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Materials and Structures (2008) 41:16571679

DOI 10.1617/s11527-008-9356-z

ORIGINAL ARTICLE

Durability of self-consolidating concrete to combined effects


of sulphate attack and frost action
M. L. Nehdi M. T. Bassuoni

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

M. L. Nehdi (&)  M. T. Bassuoni


Department of Civil and Environmental Engineering,
The University of Western Ontario, London, Ontario,
Canada
e-mail: mnehdi@eng.uwo.ca

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].

1.2 External sulphate attack


Dissolved sulphate salts can enter into chemical
reactions with cement-based materials causing expansion, cracking and spalling, and/or softening and
disintegration. Hence, the action of sulphates on
concrete has been a key durability issue, and a subject
of extensive investigation for many decades [8]. The
classical form of sulphate attack involves alkali
sulphates such as sodium sulphate (Na2SO4), which
reacts with portlandite (CH) and monosulphate and

unreacted C3A to form gypsum (C-S-H)
and ettringite

(C-A-S-H), which can cause expansion, cracking, and
deterioration of concrete. Yet, the exact mechanism of
expansion and the role of gypsum and ettringite in the
deterioration process remain subjects of controversy
[9]. Santhanam [10] pointed out the role of gypsum
formation in the expansion and deterioration of
cementitious matrices under external sulphate attack.
Brown and Taylor [11] reviewed the mechanisms
(topochemical growth, through-solution reactions,
oriented crystal growth, etc.) by which ettringite can
cause disruptive pressures in cement-based materials.
Migration of SO2
4 ions into concrete causes the
following chemical reactions:
2
SO2
2H2 O ! CaSO4  2H2 O
4 Ca

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

than 8%) have high resistance, but are not completely


immune to alkali sulphates [8, 9].

1.3 Dual damage: sulphate attack and frost action


Although there are numerous studies in the open
literature both on sulphate attack and frost action on
concrete, there is dearth of information on their
combined effects. To investigate the premature
failure of concrete pavements in Wisconsin, Detwiler
and Powers-Couche [12] used rapid freezethaw tests
following the ASTM C 666 procedure A guidelines
on concrete mixtures similar to that of the deteriorated pavements. In these tests, 3% sodium chloride
contaminated with traces of gypsum was used instead
of water. Some mixtures had ordinary cement with
additional gypsum to increase the content of sulphates (internal sulphate attack). The study showed
no evidence of sulphate attack, and the prevailing
damage mechanism was the classical frost action on
improperly air-entrained concrete, which was caused
by the additional gypsum incorporated in some
mixtures [12].
Miao et al. [13] investigated the combined effect
of sodium sulphate (external sulphate attack) and
rapid frost action on non-air-entrained fibre-reinforced concrete using the ASTM C 666 procedure A,
except that 5% sodium sulphate was used instead of
water. The study confirmed the superior physicomechanical behaviour of fibre-reinforced concrete
specimens compared to that of normal concrete even
under dual damage mechanisms. Unfortunately, the
study did not include microstructural analysis to
explain the real mechanisms behind the results and
whether the damage process was similar to that
reported by Detwiler and Powers-Couche [12].

1.4 Self-consolidating concrete and sulphate


attack
Self-consolidating concrete (SCC) readily flows and
consolidates under its own weight with little or no
vibration. It is particularly suitable for precast
applications, hard-to-reach areas and heavily reinforced sections. The mixture design of SCC usually
incorporates an efficient superplasticizer, relatively
high amounts of fine materials, low water-to-powder

Materials and Structures (2008) 41:16571679

ratio, and controlled proportions of coarse aggregates


with adequate particle size and gradation. Viscositymodifying admixtures can be used in SCC to enhance
stability of the flowable material and inhibit segregation and bleeding [14]. Hence, the fresh properties
and rheological characteristics of SCC are different
than that of normal concrete, but both SCC and
normal concrete may exhibit comparable mechanical
properties if designed for similar strength grades. Yet,
due to the difference in mixture design, placement
and consolidation techniques, the durability of SCC
may be different than that of normal concrete, and
thus needs thorough investigation [15, 16].
Persson [17] investigated the resistance of SCC to a
solution of 1.8% Na2SO4 at a temperature of 5C up to
900 days. The SCC concrete mixtures incorporated a
cement content of 409427 kg/m3, high amounts of
limestone filler (94375 kg/m3), water-to-cement ratio
(w/c) of 0.39 and entrained air content of 58%. Some
SCC mixtures immersed in the Na2SO4 solution
suffered significant mass loss without a corresponding
decrease in internal fundamental frequency. This was
ascribed to the mixing sequence since limestone filler
was introduced last during the mixing stage, which
may have caused inadequate dispersion of limestone
particles in the matrix. Therefore, loose limestone
particles at the concrete surface were in direct contact
with the sulphate solution leading to surface scaling
[17]. Nehdi et al. [18] evaluated the sulphate resistance
(ASTM C 1012 Standard Test Method for Length
Change of Hydraulic-Cement Mortars Exposed to a
Sulphate Solution) of environmentally efficient SCC
prepared with high-volume replacement binary (two
component), ternary (three component) and quaternary
(four component) composite cements and water-tocementitious materials ratio (w/cm) of 0.38. Bars of
mortar extracted from SCC mixtures were immersed in
a 5% Na2SO4 solution to observe the length change
with time for 9 months. It was observed that quaternary SCC mixtures made with 50% OPC, 24% Class F
fly ash or slag, and 6% silica fume or rice husk ask had
the lowest expansion compared to that of other
mixtures [18].

2 Research significance
Concrete deterioration under either sulphate attack or
frost action has been extensively described in the

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open literature. Yet, there is a dearth of information


on the coupled effects of these prominent damage
mechanisms. In real field exposure, the damage of
concrete structures often occurs due to a multitude of
mechanisms (e.g. chemical and physical attacks)
acting in a synergistic manner. For instance, several
concrete elements such as pavements, shallow foundations and partially embedded structures can be
vulnerable to sulphate attack combined with frost
action. There is a need to develop performance tests
that combine multiple damage mechanisms to
improve the understanding of their mutual effects
on concrete, and hence allow a better modelling of
the life-cycle performance of structures. Such tests
can also better assess the performance of emerging
concrete types such as SCC, which involve many
variables such as the use of composite cements (e.g.
ternary and quaternary) with a considerably larger
volume fraction of supplementary cementitious materials (SCMs). The present study responds to this need
by investigating the resistance to the combined attack
of sodium sulphate and frost action of a wide range of
SCC mixtures incorporating single, binary, ternary
and quaternary binders, with and without fibre
reinforcement. The effects of the coarse aggregate
volume fraction (a key parameter in the mixture
design of SCC) and air-entrainment were also
explored. The study should contribute to the move
towards performance-based specifications and durability-based design of concrete structures.

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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to enhance the stability of the SCC mixtures. The


dosages of HRWRA and VMA were adjusted to
maintain a slump flow of 650 30 mm and L-box (3
10 mm bars with 50 mm gaps) ratio (H2/H1) not
less than 0.70 for all mixtures. A multi-component
synthetic air-entraining admixture (AEA) based on
tall oil, with a specific gravity of 1.01, was used in
groups B and C mixtures to obtain a fresh air content
of 5 1%, while achieving the target slump flow and
L-box values.
In group C mixtures, micro-reinforcement of
polypropylene fibrillated fibres with a specific gravity
of 0.91 and graded length, complying with ASTM C
1116 (Standard Specification for Fibre-Reinforced
Concrete Type III 4.1.3), were added at a single
dosage of 0.1% by volume. In addition, macroreinforcement of crimped steel fibres, complying with
ASTM A 820 (Standard Specification for Steel Fibres
for Fibre-Reinforced Concrete), with a specific gravity of 7.85, length of 38 mm, aspect ratio of 34, and
tensile strength of 9661,242 MPa were used at a
dosage of 0.4% by volume. Based on trial mixtures,
these fibre shapes, lengths, and low volumes of
micro- and macro-fibre reinforcement have proven
adequate for achieving the characteristic flowability
and passing ability of SCC with minimal clustering of
fibres.

Class F fly ash (FA), slag (S), and limestone filler


(LF). The chemical and physical properties of the
various binders are listed in Table 1. Single binders
were 100% OPC (control) or 100% SRPC, binary
binders contained 92% OPC and 8% SF, and ternary
binders contained 50% OPC, 5% SF and 45% S.
Quaternary binders comprised 50% OPC, 15% LF,
20% S and 15% FA, or 50% OPC, 5% SF, 25% S and
20% FA.
The total cementitious materials (binder) content
was kept constant at 470 kg/m3 to provide a relatively
high volume fraction of fine materials (paste volume
of 325350 l/m3), conforming to common SCC
mixture design guidelines [e.g. 19]. The fine aggregate was natural siliceous sand with a fineness
modulus of 2.80, a saturated surface dry specific
gravity of 2.65 and water absorption of 1.5%.
Crushed stone (mostly siliceous gravel with a fraction
of limestone aggregate) with a maximum nominal
size of 19 mm, a saturated surface dry specific
gravity of 2.68 and water absorption of 0.8% was
also used. A polycarboxylate-based high-range waterreducing admixture (HRWRA) with a specific gravity
of 1.07 and a solid content of 43% was incorporated
in all mixtures. A viscosity-modifying admixture
(VMA) based on a solution of modified polysaccharide with a specific gravity of 1.0 was also employed
Table 1 Chemical and physical properties of cement and SCMs
OPC

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

Loss on ignition (%)

2.5

0.9

4.7

0.3

Specific surface area (m2/kg)

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

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3.2 Experimental procedures


Constituent materials were mixed in a mechanical
mixer in accordance to the ASTM C 192 (Standard
Practice for Making and Curing Concrete Test
Specimens in the Laboratory). Tables 2 and 3 show
the proportions of the tested SCC mixtures. For each
mixture, replicates of 75 9 75 9 285 mm concrete
prisms were prepared without compaction. All specimens were demolded after 24 h and moist cured at
20C and 95% RH for 56 days. A reference exposure
was similar to that for ASTM C 1012 [20] (Standard
Test Method for Length Change of HydraulicCement Mortars Exposed to a Sulphate Solution) in
which specimens were fully immersed in a 5%
sodium sulphate solution up to 20 months. The
temperature of the solution was maintained around
20 2C. The solution was renewed each 18 weeks,
and the pH was controlled at a range of 6.08.0 by
titration with diluted sulphuric acid solutions at
regular time intervals (5 days). Regular stirring was
conducted to allow for a homogenous distribution of
the solution. While controlling the pH of the sulphate
solution was not specified in the ASTM C 1012, the
importance of a controlled pH (6.08.0) of a sulphate
solution correlates to field conditions in which
concrete exists in a neutral environment with continual supply of sulphate ions [9].
A second exposure involved concomitant chemical
and physical attacks: sodium sulphate and frost
action. This simulates conditions for concrete elements under external sulphate attack and seasonal
temperature changes in cold climates. Prismatic
specimens were fully immersed for 2 days in a 5%
sodium sulphate solution followed by 2 days of
freezing at -18C. After 365 days (approximately
90 freezingthawing cycles), the procedure was
accelerated. Specimens were subjected to successive

freezingthawing cycles interrupted by wetting and


drying periods. A full exposure cycle consisted of
5 days of immersion in 5% sodium sulphate solution
at 20C, 5 days (26 freezingthawing cycles) in an
automated freezingthawing cabinet adjusted to the
ASTM C 666 procedure A [21] (Standard Test
Method for Resistance of Concrete to Rapid Freezing
and Thawing in Water) expect that a 5% sodium
sulphate solution was used instead of water, and
2 days of drying at 20C and 50% RH. Subsequent to
the initial 90 freezingthawing cycles, the predetermined number of accelerated cycles for specimens
from groups A, B and C were selected to be 10, 15
and 20 cycles, respectively. This is equivalent to 350,
480, and 610 freezingthawing cycles, respectively.
Replacement of solutions and pH control was done
similar to the initial full immersion exposure.
Before exposure, the initial physico-mechanical
properties of specimens were determined. For all
specimens, the initial mass, length (ASTM C 1012),
dynamic modulus of elasticity, Ed (ASTM C 215 [22]
Standard Test Method for Fundamental Transverse,
Longitudinal, and Torsional Resonant Frequencies of
Concrete Specimens, calculated as the square of the
fundamental transverse frequency according to the
ASTM C 666 guidelines), and flexural strength
(ASTM C 78 [23] Standard Test Method for Flexural
Strength of Concrete [Using Simple Beam with
Third-Point Loading]) were recorded to calculate
the change in mass, length and Ed versus time of
exposure, and the residual flexural strength at the end
of dual exposure conditions, respectively.
Specimens were removed from the sulphate solutions at specified time intervals, and the length of
prisms was immediately measured. Subsequently,
debris, if any, were removed by a nylon brush, and
the specimens were left to dry under 20C and 50%
RH for 30 min before visual inspection and

Table 2 Proportions of binders per cubic meter of concrete


Binder description

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

50% OPC, 5% SF, 45% S

A3, B3 or C3 235

25

210

95

70

70

25

120

90

50% OPC, 15% LF, 20% S, 15% FA A4, B4 or C4 235


50% OPC, 5% SF, 25% S, 20% FA

A5, B5 or C5 235

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Table 3 Proportions of groups A, B and C mixtures per cubic meter of concrete


Binder code

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

measurement of mass and fundamental transverse


frequency. The cumulative change of mass and length
at each time interval were calculated by


Xt  Xi
XLt
 100
3
Xi
where
XLt = Change of mass or length at time t (%)
Xt = Mass or length at time t (kg, mm)
Xi = Initial mass or gauge length before exposure
to sulphate solutions (kg, 250 mm)
The change in Ed (REd) and flexural strength (RF)
after exposure relative to their initial values were
calculated by

 
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

Materials and Structures (2008) 41:16571679

the surface (within a range of 015 mm from the


exposed surface) of selected specimens. To complement the results obtained by DSC, X-ray diffraction
(XRD, Cu-Ka) was conducted on the same powder
samples. To further assess the deterioration of the
microstructure, polished sections were prepared for
optical microscopy. Backscattered and secondary
scanning electron microscopy (BSEM, SEM) with
energy dispersive X-ray analysis (EDX) were also
used on selected thin sections and fracture surfaces to
supplement the findings of optical microscopy.

4 Exposure I: sodium sulphate attack


Table 4 lists the results of expansion, change in
dynamic modulus of elasticity (REd) and mass gain
for the SCC specimens immersed in the sodium
sulphate solutions after 12 and 20 months. Even after
20 months of immersion, specimens had a relatively
low expansion that did not exceed 0.05 %. REd
showed a small but consistent increase with time
(maximum of 12%). The expansion and increase in
REd were accompanied by a slight (about 1%)
increase in the mass of specimens.
The results suggest that the rate of damage for the
SCC specimens immersed in the sodium sulphate
solutions was slow. At 12 months, which is the
exposure interval recommended by the ASTM C
1012, there was a general increase in mechanical
properties due to solution absorption and filling of
voids with reaction products as suggested by previous
studies [e.g. 10, 24]. Despite the relatively high
concentration (33,800 ppm SO2
4 ) of the sulphate
solution used, specimens did not show any evidence
of softening or significant expansion. According to
the Frearsons [25] criterion for evaluating the
sulphate resistance of concrete based on expansion,
sulphate resistant concrete shows an expansion in the
range of 00.05% after 12 months of exposure. A
higher acceptance limit is set by ASTM C 1012
which allows an expansion of up to 0.10% after
12 months of immersion in a 5% sodium sulphate
solution [20]. For blended binders subjected to Class
3 sulphate exposure (more than 10,000 ppm SO2
4 ),
ACI 201.2R (Guide to Durable Concrete) permits an
expansion of up to 0.10% after 18 months of
exposure following the ASTM C 1012 procedure
[26]. Hence, the SCC mixtures studied herein can be

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classified as sulphate resistant based on all of the


preceding performance criteria.
In addition, the mechanical properties of tested
specimens were not affected as indicated by the
results. This behaviour can be physically correlated to
the low penetrability of this type of high-performance
concrete (w/cm 0.38, and high powder content) that is
produced without vibration (homogenous microstructure), and the chemical resistance of the type of
cementitious materials used, particularly those incorporating pozzolanic additions or containing SRPC.
Blended binders used in this study were designed
to discount the CH content in the hydrated cementitious matrix, thus improving the resistance to alkali
sulphates. From a mixture proportioning perspective,
there is a dilution effect of cement especially at a
high replacement level (50%) in ternary and quaternary binder mixtures compared to only 8% in the
binary mixture. SCMs react with CH and water to
produce CSH (pozzolanic reaction). Increasing the
replacement level of OPC by SCMs is inversely
proportional to the amount of CH formed in the paste.
This is depicted by the DSC results in Fig. 1, where
enthalpies of CH for the ternary and quaternary
binder mixtures were significantly lower than that of
the binary and control mixtures. Thus, blended binder
matrices with lower portlandite contents can reduce
the potential for gypsum formation when exposed to
alkali sulphates (Eq. 1). Based on the performance of
the SCC mixtures in the ASTM C 1012 test, they can
qualify for use in severe exposure to alkali sulphates.
Yet, whether those mixtures can maintain their
performance when frost action is also involved, and
what could be the mutual effects of sulphate attack
and frost action on those cementitious matrices are
aspects not captured by the ASTM C 1012 test that
need to be investigated.

5 Exposure II: sodium sulphate and frost action


5.1 Experimental results
5.1.1 Visual inspection
After the termination of the tests of dual exposure to
sodium sulphate and freezingthawing cycles, specimens incorporating various binders could be
distinguished based on visual features. The control

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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 (%)

Mass gain (%)

Expansion (%)

REd (%)

Mass gain (%)

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

Notes: SRPC: 100% sulphate resistant portland cement


A1, B1, or C1: 100% OPC. A2, B2, or C2: 92% OPC + 8% SF. A3, B3, or C3: 50% OPC + 5% SF + 45% S. A4, B4, or C4: 50%
OPC + 15% LF + 20% S + 15% FA. A5, B5, or C5: 50% OPC + 5% SF + 25% S + 20% FA
N: non air-entrained, A: air-entrained
50, 40, 60: S/A is 50%, 40% and 60%, respectively
H: hybrid fibres

specimens made with 100% OPC suffered notable


surface scaling on all of their faces, along with
disintegration at the edges accompanied by significant swelling and transverse macro-cracks (Fig. 2a).
Specimens made with 100% SRPC were quite intact
with moderate surface scaling and minor pop outs and
no evidence of significant expansion (Fig. 2b).
Unlike the control specimens, specimens made
with blended (binary, ternary and quaternary) binders
did not exhibit severe surface scaling. Transverse
macro-cracks were the principal feature of failure of
those specimens that suffered damage (e.g. Fig. 2c).
When fibre reinforcement was used, tensile cracks

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).

5.1.2 Relative dynamic modulus of elasticity (REd)


The change in REd should capture any internal
damage of concrete specimens exposed to chemical

Materials and Structures (2008) 41:16571679

1665

70
Before Exposure
After Exposure

60

SRPC = 100% SRPC


A1 = 100% OPC
A2 = 92% OPC+8% SF
A3 = 50% OPC+5% SF+45% S
A4 = 50% OPC+15% LF+20 S
+15% FA
A5 = 50% OPC+5% SF+25% S
+20 FA

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

Fig. 1 DSC results for CH peaks at about 440C

and/or physical attack. The results of change in REd


versus the number of freezingthawing cycles for
groups A, B and C specimens are shown in Fig. 3ac,
respectively. Up to 100 freezingthawing cycles,
specimens from all mixtures consistently showed
slight increase in the REd. Subsequently, a decreasing
trend in REd was observed till the termination of
experiments. Some specimens showed complete
disintegration or failure by transverse macro-cracks,
which was expressed by zero REd. This is clearly in
contrast with the results of ASTM C 1012 exposure
discussed earlier.
For group A specimens, the type of binder had a
pronounced effect on the REd results. This is
supported by the analysis of variance (ANOVA) at
a significance level a = 0.05. ANOVA of the REd
results showed that variation of the type of binder had
Fig. 2 Specimens made
with (a) 100% OPC, (b)
100% SRPC, (c) 50%
OPC + 15% LF + 20%
S + 15% FA, and (d) 50%
OPC + 15% LF + 20%
S + 15% FA and hybrid
fibres

an F value of 7.6, which is larger than the


corresponding critical F value of 4.3. According to
Montgomery [27], exceeding the critical value of an
F-distribution density function reflects that the tested
variable affects the mean of results. After 350
freezingthawing cycles, the control SCC (A1-N50) specimens from mixtures prepared with 100%
OPC failed the 60% REd threshold recommended by
ASTM C 666 guidelines for durable concrete subjected to freezingthawing cycles. Conversely, SRPC
specimens from mixtures prepared with 100% sulphate resistant portland cement had a consistently
high REd above 100%. Specimens from mixtures
made with binary binders (B specimens) and ternary
binders (T specimens) showed comparable behaviour
over the time of exposure (Fig. 3a) with REd values
of 100 and 87%, respectively. On the contrary,
specimens from quaternary binders (Q specimens)
fell short of the 60% limit, though with varying
degrees, depending on the proportions and combinations of the quaternary binder. In particular, Q
specimens (A4-N-50) made with 50% OPC, 15%
LF, 20% S and 15% FA were markedly deteriorated
at about 180 freezingthawing cycles with a durability factor of 30% (Fig. 3a).
Figure 3b shows that air-entrained SCC specimens
sustained a higher number of combined sulphate
attack/freezingthawing cycles than that of corresponding non-air-entrained SCC specimens from
group A mixtures. Except for the Q specimens (B4A-40 and B4-A-60), no single specimen had a drop in

1666

Materials and Structures (2008) 41:16571679

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

sudden manner at 480 cycles. The binder effect


varied with the S/A level. At S/A of 40%, only the B
specimens (B2-A-40) passed the REd 60% threshold
after 480 cycles, whereas the control, T and Q
specimens failed this limit, though with varying
degrees. At S/A of 60%, only the Q specimens (B5A-60) passed the REd 60% limit, while the other
mixtures failed this limit after 480 cycles. Similar to
the quaternary binder specimens (A4-N-50) without
air-entrainment, air-entrained specimens from the
quaternary binder mixture incorporating 50% OPC,
15% LF, 20% S and 15% FA (B4-A-40 and B4-A-60)
failed the 60% limit at a lower (around 240) number
of cycles than that of the other mixtures.
Group C specimens had REd values in the range of
5090% after 610 cycles (Fig. 3c). Generally, airentrained specimens with hybrid fibre reinforcement
did not exhibit a high intensity of macro-cracks
despite being exposed to a higher number of cycles.
Apparently, the role of the different binders was
masked by the effect of the fibre reinforcement. The
decline in REd was generally gradual, and at some
stages showed a plateau with no sudden drop as
observed for groups A and B specimens. The results
indicate that using hybrid fibres, even at a low
volume of 0.5%, generally reduced the degradation of
SCC specimens made with various binders under
coupled sulphate attack and frost action, in comparison to corresponding specimens from groups A and
B mixtures.

C3-A-H

60

C4-A-H
40
C5-A-H

5.1.3 Relative flexural strength (RF)

20
0
0

50 100 150 200 250 300 350 400 450 500 550 600 650

Number of Cycles

Fig. 3 Relative dynamic modulus of elasticity vs. the number


of cycles for groups (a) A, (b) B, and (c) C specimens. Notes:
SRPC: 100% sulphate resistant portland cement. A1, B1, or
C1: 100% OPC. A2, B2, or C2: 92% OPC + 8% SF. A3, B3,
or C3: 50% OPC + 5% SF + 45% S. A4, B4, or C4: 50%
OPC + 15% LF + 20% S + 15% FA. A5, B5, or C5: 50%
OPC + 5% SF + 25% S + 20% FA. N: non-air-entrained, A:
air-entrained. 50, 40, 60: S/A is 50, 40 and 60%, respectively.
H: hybrid fibres

REd below 60% prior to 400 freezingthawing cycles.


The prolonged dual exposure showed that some
specimens, irrespective of the binder type, failed in a

Average results of the relative flexural strength (RF) at


the end of the dual exposure are shown in Fig. 4. The
ranges of RF for groups A, B and C specimens were
099%, 061%, and 4375%, respectively. Specimens
that showed wide transverse cracks generally had little
or no measurable flexural strength. No specimens with
fibre reinforcement (group C) had completely disintegrated or broken after the dual exposure. At the end of
exposure, there was evidence of flexural strength loss
indicated by a softening of specimens. Generally, RF
results agreed well with the observed REd trends
(Fig. 5), confirming the internal damage of specimens.
An RF of 50% corresponded to REd of less than 60%.
Such an observation paves the way for performance
testing based on multiple damage mechanisms.

Materials and Structures (2008) 41:16571679


Fig. 4 Relative flexural
strength at the end of the
dual exposure

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

corresponding critical F value of 4.38. Specimens


from mixture SRPC showed a low expansion of
0.09%, whereas the Q specimens (A4-N-50) had the
highest expansion of 0.34%, corresponding to zero
REd and RF. The B (A2-N-50) and T (A3-N-50)
specimens had lower expansion values comparable to
that of the SRPC specimens.
Using air-entrainment in group B mixtures
reduced the expansion of specimens compared to
that of the corresponding non-air-entrained specimens from group A. This improvement depended on

1668

Materials and Structures (2008) 41:16571679

Fig. 6 Expansion results at


the end of the dual exposure

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

the type of binder and S/A. Air-entrained specimens


exhibited delayed expansion and/or tolerated higher
expansion at failure than that of the corresponding
non-air-entrained specimens. For example, Fig. 7
shows delayed and lower (43% reduction) expansion
of air-entrained Q specimens (B5-A-60) relative to
the corresponding non-air-entrained specimens (B5N-50) made from the same quaternary binder.
Comparatively, at failure, the Q specimens (B4-A40 and B4-A-60) had higher expansion values of 1.1
and 1.8, respectively, relative to the expansion value

of the corresponding non-air-entrained specimens


(A4-N-50) from group A, which was 0.34%. The S/A
had a mixed effect on expansion results for group B
mixtures.
Figure 6 illustrates that hybrid fibre-reinforced
SCC specimens could sustain an expansion well above
0.2% under a prolonged dual exposure of up to 610
cycles. High expansion of those specimens did neither
correspond to a marked intensity of macro-cracks nor a
significant decline in mechanical properties. For
mixtures comprising hybrid fibres, the effect of the

Materials and Structures (2008) 41:16571679

1669

materials, especially with the existence of dissolved


salts [8]. Visual inspection and mass loss results
showed that such a phenomenon can also occur, when
sodium sulphate solutions are coupled with freezing
thawing cycles. The severity of surface scaling
depended on the type of binder. Apparently, specimens prepared with 100% OPC were more vulnerable
to surface scaling than that of specimens from binary,
ternary and quaternary binders. The resistance to
surface scaling is in part a function of the outer skin
quality, which is correlated to absorption, capillary
porosity and characteristics of the aggregate/paste
interfacial transition zone (ITZ).
Blended binders, especially those with multicomponent SCMs of variable particle sizes and
reactivity presumably produce a dense and discontinuous pore structure due to complementary physical
filling and pozzolanic effects. As pointed out by Dhir
et al. [28], absorption tests may reflect the quality of
the concrete surface pore structure based on the rate
of water uptake. Water absorption tests were conducted for selected SCC mixtures based on the
guidelines of ASTM C 1585 (Standard Test Method
for Measurement of Rate of Absorption of Water by
Hydraulic Cement Concrete) [29] to determine the
initial sorptivity indices for specimens prepared with
blended and control binders. Water absorption tests
showed that blended binders had up to 45% less water
uptake (2.25 9 10-6 g/mm2/s1/2) than that of control

binder type on expansion results was masked, likely


because it was offset by the effect of fibres.

5.1.5 Mass change


Figure 8 shows a typical behaviour of mass change of
SCC specimens under the dual (sulphate attack-frost
action) exposure. Specimens from all SCC mixtures
initially had a slight gain in mass followed by a
decreasing trend at later stages of the test. The final
mass for some specimens was slightly lower than the
corresponding initial value before exposure (maximum mass loss of 2%), but no severe mass loss was
observed. The trends of mass change primarily
depended on the cementitious materials type with
marginal effects of S/A and fibre reinforcement.
Specimens from single binders prepared with 100%
OPC tended to lose more material at their surfaces in
comparison to other specimens from blended binders
(Fig. 2).

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

Mass Change (%)

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

1670

Materials and Structures (2008) 41:16571679

specimens prepared from 100% OPC (sorptivity of


5 9 10-6 g/mm2/s1/2). The absorption of 100% OPC
specimens likely increased the uptake of the sodium
sulphate solution in the surface skin, which gradually
became supersaturated. Subsequently, precipitation
and crystallization of sodium sulphate led to series of
osmotic pressures resulting in progressive removal of
the concrete skin in a manner similar to that of
conventional de-icing salts.
DSC analysis on powder samples from group A
specimens showed endothermic peaks of CH, which
were considerably lower in magnitude than their
initial values before exposure as indicated by the
enthalpy values in Fig. 1. Consumption of CH is
primarily attributed to the chemical reaction with the
sodium sulphate solution. Also, DSC results indicated
the potential coexistence of gypsum and ettringite by
the wide dehydroxylation peaks around 100C. This
implied intermixed reaction phases, which could not
be differentiated in DSC curves. The separation of
reaction phases by DSC is more complex when
thaumasite (CaSiO3  CaCO3  CaSO3  15H2O) is
also formed. Figure 9 shows that specimens prepared
from 100% OPC and 100% SRPC had comparable
enthalpies of CH and intermixed ettringite-gypsum
phases (13.15 and 13.83 J/g, respectively). XRD
showed similar diffractorgrams (Fig. 10) for both
binders. Gypsum was the dominant reaction product,
while ettringite appeared as a trace element in the

Fig. 9 DSC curves for


100% OPC and 100%
SRPC after the dual
exposure

100% OPC specimens. SEM (e.g. Fig. 11a) also


confirmed gypsum formation on the surface of
specimens from mixtures incorporating both binders.
Comparatively, in deeper regions of specimens (more
than 10 mm from the surface), acicular ettringite
clusters (e.g. Fig. 11b) were only observed in specimens from mixtures prepared with 100% OPC. The
absence of ettringite in specimens from SRPC was
likely due to its lower C3A content.
DSC curves (Fig. 12) showed quite similar enthalpies for powder samples from single (A1-N-50) and
B (A2-N-50) specimens (13.83 and 13.81 J/g, respectively). Nevertheless, the B specimens performed
much better in terms of physico-mechanical parameters than that of specimens from 100% OPC
specimens. Surface scaling and the progressive
removal of reaction zones from the surface 100%
OPC specimens might have caused this inconsistency
between the abundance of reaction products and
physico-mechanical behaviour. Due to the absence of
surface scaling in blended binders, deterioration in
the physico-mechanical parameters could be correlated to the quantity of reaction products represented
by intermixed phases. For instance, powder samples
from the Q (A4-N-50) specimens had the highest
enthalpy of 21.21 J/g at the wide peak area (Fig. 12)
corresponding to inferior physico-mechanical measurements. Conversely, samples from the B (A2-N50) and T (B3-N-50) specimens had enthalpies of

0.2
A1-N-50
SRPC

Heat Flow (W/g)

-0.2

-0.4

-0.6

-0.8
0

100

200

300

Temperature (C)

400

500

600

Materials and Structures (2008) 41:16571679


Fig. 10 XRD for powder
samples from 100% OPC
and 100% SRPC after the
dual exposure

1671

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

13.81 and 9.6 J/g, respectively corresponding to good


physcio-mechnical measurements. Similar trends
were observed for group B specimens as severely

deteriorated specimens had high enthalpy at the wide


peak area (e.g. powder samples from Q (B4-A-40)
specimens had an enthalpy of 54 J/g at a temperature

1672

Materials and Structures (2008) 41:16571679

Fig. 12 DSC curves for


group A specimens after the
dual exposure

0.2
A1-N-50
A2-N-50
A3-N-50
0

A4-N-50

Heat Flow (W/g)

A5-N-50
-0.2

-0.4

-0.6

-0.8
0

100

around 101C). Generally, the extent of damage and


its relation to the formed reaction products depended
on the synergetic effects of sulphate attack and frost
action as will be explained later in the text.
As discussed earlier, blended binders were
designed to limit the attack of alkali sulphates.
According to the classical ASTM C 1012 evaluation
criteria, all mixtures can qualify for use in severe
sulphate exposure environments. However, some of
these binders failed to perform adequately under the
dual sulphate attack/freezingthawing exposure due
to different considerations. In groups A and B, Q
specimens prepared from 50% OPC, 15% LF, 20% S
and 15% FA (A4-N-50, B4-A40 and B4-A-60)
constantly showed inferior physico-mechanical
parameters, when exposed to the dual exposure.
The use of limestone powder in SCC is known to
improve flowability and rheological characteristics.
Except for surface scaling that was ascribed to the
sequence of mixing, data from Persson [17] showed
no adverse effects of using limestone filler in SCC
specimens immersed in 1.8% Na2SO4 maintained at
low temperature (5C) up to 900 days. Conversely,
data from this study show a different effect of
limestone powder at a higher sodium sulphate
concentration combined with freezingthawing
cycles. DSC curves showed that Q specimens
containing 15% limestone powder had the highest
enthalpy values at the intermixed peak region compared to that of other mixtures in groups A and B.

200

300
Temperature (C)

400

500

600

XRD (e.g. Fig. 13) showed evidence of thaumasite


formation in those mixtures, though with varying
levels depending on the extent of chemical damage as
will be explained in the succeeding section. Optical
microscopy (e.g. Fig. 14a) on thin sections from
these mixtures showed a general feature of whitepowdery material filling voids dispersed in the
matrix. BSEM with EDX (Fig. 14bd) confirmed
the formation of thaumasite in these matrices, which
suffered severe damage.
Progressive formation of thaumasite along with
other reaction products such as ettringite and gypsum
softened those cementitious matrices and made them
more vulnerable to the dual exposure than matrices
from other blended binders. It was argued [30] that
thaumasite formation does not necessarily lead to the
deterioration of cementitious systems. However,
results from this study suggest that Q mixtures
incorporating 15% limestone powder (a finely
divided source of carbonates) suffered an initial stage
of thaumasite sulphate attack (TSA) that contributed
to earlier damage, higher expansion and severe loss
of mechanical properties. According to Crammond
[31], the main parameters conductive to TSA are the
availability of sulphates, carbonates and water under
low temperature (around 5C). In this study, TSA was
detected at temperatures cycling from freezing to
thawing.
Other blended binders, which did not contain
limestone filler, showed products of chemical

Materials and Structures (2008) 41:16571679


Fig. 13 XRD for powder
samples from Q (A4-N-50)
specimens after the dual
exposure

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

Fig. 14 Thin section analysis for the Q (A4-N-50) specimens


showing the mottled appearance of the matrix with thaumasitefilled voids and cracks: (a) under polarized light, (b) BSEM,

(c) higher magnification of area A in (b), and (d) EDX


spectrum for thaumasite

1674

reactions with sodium sulphate. SEM indicated the


conventional sulphate attack secondary deposits (gypsum and ettringite) in all of these matrices conforming
to DSC and XRD results. Incidental features of
thaumasite formation have also been observed likely
due to the existence of a fraction of dolomite/dolomitic
aggregates in the used crushed stone.

5.2.2 Effect of air-entrainment


Results of group A specimens may suggest that SCC
specimens made with some binders could perform
well under frost action without the need for airentrainment. However, these results should be treated
with caution especially that a high-performance
quaternary binder such as A5-N-50 failed under
exposure primarily due to the lack of air-entrainment.
Irrespective of the binder type, air-entrainment had a
positive effect on delaying expansion and/or tolerating higher expansion for group B compared to group
A specimens (Fig. 7) resulting in higher durability. It
is well-documented that microscopic air bubbles act
as relief chambers for accommodating expansive
pressures induced in hydrated cement matrices
exposed to freezingthawing cycles [7]. It is also
conceivable that a network of well dispersed air
bubbles accommodated pressures exerted by frost
action and growth of reaction products from sulphate
attack. Similar observations [e.g. 10] of air-entrainment effect on expansion were reported for mortar
specimens immersed in sodium and magnesium
sulphate solutions.
In the case of coupled external sulphate attack and
frost action, continual infilling of air bubbles with
reaction phases, which apparently migrate and preferentially recrystallize at these locations, can pose a
problem at later ages, especially for blended binders.

Fig. 15 SEM micrographs


for fracture surfaces
showing filling of air voids
with associated microcracks [indicated by the
arrows] in specimens from:
(a) a single binder (B1-A40), and (b) a binary binder
(B2-A-40)

Materials and Structures (2008) 41:16571679

For example, Fig. 15a, b show extensive filling of


entrained air bubbles in cementitious matrices from
specimens prepared with different binders. Microcracks (e.g. Fig. 15a) emanated from the filled air
bubbles suggesting a contributing role of sulphate
attack to damage in this case. Alteration of the airentrained matrix because of sulphate reactions rendered its performance less effective with prolonged
freezingthawing cycles. Due to the high-sulphate
resistance of these mixtures (particularly those
prepared with blended binders) as shown by the
ASTM C 1012, the rate of sulphate reactions and
consequently the rate of pores filling with reaction
products was slow. Once those cementitious matrices
reached a critical filling condition, further hydraulic
and osmotic pressures led to failure, which was at
some cases sudden (e.g. B2-A-60 and B3-A-40 in
Fig. 3b).

5.2.3 Effect of sand-to-aggregate ratio


S/A had a mixed effect on the results of group B
mixtures. Whilst it did not have a statistically
significant effect on expansion and mass change
results, it affected the REd and the RF results. For
example, for the mass change and RF results,
ANOVA at a significance level a = 0.05, showed
that the change of S/A (4060%) had an F value of
2.80 and 6.28, respectively, compared to a critical F
value of 4.96. This indicates that the change of S/A
from 40% to 60% was an insignificant parameter in
the mass change results, whereas it was an influential
factor in the RF results. This is attributed to the prime
dependence of the mass change and the expansion
results on the characteristics of the cementations
paste, which nearly had a constant volume fraction
(from 325 to 350 l/m3) for each binder type.

Materials and Structures (2008) 41:16571679

1675

Fig. 16 (a) Loss of


bonding between coarse
aggregate and cementitious
pate (specimen B2-A-40,
magnification 259-plain
light), and (b) crack
arresting by micro-fibres
(specimen C5-A-H,
magnification 509-plain
light)

Generally, specimens with S/A of 60% had higher


residual flexural strength than that of corresponding
specimens with S/A of 40%. Mechanical properties
of concrete such as the flexural strength are generally
sensitive to the volume of coarse aggregates and the
interfacial zone with the cementitious matrix. Optical
microscopy showed that with repeated freezing
thawing cycles, adhesion between the cementitious
matrix and coarse aggregates can be completely lost.
For example, Fig. 16a shows full separation/cracking
surrounding coarse aggregate particles in the surface
of a B (B2-A-40) specimen. Indeed, the probability of
occurrence of debonding is higher at a higher coarse
aggregate content (lower S/A) resulting in lower
residual flexural strength.

5.2.4 Effect of fibres


Variation in the binder type did not have a significant
effect on the physico-mechanical properties of airentrained SCC specimens with hybrid fibre reinforcement. The use of 0.4% steel and 0.1% polypropylene
fibres was effective at improving the resistance of
SCC specimens to the dual exposure. Hybrid fibre
reinforcement controlled cracking which led to an
increased matrix integrity, and in turn it discounted
the rate of deterioration. The rationale behind incorporating hybrid fibres is the combination of the
advantageous effects of polymer micro-fibres and
steel macro-fibres. According to Johnston [32],
polymer micro-fibres contribute to enhancing the
pre-crack behaviour by impeding the nucleation and
coalescence of micro-cracks, while steel macro-fibres
can bridge macro-cracks, thus contributing to the
control of crack propagation. The positive effect of
hybrid fibres is evident in group C mixtures that

withstood 610 cycles of dual exposure and high


expansion values (above 0.3%) without significant
decline in mechanical properties.
Microscopy highlighted the pronounced effect of
fibres in controlling the cracking behaviour of the
cementitious matrix. Figure 16b shows a typical
crack arresting pattern in the Q specimen (C5-A-H).
The importance of cracking control lies in maintaining the integrity of the matrix at the surface and in the
inner core. Reducing surface cracking can limit the
penetrability of the sodium sulphate solution. Consequently, the rate of chemical reaction between the
sodium sulphate and the cementitious paste can be
significantly reduced. For instance, microscopy on
polished sections of the Q binder specimen (C5-A-H)
showed no significant deposition of reaction phases in
air bubbles (Fig. 16b), which corresponds to a low
expansion of about 0.1%. For other binders, fibre
reinforcement also proved effective at withstanding
high expansion and prolonged exposure, since the
matrix integrity was maintained at the inner core. The
observed surface scaling in the hybrid fibre-reinforced specimens might be attributed to the exposure
to a higher number of cycles than that of corresponding group B specimens. Also, debonding of corroded
steel fibres from the surface might have contributed
to weakening of the surface skin and making it more
vulnerable to scaling.

5.3 Coupled effects of sodium sulphate and frost


action
As suggested by the XRD and DSC results, there was
insignificant development of sulphate attack in group
A specimens that were exposed to a lower number of
test cycles. Therefore, it is reasonable to assume that

1676

Materials and Structures (2008) 41:16571679

With the continual supply of the sodium sulphate


solution, supersaturation and consequently crystallization of sodium sulphate occurred. Salt
crystallization together with sulphate reaction products in the confined pore space can exert large tensile
stresses leading to cracking. The occurrence of this
complex form of salt crystallization with sulphate
attack reaction phases was shown by SEM (e.g.
Fig. 18) and XRD (e.g. Fig 17), especially for
specimens incorporating blended binders which did
not tend to lose their surfaces. It seems that deposition of sulphate attack reaction products and salt
crystallization in air bubbles at and near the exposed
surfaces induced expansive stresses, which held the
inner concrete in tension resulting in detrimental
effects and sudden failure.

specimens in group A (e.g. A1-N-50 and A5-N-50)


failed most likely due to a lack of air-entrainment,
which primarily reduced the salt-frost resistance of
SCC. In group A, the synergistic effects of sodium
sulphate and frost action could be observed in the
surface scaling of single binders and the incipient
formation of TSA in specimens made with quaternary
binders comprising limestone powder.
In group B specimens, the effects of sulphate
reactions were more pronounced as indicated by the
DSC and XRD (e.g. Fig. 17) results showing higher
quantities and intensities of reaction products. Prolonged freezingthawing cycles induced micro- and
sub-parallel cracks (similar to Fig. 14b) on the
exposed surfaces providing direct paths for the
intrusion of sodium sulphate solution. Subsequently,
reaction of the solution with the paste led to the
formation of gypsum, ettringite, and in some cases
thaumasite. Those reaction products were detected
after exposure to temperatures cycling from freezing
to thawing. Microscopy analysis showed the cumulative deposition of these reaction products in air
voids (Fig. 15a, b). Indeed, the penetration of the
sodium sulphate solution depressed the freezing point
(i.e. reduced the freezing temperature) in the capillary
pores, thus reducing hydraulic pressures. However,
due to differential salt concentrations within the
surfaces of specimens, osmotic pressures may have
primarily contributed to the damage.

Fig. 17 XRD for powder


samples from T (B3-A-40)
specimens after the dual
exposure showing the
coexistence of sulphate
reaction products and salt
crystallization

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

Materials and Structures (2008) 41:16571679

1677

Fig. 18 A typical SEM micrograph and associated EDX


spectra for specimen from a blended binder (B5-A-60) showing
accumulation of sulphate reaction phases (T = Thaumasite;

E = Ettringite; G = Gypsum)
(Th = Thenardite)

The conventional immersion test (ASTM C 1012)


in a 5% sodium sulphate solution suggested that
all SCC mixtures tested in this study were
resistant to sodium sulphate. However, this test
could not capture potential risks that may arise if
frost action is combined with sodium sulphate in a
synergistic manner.
The combination of sulphate attack with frost
action in a performance testing procedure showed
potential durability problems of different binders
such as excessive surface scaling of 100% OPC
binders and incipient TSA of binders incorporating limestone powder.
Whilst air-entrainment initially enhanced the
resistance of SCC to the combined chemical
physical attack, the degradation was only delayed
and the cementitious matrices were not completely immune to degradation, irrespective of the
binder type.

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

0.2% (a higher limit may be allowed if fibres are


incorporated); a maximum mass loss of 3%; a
minimum relative dynamic modulus of elasticity
(REd) of 60%; a minimum relative flexural
strength (RF) of 50%.
With further research, such combined performance procedures can be confirmed and/or
improved to validate its robustness and refine
the abovementioned failure criteria.
To develop performance-based standards for
concrete, there is need to develop multi-damage
performance tests able to capture synergistic
damage mechanisms that cannot be identified by
current standard tests that subject concrete to a
single aging mechanism at a time.

Acknowledgements The continued support of the Natural


Science and Engineering Research Council of Canada
(NSERC) and the Ontario Premiers Research Excellence
Award to M. L. Nehdi are highly appreciated. Also, funding of
the Ontario Innovation Trust (OIT) and the Canada Foundation
for Innovation (CFI) that allowed creating a sate-of-the-art
laboratory in which these experiments were conducted has
been crucial to this research. M. T. Bassuoni acknowledges the
Ontario Graduate Scholarship (OGS) for supporting his
doctoral studies.

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