sulfate attack
a combined approach of mechanical, mineralogical, and microstructural methods was applied.
Gypsum and bassanite neo-formations related linearly to the expansion during sulfate exposure,
except for one sample where ettringite co-precipitated. Thaumasite formation was not observed in spite
of potentially favorable conditions. This is considered to be related to the evolution of the experimental
solutions, kinetic effects, and the competing formation of CaCO3 polymorphs triggered by the usage of
superplasticizer. Both eco-friendly mixes exhibited a better sulfate resistance than their corresponding
reference samples and are therefore suggested to be applicable in low sulfate-loaded environments
according to DIN EN 206-1. Eco-friendly concrete based on CEM III/B performed superior against sulfate
attack and is expected to withstand even severe sulfate exposure despite a much higher water/cement
ratio than required by the standard.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
1.1. Principles of eco-friendly concretes
Recent cement production accounts for approximately 5% of the
global anthropogenic CO2 emissions and thus is a major driving
force for global warming and ocean acidication [1,2]. The majority
of the produced cement is currently consumed by the concrete
industry. Hence, the short- to medium-term decrease of the cement
clinker content in concrete mixtures is suggested to be essential for
the reduction of CO2 emissions connected to the concrete industry.
Such alternative mixtures are referred to as eco-friendly concretes.
They are typically developed based on a promising concept which
includes (i) the application of highly reactive cements, (ii) the
reduction of the water volume and (iii) the introduction of highly
efcient superplasticizers as well as non-reactive, pozzolanic and
latent hydraulic supplementary cementitious materials (SCMs)
Corresponding author. Tel.: +43 316 873 7159; fax: +43 316 873 7650.
1

E-mail address: f.mittermayr@tugraz.at (F. Mittermayr).


First author.

http://dx.doi.org/10.1016/j.cemconcomp.2014.09.020
0958-9465/ 2014 Elsevier Ltd. All rights reserved.

[3,4]. Commercial Portland cement (PC) can therefore be partially


replaced by e.g. limestone powder, y ash, and blast furnace slag
(BFS) in the concrete mixture. Based on this approach a reduction
of more than 30% cement clinker content in comparison to conventional concrete can be achieved, while maintaining the required
mechanical properties and durability of the concrete [3].
The positive effect of SCMs on concrete properties has been studied intensively in the last decades and their application in the concrete industry increased exceptionally [5]. However, the availability
of e.g. reactive y ash and BFS is limited in many countries and the
acquisition is often cost-intensive [6,7]. Therefore an efcient application of reactive SCMs with limited availability contributing to the
concrete performance is required. Currently, limestone powder
additives have received particular attention complying with both
ecological and economic benets and mechanical requirements
[812].
In previous studies newly developed eco-friendly concretes with
reduced cement content and low water/powder (w/p) ratio were
described [3,9,13]. Their resistance against carbonation (exposition
class XC4), slight freezethaw attack (XF1) and water penetration
depth was tested successfully, according to DIN EN 206-1 [14]

F. Mittermayr et al. / Cement & Concrete Composites 55 (2015) 364373

and DIN 1045-2 [15]. Results have shown that these eco-friendly
concretes exhibited similar (or even better) mechanical properties
than the conventional concretes as well as an acceptable durability
against freezethaw attack, water penetration and carbonation
[3,9,13]. Compared to conventional concrete containing ordinary
PC, the global warming potential of the eco-concretes is reduced
by more than 30% and up to 60% [3]. However, the durability of
these concretes against sulfate attack is still in question and therefore the aim of the present study.
1.2. The inuence of sulfate attack on concretes with limestone
During service life concrete elements often come into contact
with sulfate ions that are present in e.g. soil solutions or ground
water. In such sulfate-loaded environments, the formation of
ettringite {3CaOAl2O33CaSO432H2O}, gypsum {CaSO42H2O} and
thaumasite {CaSiO3CaCO3CaSO415H2O} is considered to cause
severe damage on concrete structures [16,17]. At temperatures
P15 C ettringite (Ett) is typically formed and is known to cause
microstructural damage to the cement paste by generating expansive forces, particularly in small pores due to high crystallization
pressure [18,19]. It is generally accepted that aluminate phases
that occur in the cement clinker (C3A and C4AF) support the formation of Ett and hence have a strong inuence on the sulfate-resistance of concrete [20,21]. Ett is often accompanied by gypsum
(Gp) formation which results in further expansion and destruction.
Gp typically forms in high sulfate-loaded environments that are
frequently used for testing of concrete and mortar in the lab
[22,23].
The sulfate resistance of concrete can be strongly improved by
using cement with a low C3A and C4AF content and/or with reactive
SCMs. For instance, Skaropoulou et al. [24] have reported that based
on lab tests mortar specimens with BFS or metakaoline showed a
better performance against sulfate attack than PC based ones independent from their limestone content. Gutteridge and Dalziel [25]
have shown that limestone additives can enhance the concrete
strength by improving the hydration rate and Bonavetti et al. [10]
suggested that limestone may react with alumina phases to form
stable calcium monocarbonate aluminate hydrate. Furthermore,
Matschei et al. [26] have demonstrated that limestone has a significant inuence on the distribution of lime, alumina and sulfate
phases during concrete hydration. Although the addition of limestone can improve the concretes performance, cements with high
amounts of calcium carbonate llers are known to be prone to
the thaumasite form of sulfate attack (TSA). Numerous experimental studies have shown that cementitious materials with limestone
llers are susceptible to TSA, especially at low temperatures
(<10 C) and in high sulfate-loaded environments [2733]. Thaumasite (Tha) formation is typically attributed to progressing decomposition of CSH-phases, but the precipitation rates are expected to
be signicantly lower compared with that of Ett and Gp. Severe
damage of concrete due to intense TSA has also been reported from
various eld sites, where it typically occurs in cold environments
and in underground structures [3441]. In order to evaluate the
resistance of the two newly developed cement-reduced ecoconcretes with high limestone powder contents against sulfate
attack, laboratory experiments were performed by aging standard
test specimens in 30 g l 1 Na2SO4 solution at 8 C for 200 days.
2. Mix design, experimental procedure and methods
2.1. Materials and mix design approach
The sulfate resistance of the aforementioned cement-reduced
eco-friendly concretes and conventional concretes was tested on

365

mortar specimens that were stored under well-dened lab conditions. The mortar mixes are in accordance to the original concrete
mixes without using the aggregate fractions 28 mm and
816 mm [3,9,13]. The mix design of the mortars is shown in
Table 1. In total, four cement-reduced mortars containing limestone powder and y ash as well as three conventional reference
mortars were tested. In order to investigate the effect of the
cement type on sulfate resistance, three normative cements,
namely (I) PC (CEM I 32.5R), (II) Portland-slag cement (CEM II/A-S
52.5 N), and (III) BFS cement (CEM III/B 42.5 N) were used. The
applied limestone powder had a calcium carbonate content
of > 98 wt.%, a median diameter value (D50 volume based) of
15 lm and a Blaine value of 330 m2/kg. The y ash had a similar
grain size but a slightly lower Blaine value of 300 m2/kg. In all
mixtures the CEN standard reference sand (EN 1961 [42]) with
a maximum grain size of 2.0 mm was used.
Mixtures Ref I, Ref II and Ref III, made of the respective cement
types (I), (II) and (III), represent conventional reference mortars
with a water/cement (w/c) ratio of 0.60. This is the maximum value
according to the German standard for concrete (DIN EN 206-1/
DIN 1045-2) for exposure class XA1 with a sulfate concentration
in groundwater of 200 < SO24 6 600 mg l 1. The cement
content of these reference mortars was in accordance with EN
196-1 Methods of testing cement. Mixtures Ref II and Ref III
reect semi-reference mortars which both have a w/p ratio of
0.60 but correspondingly higher w/c ratios of 1.07 and 0.76, respectively. The mix designs of the cement-reduced eco-mortars were
characterized by high limestone powder content and a low w/pratio of 0.35 (Eco II and Eco III). The lower w/p-ratio was chosen
to fulll the concept of clinker-reduced concretes and to attain a
sufcient durability [3]. To maintain the aimed table ow of
180 mm according to DIN 1015-3 [43] the use of a superplasticizer
was necessary for the Eco-mixes. The percentage of cement reduction in these eco-mortars was up to 35% compared to the
corresponding concretes [3].
2.2. Casting, curing, and test procedure
Mortar specimens prisms (40  40  160 mm) and thin
prisms (10  40  160 mm) were fabricated according to EN
196-1 and demolded after 48 2 h. On the basis of the German
Building Authority (DIBt) testing procedure for sulfate resistance
[44], the specimens were pre-cured for 14 days at 20 C in saturated Ca(OH)2 solution. Afterwards, the mortar specimens were
divided into two aliquots, each of which was stored in 30 g l 1 Na2
SO4 and in saturated Ca(OH)2 reference solution at 8 C for
200 days. Distilled water was used for the preparation of the experimental solutions. During the immersion period the volume ratio of
the Na-sulfate and the Ca-hydroxide solutions to the samples was
xed at 6:1. The specimens were placed on plastic spacers about
2 cm above the bottom of the tank. The test solutions were
renewed regularly every four weeks. In order to study the effect
of hydration, the pre-curing time of three specimens of the Eco III
type was extended to 28 days (Eco III-28d), followed by immersion
in Na2SO4 and Ca(OH)2 solutions at 8 C as described above. The
strain development of the thin prisms was measured by means
of a strain gauge with an accuracy of 0.001 mm/m. Two measuring
steel points were xed on both sides of the specimens by using a
chemically resistant epoxy resin. In order to determine changes
in the expansion rate of mortar samples over time, strain measurements were carried out every two weeks on three samples of each
mix.
According to the SVA-guideline [44], mortars with an expansion
60.5 mm/m after 91 days of reaction time indicate a high sulfate
resistance. However, the w/c-ratio of the reference mixes with
regular cement contents was 0.60, instead of a required w/c-ratio

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F. Mittermayr et al. / Cement & Concrete Composites 55 (2015) 364373

Table 1
Mix design for the mortar samples. Cement types are commercially available in accordance to EN197-1.
Mix ID

Ref I

Ref II

Ref III

Ref II

Water/cement
Water/powder
Cement

0.60
0.60
CEM I 32.5R
450

450

450
270

1350

0.60
0.60
CEM II/A-S 52.5 N
405
45
450

450
270

1350

0.60
0.60
CEM III/B 42.5 N
135
315
450

450
270

1350

1.07
0.74
0.60
0.36
CEM II/A-S 52.5 N
262
293
28
32
290
325
80
90
80
256
450
671
270
233

2.9
1350
1350

Type
Clinkera
Slag
Total

Fly ash
Limestone
Total powder
Water
PCE-SP
Sand 02 mm
a

[g]
[g]
[g]
[g]
[g]
[g]
[g]
[g]
[g]

Eco II

Ref III

Eco III

0.76
0.61
0.60
0.35
CEM III/B 42.5 N
102
112
252
286
354
398
48
55
48
236
450
689
270
241

1.6
1350
1350

Denotes all constituents of the cement except for slag. (PCE-SP): polycarboxylatether superplasticizer.

of 0.50. This higher w/c-ratio was used to enable a direct comparison to the Eco-mixes. Furthermore, the temperature was set to
8 C using a climate chamber, instead of 20 C, in order to trigger
TSA. The compressive strength of the mortar prisms was determined after 56 days of storage in the experimental solutions, in
accordance with EN 196-1. Visual inspection and subsequent mineralogical and microstructural investigations were conducted on
the mortar prisms that were immersed for 200 days.
2.3. Mineralogical and microstructural analyses
Prior to the analyses the mortar prisms were dried at 40 C.
Powder X-ray diffraction (XRD) patterns were recorded for mineral
identication. Representative samples were taken and nely
ground in a ball mill for 15 min, together with 10% zincite {ZnO}
as an internal standard. Randomly oriented preparations were
made using the front loading technique and subsequently X-rayed
from 3 to 90 2h with a step size of 0.008 and a count time of 40 s
per step using a PANalytical XPert PRO diffractometer operated at
40 kV and 40 mA. Phase identication was made with the PANalytical XPert HighScore Plus software.
For microstructural analyses, representative sample pieces
were impregnated with epoxy resin under vacuum, followed by
cutting of the samples with a diamond saw and subsequent grinding with diamond grinding wheels, using ethanol cooling and polishing with 3 and 1 lm diamond oil suspensions. Back-scattered
electron (BSE) images were recorded on polished carbon-coated
specimens using a Jeol JXA-8200 SuperProbe electron probe micro
analyzer. For mineral identications semi-quantitative single spot
analyses were performed using the implemented energy-dispersive X-ray spectroscopy (EDX) system operated at 15 kV and 10 nA.
3. Results
3.1. Visual inspection
Typical appearances of mortar samples that were stored in
30 g l 1 Na2SO4 solution for 200 days are pictured in Fig. 1 and
classied in Table 2. In order to evaluate the deterioration level,
the samples were divided into four categories, reecting no damage (0), minor damage (Mi), major damage (Ma), and destroyed
(D). The Ref II and Ref II mortar mixes suffered severe damage
due to intense sulfate attack and were completely decomposed,
while Eco II and Ref I mixes developed a major degree of damage.
Ref III and Ref III showed only some, but rather less pervasive
visual cracks on the surface and were therefore classied into the
minor damage category. Eco III and Eco III-28d offered no
macroscopic damage, suggesting an outstanding sulfate resistance.

3.2. Mechanical properties


3.2.1. Compressive strength
The compressive strength values are presented in Fig. 2. They
were obtained after 14 days of pre-storage of the mortars in a saturated Ca(OH)2 solution and after the immersion period of 56 days in
Na2SO4 solution and in saturated reference Ca(OH)2 solution at 8 C.
Subtraction of the compressive strength values of Ca(OH)2
-immersed mortars from the sulfate-immersed ones yielded in
D-strength values that are reported in Table 2.
As shown in Fig. 3 the CEM II/A-S-based reference mortar
(Ref II) exhibited a compressive strength of 39 N/mm2 after
14 days of pre-storage. This value is signicantly higher than that
of the CEM I and CEM III-based reference mortars (Ref I and Ref III)
with 33 N/mm2. The Ref II and Ref III mixes, characterized by a
constant water content, but reduced cement content, displayed
lower compressive strength values of 2730 N/mm2 compared to
Ref II and Ref III. This behavior reects the increase of the w/c-ratio
from 0.60 to 1.07 and 0.60 to 0.76, respectively. The low w/p-ratio
of Eco III, as a result of water reduction, resulted in an increase of
compressive strength up to 40 N/mm2, compared to Ref III. This
is in contrary to the behavior of Eco II and the corresponding mix
Ref II. Notably, prolonged curing of 28 days (Eco III-28d) strongly
increased the compressive strength to 49 N/mm2 (see Fig. 3).
After 56 days of immersion in a saturated Ca(OH)2 solution a
signicant increase in compressive strength was recognized for
all mortar mixes (see Figs. 2 and 3). Notably, the Eco mixes (Eco II,
Eco III and Eco III-28d) exceeded the compressive strength values
of their corresponding reference mortars. However, after 56 days
of storage in Na2SO4 solution the compressive strength of all mortar mixes decreased up to 7%, except for Ref I, Ref II and Ref II. In
the latter cases the compressive strength was even slightly
improved as indicated with black arrows in Fig. 2 and by positive
D-strength values in Table 2. Interestingly, these mortars also represented the samples with the highest visual damage degree
(Fig. 1) and the largest D-expansion rates after sulfate exposure.
The compressive strength was measured after 56 days because at
this age the strain development of some thin prisms accelerated
signicantly also resulting in incipient macroscopic damage.
3.2.2. Strain
The strain development of thin mortar prisms obtained over a
91 days period is presented in Fig. 4 and the corresponding
D-expansion values are given in Table 2. The D-expansion was
determined by subtracting the strain of mortars that were stored
in saturated Ca(OH)2 solution (as control specimens) from those
immersed in 30 g l 1 Na2SO4 solution. The mortar samples designed
with CEM I 32.5 R and CEM II/A-S 52.5 N showed much higher

F. Mittermayr et al. / Cement & Concrete Composites 55 (2015) 364373

Ref I

Damage level

(Ma)

(D)

Ref II

367

was similar to that of Ref II, as seen in the comparable D-expansion


of about 1.0 mm/m. The lowest strain development was recognized
in the Eco III and Eco III-28d mortars, as indicated by the lowest
D-expansion values of 0.1 and 0.05 mm/m, respectively. It is
considerable that the D-expansion values of all mortars except for
Ref III, that were based on CEM III/B cement fullled the requirements of the SVA-guideline for sulfate resisting cement (<0.5 mm/
m), notwithstanding their higher w/c-ratio.

3.3. Mineralogical composition and microstructural evaluation

Ref II*

(D)

Eco II

(Ma)

Ref III

(Mi)

Ref III*

(Mi)

Eco III

(0)

Eco III-28d

(0)

5 cm
Fig. 1. Mortar prisms after 200 days of immersion in 30 g l 1 Na2SO4 solution at
8 C; Damage levels: (0) no visible damage, (Mi) minor damage, (Ma) major
damage, (D) destroyed.

D-expansions than the mortars made of CEM III/B 42.5 N. Ref I


exhibited the largest D-expansion of 1.5 mm/m among the reference mixtures whereas Ref II and Ref III expanded 1.0 mm/m and
0.55 mm/m, respectively. Ref II displayed a drastic elongation of
4.78 mm/m. Surprisingly, Ref III (0.31 mm/m) exhibited a lower
strain than Ref III despite the higher w/c-ratio. The behavior of Eco II

All mortar mixes were mainly composed of quartz, feldspar, and


amorphous phases with variable concentrations of calcite {CaCO3},
portlandite {CaOH2}, Ett, Gp, bassanite {CaSO40.5H2O} and vaterite
{CaCO3}. The individual proportions of these phases depended
mainly on the original mortar mix design, cement type, and amount
of limestone additives. XRD patterns of Ref I and Eco III that were
immersed in a saturated Ca(OH)2 solution and in a 30 g l 1 Na2SO4
solution for 200 days are presented in Fig. 5. In order to identify mineral alteration and decomposition features of mortars under sulfate
attack the diffracted intensities were corrected to ZnO intensities.
Subtraction of the two XRD patterns from each mortar type resulted
in background free dynamic difference diffractograms, where positive peaks reected mineral gains in terms of mineral neo-formation
and negative peaks corresponded to mineral losses, indicative of
mineral dissolution. Using this approach, Ref I was characterized by
a strong gain of sulfate minerals (D-sulfate + 4.6 wt.%), namely Gp
and bassanite (Bas), and carbonate minerals such as calcite (Cal) and
vaterite (Vtr) (D-carbonate + 3.9 wt.%), while portlandite (CH) was
completely dissolved (see the upper insert box in Fig. 5). In contrast,
Eco III exhibited a high gain of Cal and Vtr (D-carbonate + 4.6 wt.%),
with no signs of sulfate mineral neo-formation, as expressed
by the negative Gp and Ett peaks and the resultant
D-sulfate value of 1.0 wt.% (see the lower insert box in Fig. 5). It
is unlikely that the sulfate minerals have been completely dissolved
in the reacted Eco III mix, but due to the majority of co-precipitated
carbonate this negative D-sulfate value may be explained by a dilution effect due to CaCO3 gain. Notably, Gp and Bas were the most
abundant sulfate minerals in the entire set of mortar samples under
sulfate attack. Ett neo-formation was recognized only in Ref II, the
sample which showed the highest expansion. No evidence for Tha
formation was found in all mortar mixes.
Severe damage and plenty decomposition features such as
intense cracking and leaching were evident in some mortars, as
seen in the BSE images shown in Fig. 6. Obviously, two distinct
but different alteration zones had developed after 200 days of sulfate attack. In the sample interior (depth depending on the sulfate
resistance) a heavily altered sulfate mineral zone, characterized by
intense cracking, has been generated, where Ca-sulfate minerals
(Gp and Bas) were formed particularly in the pressure shadows
of large quartz or feldspar grains. In this zone cracking occurred
mostly parallel to the sample surface as well as in close proximity
to neo-formed sulfate phases. This feature most likely reects
the development of expansion forces during crystallization of
Ca-sulfate minerals. The second alteration zone is characterized
by massive occurrences of calcium carbonate minerals such as
Cal and Vtr that have been precipitated directly on the surface of
the mortars; but they were also formed in the adjoining carbonate
mineral zone. In the transient area between the sulfate mineral
zone and the mortar surface CaCO3 progressively replaced Gp.
Notably, samples with both a lower degree of visual damage and
lower expansion rates (Eco III and Ref III) displayed less evolved
alteration zones compared to the more intensively damaged Ref I,
Ref II and Eco II mortars.

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F. Mittermayr et al. / Cement & Concrete Composites 55 (2015) 364373

Table 2
Damage level degree from visual inspection (see Fig. 1). The D-expansion rate, D-compressive strength, D-sulfate phases (ettringite, gypsum and bassanite) and D-carbonate
phases (calcite and vaterite) were calculated by subtracting the individual parameters of Ca(OH)2 immersed samples from Na-sulfate ones. Negative D-values reect losses and
positive D-values reect gains.

Duration [d]

Damage
200

D Sulfate [wt.%]
200

D Carbonate [wt.%]
200

D Expansion [mm/m]
91

D Strength [N/mm2]
56

Mix ID
Ref I
Ref II
Ref II
Eco II
Ref III
Ref III
Eco III
Eco III-28d

Major
Destroyed
Destroyed
Major
Minor
Minor
No damage
No damage

4.6
2.8
1.7
3.8
1.9
0.3
1.0
0.6

3.9
3.8
0.1
3.7
2.1
1.1
4.6
0.6

1.46
1.01
4.78
0.98
0.55
0.31
0.10
0.05

0.1
2.1
1.5
4.1
3.4
0.9
0.7
0.8

50

5.0
pre-storage Ca(OH)2 14d 20C
after pre-storage Ca(OH)2 56d 8C
after pre-storage Na2SO4 56d 8C

4.5

-expansion [mm/m]

Mortar compressive strength [N/mm]

60

40

30

20

Ref I

Ref II Ref II* Eco II Ref III Ref III* Eco III Eco III
28d

Ref II

Ref II*

Eco II

Ref III

Ref III*

Eco III

Eco III-28d

1.5

1.0

SVA-guideline limit

0.5

10

max. 4.78 mm/m

Ref I

0.0
0

14

28

42

56

70

84

98

Exposure duration [d]


Fig. 2. Compressive strength of mortars after 14 days pre-storage and after 56 days
exposure in Ca(OH)2 and Na2SO4 solutions, respectively. Note that Eco III-28d was
pre-stored for 28 days.

curing
(28 + 56d)

CEM I

-Cem +FA +Cal

-H2O +Cal +SP

curing
(28d)

20

-H2O +Cal +SP

CEM I

-Cem +FA +Cal

30

-H2O +Cal +SP

CEM II/A-S

-Cem +FA +Cal

CEM III/B

50

40

14 + 56d storage in Ca(OH)2

-H2O +Cal +SP

14d storage in Ca(OH)2

-Cem +FA +Cal

compressive strength [N/mm2]

60

CEM III/B

CEM II/A-S

Ref I

Ref II

Ref III

Ref III*

Ref II*

Eco II

Eco III

Eco III-28d

Fig. 3. Evolution of compressive strength of mortars as a function of the mix design


change after 14 days pre-storage and after 56 days immersion in Ca(OH)2. (Cem):
cement; (FA): y ash; (Cal): calcite i.e. limestone; (SP): polycarboxylatether
superplasticizer.

4. Discussion
4.1. Mechanical properties
The increase of compressive strength between 14 days of prestorage and after 56 days of storage in Ca(OH)2 solution can be
attributed to the proceeding formation of hydrate phases in the
matrix. This effect was distinctive for all mortars that contained
latent hydraulic and puzzolane additives like BFS and y ash. After
56 days of sulfate exposure, slight improvements in compressive

Fig. 4. Strain development (D-expansion rate) of mortars during 91 days of


exposure at 8 in 30 g l 1 Na2SO4 and Ca(OH)2 solutions.

strength were recognized for some mortars, i.e. Ref I, Ref II and
Ref II (see Fig. 2), which reected the microstructural densication
of mortars due to the development of expansive products such as
Gp, Ett and Bas [16]. Our results revealed that specimens which
showed increasing compressive strength values after sulfate exposure exhibited also a higher expansion rate after 56 and 91 days.
This behavior leads us to suggest that the initial improvements
in strength went along with negative effects of excessive expansion
of the neo-formed sulfate minerals. Consequently, the compressive
strength results after Ca(OH)2 exposure can be used for the characterization of the mechanical properties of mortars. However, the
evolution of compressive strength of specimens during 56 days of
sulfate attack did not provide reliable information about their sulfate resistance.
Until 56 days of sulfate exposure, all mortar mixes had expansion rates below the SVA-guideline limit [44] of 0.5 mm/m (see
Fig. 4). After 56 days, a signicant expansion was observed for Ref I,
Ref II, Ref II and Eco II mortars whereas the Ref III, Ref III, Eco III,
and Eco III-28d mixes still displayed insignicant expansion until
91 days of sulfate exposure. These observations clearly indicate
that both Portland (CEM I) and Portland slag composite
(CEM II/A-S 52.5 N) cement based mortars were more susceptible
to sulfate attack, compared to BFS based (CEM III/B) ones. From
other studies it is also known that reactive hydration products such
as CH, Ett and other AFm phases can be effectively reduced when
using proper SCMs such as BFS and y ash containing cementitious
materials and thus lowering the risk of the formation of secondary
expansive phases during sulfate attack like Gp and secondary Ett
[5,45]. In our samples Gp had mainly developed in the interface
transition zone (ITZ) around aggregates and in cracks parallel to

F. Mittermayr et al. / Cement & Concrete Composites 55 (2015) 364373

369

Fig. 5. XRD patterns of Ref I (top) and Eco III (bottom) mortars after immersion in 30 g l 1 Na2SO4 and saturated Ca(OH)2 solution for 200 days, respectively. The difference
diffractograms, shown in the inserted boxes, indicate mineral gains and losses related to mineral precipitation versus dissolution during sulfate exposure. The calculated Dsulfate and D-carbonate values are reported in Table 2.

the sample surface (see Fig. 6). Commonly, the ITZ contains the
highest CH contents and a higher porosity than the rest of the
cement paste [46].
The reduction of the cement content and the addition of limestone powder generally did not increase the expansion rates of
the mortars, despite the increase of the w/c-ratio (compare Eco II
vs. Ref II and Eco III vs. Ref III in Fig. 4). Elevated w/c-ratio resulted
in weaker and potentially more porous cementitious matrixes
which were more vulnerable for SO24 ion penetration followed
by the formation of expansive phases [47]. In contrary, the reduced
cement clinker content combined with limestone and y ash led to
an increased resistance against sulfate attack (e.g. Ref III
compared to Ref III). It is suggested that the low w/p-ratios resulted

in a reduced connected porosity and y ash has effectively reduced


the CH content [48,49].
4.2. Mineralogical and hydrogeochemical aspects
Gp, Bas, and in one case Ett were found to be the main
expansive alteration products after 200 days of sulfate exposure.
These phases are considered to have caused the expansion of the
mortars and subsequently led to their damage. Although still
debated in the literature, this study clearly indicates that Gp is
creating expansion [22,23,50]. This is conrmed by the positive
linear correlation between the expansion of the mortars and
their corresponding total gains of sulfate mineral phases, as

cr
ac
ki
ng

Ref I

Na2SO4

in
te
ns
e

Gp

sample surface

F. Mittermayr et al. / Cement & Concrete Composites 55 (2015) 364373

sample surface

370

Eco II

Ca(OH)2

ne
d zo
ache

le

Qz

Qz

Ccsec

Ccsec
Qz
Cal

Ccsec

Qz

Gp

Ccsec

Qz

Qz

Ref II

Gp

Na2SO4

375 m

Eco II

sample surface

sample surface

375 m

Na2SO4
Ccsec
Qz

Pore Gp

Pore Cc

cra

Qz

intense cracking

cki
ng

Ccsec

Cal

Qz

Qz

Ref III
leached zone

Gp

Na2SO4

200 m

Eco III

sample surface

sample surface

375 m

Gp

Na2SO4

Qz

Slag
Ccsec

Qz

Cal

Slag
Fsp

Ccsec

Gp
Qz

Gp
Qz

275 m

Ccsec

crack

425 m

Fig. 6. Back-scattered electron images of Ref I, II, III and Eco II, III obtained after 200 days of exposure in 30 g l 1 Na2SO4 solution. Eco II, stored in saturated Ca(OH)2 solution,
is shown for comparison. Mineral phases identied by EDX: (Gp): gypsum, (Cal): calcite, (Ccsec): secondary calcium carbonate, (Qz): quartz, (Fsp): feldspar (Slag): blast
furnace slag grains. Note that the mortar damage degree is mainly attributed to intense cracking, leaching and widely coincided with the visual degree of damage (Fig. 1).

illustrated in Fig. 7. Ref II was the only mortar where Ett was
formed. This mix had also the highest expansion of 4.78 mm/
m, which was due to the more destructive effect of Ett compared
to Gp [51]. The generally good performance of CEM III/B is
considered to be attributed to a denser microstructure and the

reducing conditions in the pore solutions due to high amounts


of BFS [48,52,53].
Despite potentially favorable conditions for TSA such as high
limestone content in the Eco mixes, low temperature of 8 C and
the usage of highly sulfate-loaded experimental solutions, no

F. Mittermayr et al. / Cement & Concrete Composites 55 (2015) 364373


5.0

4.78 mm/m
ettringite + gypsum attack

-expansion [mm/m]

4.5

Ref I

Ref II

Ref II*

Eco II

Ref III

Ref III*

Eco III

Eco III-28d

1.5
R = 0.90

1.0

ck

ite
san

nd

a
sum

0.5

atta

bas

gyp
0.0
-1.5

-0.5

0.5

1.5

2.5

3.5

4.5

5.5

-sulfate phases [wt.%]


Fig. 7. Relation between the maximum expansion rates (D-expansion rate obtained
after 91 days) of sulfate exposure and the total gain and loss of sulfate minerals (Dsulfate phases after 200 days) in the respective mortar mixes (see Table 2).

evidence for Tha formation was found in any of the samples. The
lack of Tha can be explained by (i) its slow reaction rates, (ii) the
chemical composition and the evolution of the experimental solution, which promoted the precipitation of other Ca-sulfates and Cacarbonate minerals, and (iii) the role of polycarboxylate-ether
superplasticizer (PCE). In the following these assumptions are
elucidated.
In contrast to Tha formation, large amounts of neo-formed
CaCO3 polymorphs (Cal and Vtr) were identied. These carbonates
are commonly found in association with high pH solutions (up to
13) that occur in e.g. tunnel drainages [54]. Tha is stable at high
pH but also at lower pH values (down to about pH 8) but it possess
slow reaction kinetics and is therefore known to occur particularly
during the last stages of sulfate attack [27,32,55,56]. In the present
study, the 200 days of sulfate exposure were possibly not sufcient
to trigger Tha formation.
Another critical point is that under real eld exposure conditions, pure sodium sulfate solutions are never present. In natural
surroundings, mixtures of solutions containing different aqueous
complexes, speciations and dissolved cations and anions are considered to have decisive effects on Tha formation and sulfate attack
in general [55,5759]. Furthermore, cyclic events such as multiple
drying and wetting cycles induce strong enrichments in major and
trace element concentrations within the interstitial and pore solutions. Such processes typically enhance the formation of destructive mineral phases such as Tha and thus result in the more
rapid degradation of concrete, as demonstrated by thermodynamic
calculations, lab experiments and eld observations [47,48,55].
We can only speculate about the pore solution compositions
and crucial ion content of Ca2+, SO24 , CO23 , and silica, which are
required for Tha precipitation, but it is evident that Ca-sulfate minerals and carbonate minerals were formed and Tha formation was
suppressed. For this reason, the absence of Tha in our samples is
expected to be also attributed to the evolution of the chemical
composition of the experimental solution (i.e. ion leaching, -xation and changes in pH). Additionally the formation of CaCO3 polymorphs such as Cal, aragonite and Vtr [6062] and Tha [6366] is
strongly inuenced by organic substances. In our case, it is suggested that the PCE used in the Eco-mixtures had played an important role on controlling CaCO3 versus Tha formation.
PCEs are well known to strongly attach to positively charged
cement particles but also interact with negatively charged ions
such as SO24 in the pore solution, thereby affecting e.g. Ett formation during early hydration [6770]. Lothenbach et al. [53] did not
nd Tha in CEM III/B-SiO2 based paste samples after 3.5 years

371

where PCE was used, even though Tha formation was predicted
by thermodynamic modeling. Blanco-Varela et al. [64] investigated
the effect of organic admixtures during Tha synthesis. In the four
experiments where PCEs were used, Tha was inhibited while other
organics favored its formation.
Since in our experiments all mortar specimens were placed
together in the same containers with Na2SO4 and Ca(OH)2 solutions, it is assumable that organic molecules from the PCE were
present in the solutions and pore uids during the whole immersion period [53]. In these highly alkaline immersion solutions even
small amounts of organics can affect dissolved silica speciation
[7173]. For example partial removal of aqueous silica from the
experimental solution by adsorption onto organic molecules might
have interfered with the formation of Tha. Additionally the formation of CaCO3 polymorphs has acted as a competing reaction for
Tha precipitation that lowered the Ca2+ and CO23 concentration
in the experimental solution. Consequently it seems doubtful that
dissolution of limestone ller can occur, which would serve as a
potential carbonate source for Tha formation, because we had
found neo-formations of CaCO3 [28,74,75].
4.3. Exposure classication and application
The prediction of the performance of concrete in real practice
exposure based on laboratory-controlled accelerating tests on mortar specimens could be associated with some uncertainties. Potential variations are, for example, the higher SO24 concentrations
and/or the dened temperature prole used in conventional accelerating tests, which commonly leads to the formation of mineral
phases others than that observed in the eld and consequently noncomparable expansion rates and deterioration mechanisms. Thus,
the suitability for accurate prediction of the sulfate resistance of
concrete based on accelerating tests is challenging and should be
veried. The results presented in the previous chapters indicate that
Gp and in particular Ett were the driving forces for the deterioration
in the presence of sulfate-rich solutions, as seen in Figs. 1 and 7. Their
formation is known to cause severe damage on concrete structures.
Portland and Portland slag cement based mixtures Ref I, Ref II
and Ref II exhibited a generally low resistance against sulfate
attack. Thus, the application of these mixtures in highly sulfate
loaded environments is not recommended. However, the application in low sulfate environments (XA1) with 200 < SO24 6
600 mg l 1 is acceptable according to DIN EN 206-1/DIN 1045-2.
The cement-reduced mortar Eco II had shown a better sulfate resistance than the reference mortar Ref II with w/c = 0.60. According to
the equivalent performance concept for concrete properties
(DIN EN 206-1), a mixture like Eco II, with a w/p-ratio lower than
0.35, a compressive strength of more than 40 N/mm2 and a limestone content lower than 35% of powder, should be acceptable
for exposure class XA1.
In spite of a higher w/c-ratio than specied by the SVA-guideline
[44] Ref III, Eco III and Eco III-28d developed less than 0.5 mm/m
expansion and thus passed the test. Consequently, these concretes
are suggested to withstand moderate sulfate attack (XA2) with sulfate concentrations from 600 < SO24 6 3000 mg l 1, according to
DIN 1045-2/EN 206-1. Since the expansion rates of Eco III and
Eco III-28d were exceptionally low, concretes with such a paste
composition (w/p 6 0.35; slag P 40% of powder; limestone 6 35%
of powder; fc P 45 N/mm2) are probably suitable for application
in concrete structures that can be exposed to severe sulfate attack
(XA3), with concentrations from 3000 < SO24 6 6000 mg l 1.
5. Conclusion
Based on the results from cement-reduced eco-friendly mortars
(Eco II and Eco III) and reference mixes the following conclusions

372

F. Mittermayr et al. / Cement & Concrete Composites 55 (2015) 364373

and recommendations for cement-reduced eco-friendly concrete


can be drawn:
(i) A good correlation between expansion rate and visual damages was observed for all specimens, whereas assessing the
damage levels by means of residual compressive strength
was not benecial.
(ii) Elevated D-sulfate phase values correlated linearly with
increasing D-expansion rates for samples that contained
Gp and Bas. The appearance of both Ett and Gp caused a
much higher expansion.
(iii) Despite of potentially ideal conditions such as the presence
of limestone nes in the eco-mixes, the low temperature
of 8 C and immersion of the samples in highly sulfatebearing solutions, no Tha was detected after 200 days of
reaction time. This is believed to be related to the evolution
of the experimental solutions, the slow reaction kinetics of
Tha formation, the competing effect of Cal and Vtr precipitation, and/or the presence of organic molecules originating
from the PCE-based superplasticizer.
(iv) The cement-reduced mortars Eco II and Eco III showed less
expansion after 91 days of exposure in 30 g l 1 sodium sulfate solution compared to their corresponding reference
mortars. However, the expansion rates of BFS-based mortar
mixes were signicantly lower than those of the CEM I and
CEM II/A-S based mortars.
(v) Eco-friendly concretes with high limestone powder contents
but low water (w/p 6 0.35) and cement clinker content are
appropriate for application in environments with low sulfate
concentrations (XA1), according to DIN 1045-2/EN 206-1.
The application of BFS-based limestone-rich mortars with
low w/p-ratio (w/p 6 0.35) in moderate sulfate-loaded environments (XA2) is possible and a sufcient durability of
these concretes even under severe conditions (XA3) is also
achievable, especially after a prolonged curing period.
Acknowledgement
The authors greatly acknowledge the helpful comments by Josef
Tritthart.
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