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Study on the expansion of concrete under attack of sulfate and sulfatechloride ions
Minghua Zhang a, Jiankang Chen a,b,, Yunfeng Lv a, Dongjie Wang a, Jian Ye c
a
Department of Mechanics and Engineering Science, Ningbo University, Ningbo 315211, China
State Key Laboratory of Turbulence and Complex System, Beijing University, Beijing 100871, China
c
Department of Water Resources of Jiangsu Province, Nanjing 210029, China
b
h i g h l i g h t s
" The higher the concentration of sulfate, the greater the expansion in specimens.
" The higher the water-to-cement ratio used, the more severe the damage found.
" The chloride ions can substantially reduce the sulfate attack.
" The higher the concentration of chloride, the less the expansion in specimens.
" Expansion and damage can be described by a new model based on micromechanics.
a r t i c l e
i n f o
Article history:
Available online 26 May 2012
Keywords:
Concrete
Sulfate attack
Chloride
Expansion
Delayed ettringite
Damage evolution
a b s t r a c t
This paper describes an experimental study on the expansion and subsequent damage of concrete specimens immersed in pure water, sulfate solutions of different sulfate concentrations, and mixed solutions
of different sulfate and chloride concentrations. Based on experimentally obtained results, a theoretical
expansion model is proposed for predicting the stresses, strains and volume expansion developed during
the process of sulfate attack. The model proposed is based on the assumption that concrete may be treated as a porous visco-elastic material, and was developed by using a micromechanics approach method.
The internal expansion force produced by delayed ettringite and gypsum is considered as the main cause
of the expansion. The expansion model was validated using the experimental results obtained.
2012 Elsevier Ltd. All rights reserved.
1. Introduction
Durability of concrete materials is one of the most important
problems in the design of concrete structures. Durability deciency, which may result in premature failure and/or decrease of
serviceability, is a major concern in developing sustainable infrastructure systems [1]. Sulfate attack is one of the phenomena that
may cause gradual but severe damage to concrete structures.
Sulfate attack on concrete leads to the conversion of cement hydration products to ettringite, gypsum, and other possible phase
changes [2,3]. Accompanying the formation of gypsum and ettringite is a volume increase. The volume expansion within concrete
cannot only reduce the porosity of concrete but may also cause
damage and cracking of the concrete leading eventually to a
Table 1
Mix design of concrete specimens (wt.%).
Type
W/C
Cement
Water
Sand
Gravel
I
II
0.5
0.33
14
22
7
7
29
21
50
50
Table 2
Five different ionic solutions used in experiments (wt.%).
No
Na2SO4
NaCl
1
2
3
4
5
0
3
5
3
5
0
0
0
6
10
27
3. Experimental results
When the concrete specimens were immersed in a sulfate solution, sulfate ions penetrated into the specimens. The use of wetting
and drying cycles accelerated the penetration of ions from the
solution into the specimens. After sulfate ions entered the concrete
pores, they reacted with hydrated cement compounds and ions in
the pore solution or on the cement pore surface. The chemistry of
the reactions is rather complicated and involves numerous overlapping steps and mechanisms. The reactions lead to the formation
of tricalcium sulfoaluminate hydrate, known as ettringite, which is
expansive in nature. The formation of ettringite crystals and the
consequent volume increase in the hardened material are considered to be responsible for expansive forces and micro-cracking
[2].The following is one of the examples of these reactions [3],
28
Type I
Type II
Type I
Type II
(a)
(b)
Type I
Type I
Type II
Type II
(d)
(c)
Type I
Type II
(e)
Fig. 2. Images of specimens (after 50 days) immersed in ve different solutions. (a) Pure water, (b) 3% sodium sulfate solution, (c) 5% sodium sulfate solution, (d) 3% sodium
sulfate and 6% sodium chloride mixed solution, and (e) 5% sodium sulfate and 10% sodium chloride mixed solution.
3.0
water
3% Na2SO4
2.5
Expansion,%
5% Na2SO4
3% Na2SO4+6% NaCl
2.0
5% Na2SO4+10% NaCl
1.5
1.0
0.5
0.0
0
10
20
30
40
50
60
Exposure time,Days
Fig. 3. Axial expansion of type-I specimens immersed in ve different solutions.
in the 5% sodium sulfate solution, whereas the expansion was almost negligible in the specimens immersed in the pure water solution and in the two mixed solutions. The expansion of the
specimens immersed in the 3% sodium sulfate solution was found
to be about a half of that of the specimens immersed in the 5% sodium sulfate solution during the rst 35 days and became about
one-third of it after 35 days. It can be seen from the gure that
the expansion undergoes a slow-quick-slow-quick process. It is believed that the rst slow expansion is attributed to the hydration of
cement paste, since 28 days hydration may not be sufcient so that
the concrete will continue to hydrate when it is immersed in
water, resulting in a slight expansion of the specimen. The second
quick expansion is due to local expansion caused by sulfate attack
in the region where pores are small. The third slow expansion is
the overall volume increase generated while the sulfate products
are lling the pores. The last quick expansion is mainly due to
the macro-cracking.
Fig. 4 shows the evolutions of the average axial strains of the
type-II specimens immersed in the ve different solutions. Compared to the type-I specimens, the type-II specimens have only
small expansions. For example, the maximum average axial strains
of the type-II specimens immersed in 3% and 5% sodium sulfate
solutions are only 0.315% and 0.259%, respectively, whereas the
maximum average axial strains of the type-I specimens immersed
in 3% and 5% sodium sulfate solutions are 0.922% and 2.67%,
respectively. This indicates that the water-to-cement ratio has a
large inuence on the sulfate attack. It should be pointed out that,
the marginally larger average axial strain found in the specimens
29
0.35
water
3% Na2SO4
0.30
The expansion of concrete under the attack of sulfate and chloride ions can be represented by the model shown in Fig. 5, in which
the pressure in the voids, P, and the micro-cracks in the matrix are
induced by delayed ettringite. Therefore, the concrete can be treated as a composite material consisting of micro-voids and viscoelastic matrix with micro-cracks. In the present model the microcracks are denoted by a dimensionless factor, D, which is a function
of time t and can be determined by experimental methods.
The following linear, visco-elastic constitutive relation can be
assumed for concrete materials with damage [21]:
5% Na2SO4
3% Na2SO4+6% NaCl
Expansion,%
0.25
5% Na2SO4+10% NaCl
0.20
0.15
0.10
0.05
rm 1 D
Lt s : e_ m sds
0.00
0
10
20
30
40
50
60
Exposure time,Days
Fig. 4. Axial expansion of type-II specimens immersed in ve different solutions.
immersed in the 3% sodium sulfate solution than in those immersed in the 5% sodium sulfate solution was probably due to
the non-uniform expansion in the specimens and experimental
errors.
It may be observed from Fig. 4 that the specimens immersed in
pure water and those immersed in the mixed solution of 5% Na2SO4
and 10% NaCl have very close expansion evolutions, whereas those
immersed in the 3% and 5% sodium sulfate solutions have similar
expansion evolutions. The former indicates that the presence of
chlorides can indeed mitigate the sulfate attack. In the early stages
continuing hydration will lead to a slight expansion of the specimens. Because the diffusion rate of chloride ions is faster than that
of sulfate ions, when expansion and cracks resulting from sulfate
attack develop in the specimens, the chloride ions will penetrate
deep into the specimen through both concrete pores and the micro-cracks. In the presence of calcium hydroxide, chloride ions will
react with hydrated calcium aluminate to form single- and tricalcium chloroaluminates which will block the formation of ettringite. This is why a high chloride concentration in the solution can
result in the reduction of expansion of the specimens. The decrease
of chloride concentration in the solution will reduce the blocking
effect on the formation of ettringite and thus increase the expansion of the specimen, as is demonstrated by the expansion curve
of the specimens immersed in the mixed solution of 3% Na2SO4
and 6% NaCl.
em
1
1D
Jt s : r_ m sds
where rm and r_ m are the stress and stress rate tensors, em and e_ m
are the strain and strain rate tensors, L(t) is the fourth order relaxation modulus, and J(t) is the fourth order creep compliance. Note
that L(t) can be expressed as follows,
Lt ltL0
L0 3km0 Im 2lm0 Is
where lt exp stm if the Maxwell model is used, sm = 0.3375
day is the relaxation time of the concrete material, and L(0) is the
initial fourth order relaxation modulus, which can be expressed,
in which
1
i0 i0 ; Is I Im ;
3
Em0
21 mm0
Im
km0
Em0
;
31 2mm0
lm0
where i0 and I are the unit tensors of the second- and fourth-order,
respectively, Em0 = 2.7 GPa is the initial modulus and vm0 = 0.2 is the
Poissons ratio. The incremental form of the constitutive Eq. (1) can
be expressed as:
Drm 1 Dt Dt
tDt
: e_ m sds 1 Dt
Lt Dt s
Z
Lt s : e_ m sds
Lt Dt s Lt s
Dt Dt Dt
Microcrack
@Lt s
Dt
@t
@D
Dt
@t
Substituting Eqs. (6) and (7) into (5), and using the mid-value theorem of integration, we obtain,
Z t
@Lt s
Dt
@t
0
Z t
dD
: e_ m sds
Dt
Lt s : e_ m sds 1 DtL0
dt
0
: e_ m sDt
Drm 1 Dt
30
rm f trm0
em gtem0
10
nv
DP
1 nv
and hDrmij i
ij
18
and substituting Eqs.(9) and (10) into (3) and (4), it yields,
gt
1
1 Dt
jt sf_ sds
H1 H1
1122 H1133 DP
1 nv 1111
11
0 if
Drm HDem
12
and hDemij i
ij
19
in which
H GtL0
hDeij i 0 if
Z t
1
@lt s
_ sds
g
Gt 1 Dt
Dt
_
@t
gt
0
Z t
dD 1
_ sds 1 DtDt
Dt
lt sg
_
dt gt
0
q1
q2
1
H1
kl22 Hkl33
21
To simplify the analysis, only the linear and quadratic terms are
considered in the above pressure expression. Therefore,
DP
dP
Dt C 1 2C 2 tDt
dt
22
14
20
P C 1 t C 2 t2 . . .
13
1
De2
v DPH : i0
1
H1
1122 H 1133
1
1
I11kl S11kl Hkl11
2
Dev De1 S : De1
v Dev
ij
H1
1111
15
t
Dt a0 1 exp aD
t0
16
17
where nv is the porosity of the concrete material and dij is the component of the unit tensor of second-order, i0. Note that
hDr11 i hDr22 i hDr33 i 0 because there is no external force applied to the material. Hence, Eq. (16) can be further simplied as
follows,
Table 3
Parametric values of a0 and nv.
Type
nv
a0
I
II
0.1717
0.1547
0.8283
0.8453
23
Table 4
Parametric values of aD (to = 730 days).
Solution
0% Na2SO4 + 0% NaCl
3% Na2SO4 + 0% NaCl
5% Na2SO4 + 0% NaCl
3% Na2SO4 + 6% NaCl
W/C = 0.5
W/C = 0.33
0.5
1.0
3.7
2.6
6.2
3.5
0.6
1.3
0.5
1.0
31
1.0
0.08
0.06
Expansion,%
Expansion,%
0.8
0.04
Experimental result for Type I
Experimental result for Type II
Theoretical model for Type I
Theoretical model for Type II
0.02
0.00
0.6
0.4
0.2
0.0
10
20
30
40
50
60
10
20
Exposure time,Days
(a)
0.18
Experimental result for Type I
Experimental result for Type II
Theoretical model for Type I
Theoretical model for Type II
50
60
0.16
0.14
Expansion,%
Expansion,%
2.5
40
(b)
3.5
3.0
30
Exposure time,Days
2.0
1.5
1.0
0.12
0.10
0.08
0.06
0.04
0.5
0.02
0.0
0.00
0
10
20
30
40
50
60
Exposure time,Days
10
20
(c)
40
50
60
(d)
0.09
0.08
0.07
Expansion,%
30
Exposure time,Days
0.06
0.05
0.04
0.03
0.02
0.01
0.00
0
10
20
30
40
50
60
Exposure time,Days
(e)
Fig. 6. Axial strains of specimens immersed in ve different solutions. (a) Pure water, (b) 3% sodium sulfate solution, (c) 5% sodium sulfate solution, (d) 3% sodium sulfate and
6% sodium chloride mixed solution, and (e) 5% sodium sulfate and 10% sodium chloride mixed solution.
Table 5
Parametric values used for the expansion force.
Solution
0% Na2SO4 + 0% NaCl
3% Na2SO4 + 0% NaCl
5% Na2SO4 + 0% NaCl
3% Na2SO4 + 6% NaCl
W/C = 0.5
W/C = 0.33
C1 = 1, C2 = 0.1
C1 = 1, C2 = 0.1
C1 = 1, C2 = 1
C1 = 1, C2 = 0.8
C1 = 1, C2 = 2
C1 = 1, C2 = 1.2
C1 = 1, C2 = 0.2
C1 = 1, C2 = 0.3
C1 = 1, C2 = 0.1
C1 = 1, C2 = 0.2
32
6. Conclusions
This paper has presented an experimental study on the expansion and damage of concrete specimens with two different waterto-cement ratios, immersed in pure water, sulfate solutions of different sulfate concentrations, and mixed solutions of different sulfate and chloride concentrations. From the present study the
following conclusions can be drawn.
The concentration of sulfate ions in the solution has important
effect on the expansion and damage developed in concrete
specimens immersed in the solution. The higher the concentration of sulfate ions in the solution, the greater the expansion
and the more severe the damage found in the concrete
specimens.
Water-to-cement ratio has signicant inuence on the sulfate
attack in concrete. The higher the water-to-cement ratio used,
the greater the expansion and the more severe the damage
found in the concrete specimens.
The presence of chloride ions in the concrete pore solution can
substantially reduce sulfate attack. The higher the concentration of chloride ions in the solution, the lower the expansion
and the less the damage found in the concrete specimens.
The expansion and damage in concrete induced by the sulfate
attack can be described by the theoretical expansion model
based on the concept of micromechanics. The model can be
used to predict the stresses, strains and volume expansion
developed during the process of sulfate attack.
Acknowledgments
The authors would like to acknowledge the nancial support received from the China National Natural Science Foundation (Grants
#10932001 and #51079069), the National Basic Research Program
of China (973 Program, 2009CB623203), the Key Research Program
of Ministry of Education of China (No. 20103305110001), the Impact and Safety of Coastal Engineering Initiative, a COE Program
of Zhejiang Provincial Government at Ningbo University (Grant
No. zj1003), and K.C. Wong Magna Fund in Ningbo University.
References
[1] Idiart AE, Lpez CM, Carol I. Chemo-mechanical analysis of concrete cracking
and degradation due to external sulfate attack: a meso-scale model. Cem Concr
Compos 2011;33(3):41123.