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DOI 10.1617/s11527-008-9356-z
ORIGINAL ARTICLE
Received: 17 June 2007 / Accepted: 10 January 2008 / Published online: 22 January 2008
RILEM 2008
Abstract The worldwide shift towards performancebased standards for concrete demands the advent of
performance tests that combine more than one damage
mechanism. Such tests can be more reliable in
evaluating emerging concrete types such as selfconsolidating concrete (SCC). Several applications
of SCC involve its exposure to both freezingthawing
cycles and chemical attack, particularly to sulphaterich media. This study aims at investigating the
durability of SCC to sulphate attack coupled with
frost action. Potential performance risks of SCC under
this dual exposure were identified in terms of various
mixture design parameters. Deterioration in physicomechanical parameters was related to thermal, mineralogical and microscopy analyses, which demonstrated
the complex mutual effects of sulphate attack and frost
action on SCC specimens. It is shown that SCC mixtures
that perform well under the classical ASTM C 1012 test
can fail under coupled exposure to freezingthawing
cycles and sulphate attack.
Keywords Sulphate attack
Freezingthawing cycles Performance-based tests
Standards Self-consolidating concrete
1 Introduction
1.1 Frost action
Frost action is among the prominent durability problems of concrete structures in cold climates.
Deterioration of cement-based materials due to freezingthawing cycles has been ascribed to hydraulic [1]
and osmotic [2, 3] pressures. The migration of supercooled water from small to large pores has been
attributed to the difference in vapour pressure [4], or
diffusion due to high free energy [5]. Supercooled water
will migrate from small pores to locations in the outer
surfaces and/or larger pores, which contain ice, to be
able to freeze [4, 5]. Eventually, the gradual build-up of
ice in capillary pores exerts tensile stresses, and
consequently micro-cracking of the cement paste [15].
All the aforementioned theories [15] agree that
repeated freezingthawing cycles cause internal
cracks of cement paste, which grow larger at each
freezing cycle and are subsequently filled with water
during thawing cycles leading to more rapid deterioration. Litvan [6] pointed out that during freezing
thawing cycles, de-icing salts aggravate frost action.
Once concrete is saturated with a saline solution,
evaporation will only commence at a relatively lower
relative humidity, leading to high moisture content,
which explains the severe frost damage associated
with de-icing salts.
The role of air-entrainment in improving the
resistance of concrete to frost action has been well
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established and recommended by national and international building codes. Yet, the need for airentrainment in high-performance concrete (HPC)
remains a subject of controversy [7]. Other factors
that affect the resistance of concrete to frost action
include the degree of saturation, quality of aggregates, water-to-cementitious materials ratio (w/cm)
and curing [5].
2
2SO2
Ca4 Al2 (OH)12 SO4 6H2 O
4 2Ca
! Ca6 Al2 (OH)12 (SO4 )3 26H2 O
The above equations indicate the possible decomposition of CH and CSH leading to softening along
with expansion. Hydroxyl ions (OH-) may leach
away to the surrounding solution resulting in a pH
increase. In the case of alkali sulphates, alkali ions
such as Na+ may migrate to the pore solution, which
increases the risk of alkali-aggregate reaction. Pozzolanic cements with limited portlandite content and
sulphate resistant cements with low C3A content (less
2 Research significance
Concrete deterioration under either sulphate attack or
frost action has been extensively described in the
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3 Experimental programme
3.1 Materials
Twenty one SCC mixtures with a w/cm of 0.38 were
prepared using single, binary (two component),
ternary (three component) and quaternary (four
component) binders. The mixtures were divided into
three groups: Group A (non-air-entrained SCC with a
sand-to-total aggregates mass ratio [S/A] of 50%);
Group B (air-entrained SCC mixtures with S/A of 40
and 60%); and Group C (air-entrained SCC with fibre
reinforcement and sand-to-total aggregates plus fibres
mass ratio of 50%). The binders used included CSA
Type 10 (ASTM Type I) ordinary portland cement
(OPC), CSA Type 50 (ASTM Type V) sulphate
resistant portland cement (SRPC), silica fume (SF),
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SRPC
Silica fume
Fly ash
Slag
Limestone filler
SiO2 (%)
19.8
22.3
94.0
48.9
35.0
0.3
CaO (%)
63.2
63.8
0.4
3.8
36.1
Al2O3 (%)
5.0
3.5
0.1
23.3
11.2
Fe2O3 (%)
MgO (%)
2.4
3.3
4.0
2.8
0.1
0.4
14.9
0.7
0.5
11.4
K2O (%)
1.2
0.4
0.9
1.7
0.5
SO3 (%)
3.0
2.1
1.3
0.2
3.3
Na2O (%)
0.1
0.1
0.1
0.6
0.5
TiO2 (%)
0.3
0.3
0.6
CaCO3 (%)
99.0
2.5
0.9
4.7
0.3
410
377
19,530
280
468
3,200
Specific gravity
3.17
3.15
2.12
2.08
2.90
2.70
C3S
61
54
C2S
11
23
C3A
C4AF
14
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Binder code
Cement (kg) Silica fume (kg) Slag (kg) Fly ash (kg) Limestone (kg)
100% SRPC
SRPC
470
100% OPC
A1, B1 or C1 470
92% OPC, 8% SF
A2, B2 or C2 430
40
A3, B3 or C3 235
25
210
95
70
70
25
120
90
A5, B5 or C5 235
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Mix. ID
Steel fibres
(kg)
Polypropylene
fibres (kg)
Fine
aggregate (kg)
Coarse
aggregate (kg)
Air-entraining agent
(ml/100 kg of binder)
SRPC
SRPC
870
870
A1
A1-N50
870
870
A2
A2-N50
860
860
A3
A3-N50
855
855
A4
A4-N50
845
845
A5
A5-N50
840
840
B1
B1-A-40
B1-A-60
655
1,015
1,015
655
45
35
B2
B2-A-40
640
990
70
B2-A-60
990
640
50
B3-A-40
640
985
70
B3-A-60
985
640
60
B4-A-40
625
970
110
B4-A-60
970
625
95
B5-A-40
625
965
120
B5-A-60
965
625
100
C1
C1-A-H
30
830
805
40
C2
C2-A-H
30
825
795
60
C3
C3-A-H
30
820
790
65
C4
C4-A-H
30
805
780
100
C5
C5-A-H
30
800
775
105
Group A
Group B
B3
B4
B5
Group C
Yt
100
YLt
Yi
where
YLt = REd at time t or RF upon termination of
experiments (%)
Yt = Ed at time t (kHz2), or final flexural strength
at the end of exposure (MPa)
Yi = Initial Ed (kHz2), or flexural strength before
exposure (MPa).
To analyse the reaction products associated with
damage, differential scanning calorimetry (DSC) at a
heating rate of 10C/min was conducted on powder
samples passing #200 sieve (75 lm) collected from
1663
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Table 4 Results of expansion, REd and mass gain for specimens immersed in the sodium sulphate solution for up to 20 months
Mix. ID
12 Months
Expansion (%)
20 Months
REd (%)
Expansion (%)
REd (%)
Group A
SRPC
0.02
109
0.62
0.02
108
0.51
A1-N-50
0.04
106
0.61
0.05
106
0.40
A2-N-50
0.02
107
0.65
0.02
109
0.71
A3-N-50
0.01
107
0.63
0.02
107
0.63
A4-N-50
0.02
109
0.57
0.03
109
0.64
A5-N-50
-0.01
108
0.23
0.00
108
0.22
B1-A-40
0.02
107
1.01
0.04
106
1.09
B1-A-60
0.02
106
1.18
0.03
108
1.37
B2-A-40
0.02
107
0.88
0.02
107
1.05
B2-A-60
0.03
108
1.10
0.04
107
1.41
B3-A-40
0.01
109
1.00
0.02
108
1.04
B3-A-60
0.02
108
0.78
0.02
107
0.76
B4-A-40
B4-A-60
0.02
0.02
109
107
0.38
0.36
0.03
0.02
109
107
0.35
0.27
B5-A-40
0.05
109
0.77
0.05
109
0.79
B5-A-60
-0.01
109
0.76
0.00
110
0.85
C1-A-H
0.03
107
0.96
0.04
107
1.08
C2-A-H
0.02
106
1.03
0.03
106
0.55
C3-A-H
0.02
109
0.92
0.02
109
0.78
C4-A-H
0.01
111
0.55
0.02
112
0.64
C5-A-H
0.02
110
0.74
0.02
110
0.87
Group B
Group C
were better controlled and their intensity was discounted or diminished. Corrosion of surface steel
fibres could be observed (Fig. 2d). Yet, specimens
made with blended binders and incorporating hybrid
fibres had more surface scaling compared to that of
corresponding specimens without fibres (compare
Fig. 2dc).
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70
Before Exposure
After Exposure
60
Enthalpy (J/g)
50
40
30
20
10
0
SRPC
A1-N-50
A2-N-50
A3-N-50
A4-N-50
A5-N-50
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120
(a)
100
SRPC
REd (%)
80
A1-N-50
60
A2-N-50
A3-N-50
40
A4-N-50
20
A5-N-50
0
0
50
100
150
200
250
300
350
400
Number of Cycles
120
(b)
100
B1-A-40
B1-A-60
B2-A-40
B2-A-60
B3-A-40
B3-A-60
B4-A40
B4-A-60
B5-A-40
B5-A-60
REd (%)
80
60
40
20
0
0
50
100
150
200
250
300
350
400
450
500
Number of Cycles
120
(c)
100
C1-A-H
REd (%)
80
C2-A-H
C3-A-H
60
C4-A-H
40
C5-A-H
20
0
0
50 100 150 200 250 300 350 400 450 500 550 600 650
Number of Cycles
1667
120
Group B
480 Cycles
Group C
610 Cycles
99
Group A
350 Cycles
85
100
43
60
C2-A-H
58
56
54
45
39
46
44
37
29
40
C1-A-H
61
75
60
52
RF (%)
80
14
120
C5-A-H
C4-A-H
C3-A-H
B5-A-60
B5-A-40
B4-A-40
B4-A-60
B3-A-60
B3-A-40
B2-A-60
B1-A-60
B2-A-40
B1-A-40
A5-N-50
A3-N-50
A2-N-50
SRPC
Fig. 5 Relationship
between relative dynamic
modulus of elasticity,
relative flexural strength
and expansion
A 1-N-50
A4-N -50
14
20
0.7
RF
Expansion
0.6
100
RF(%)
0.4
60
0.3
40
Expansion (%)
0.5
80
0.2
20
0.1
0
0
20
40
60
80
100
0
120
RE d (%)
5.1.4 Expansion
The results of expansion for specimens from groups
A, B and C after the dual exposure are shown in
Fig. 6. Generally, the results of expansion corresponded well with the REd and RF results (Fig. 5).
An expansion beyond about 0.2% coincided with a
marked drop in REd below 60%. In group A,
ANOVA showed that variation in the type of binder
affected the mean of the expansion results since it had
an F value of 10.56, which is larger than the
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0.8
Group B
480 Cycles
Group C
610 Cycles
0 .6 1
Group A
350 Cycles
0.33
0.28
0.2 1
0.26
0.36
0.38
0.1 0
0.12
0.18
0.15
B2-A-60
0.2 5
0.17
0.09
0.10
0.0 8
0.09
0.2
B2-A-40
0.2 1
0.26
0.34
0.4
0 .2 2
Expansion (%)
0.6
Fig. 7 Development of
expansion of air-entrained
vs. non-air-entrained
specimens
C4-A-H
C5-A-H
C3-A-H
C1-A-H
C2-A-H
B5-A-60
B5-A-40
B4-A-60
B3-A-60
B4-A-40
B3-A-40
B1-A-40
B1-A-60
A4 - N- 50
A 5 -N -5 0
A3 - N- 50
A2-N -50
A1-N -50
SRPC
0.25
B5-N-50
B5-A-60
Expansion (%)
0.2
0.15
0.1
0.05
0
0
100
200
300
400
500
600
Number of Cycles
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5.2 Discussion
5.2.1 Effect of binder type
It is well-documented that repeated freezingthawing
cycles can cause surface scaling of cement-based
Fig. 8 A typical behaviour
of mass change vs. the
number of cycles for group
A specimens
3
2.5
2
1.5
1
0.5
0
0
50
100
150
200
-0.5
SRPC
-1
A1-N-50
-1.5
A2-N-50
-2
A3-N-50
A4-N-50
-2.5
A5-N-50
-3
Number of Cycles
250
300
350
400
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0.2
A1-N-50
SRPC
-0.2
-0.4
-0.6
-0.8
0
100
200
300
Temperature (C)
400
500
600
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E = Ettringite
G = Gypsum
P = Portlandite
D = Dolomite
Q = Quartz
Th = Thenardite
C = Calcite
Q
D
SRPC
P
E
C
D
Th
C
QD
A1-N-50
10
15
20
25
30
35
40
Fig. 11 (a) An SEM micrograph showing gypsum formation on the surface of a specimen prepared with 100% SRPC, and (b) an
BSEM micrograph showing acicular ettringite at a deep region (12 mm from the surface) of a specimen prepared with 100% OPC
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0.2
A1-N-50
A2-N-50
A3-N-50
0
A4-N-50
A5-N-50
-0.2
-0.4
-0.6
-0.8
0
100
200
300
Temperature (C)
400
500
600
1673
E = Ettringite
T = Thaumasite
G = Gypsum
P = Portlandite
D = Dolomite
Q = Quartz
Th = Thenardite
C = Calcite
C
Q
C
G
Th
ET
Q
Th
G
E
10
15
D
T
20
25
30
35
40
1674
1675
1676
6 Conclusions
With the growing use of SCC in various infrastructure applications exposed to combined sulphate
attack and frost action, it has become necessary to
investigate the suitability of a wide range of SCC
mixture designs to such environments. Considering
the mixture designs, concentration and type of
sulphate solution and the combined testing approach
implemented in the present study, the following
conclusions can be drawn:
E = Ettringite
G = Gypsum
P = Portlandite
D = Dolomite
Q = Quartz
Th = Thenardite
C = Calcite
C
Q
G
C
C
C
E
E
E
Th D
10
15
Th
Th
E
Q
20
25
30
35
Th
40
1677
E = Ettringite; G = Gypsum)
(Th = Thenardite)
with
salt
crystallization
With time, accumulation of sulphate attack reaction products together with salt crystallization in
air voids had detrimental effects under prolonged
exposure with the risk of a sudden failure,
especially for specimens prepared with blended
binders that did not tend to scale off.
While the effect of increasing sand-to-aggregate
ratio was only notable in maintaining the mechanical properties of the SCC specimens, the
incorporation of hybrid (micro- polypropylene
with macro-steel) fibres achieved an overall
improvement of the durability of group C specimens due to an effective control of cracking that
discounted the damage.
Based on the present study, the following qualitative failure limits are suggested as damage
indicators for similar high-performance concretes
under dual exposure of sodium sulphate and frost
action after 350 cycles: a maximum expansion of
1678
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