Construction and Building Materials 264 (2020) 120525

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Construction and Building Materials

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

The damage mechanism and failure prediction of concrete under

wetting–drying cycles with sodium sulfate solution
Jingge Ren a,b, Yuanming Lai a,b,⇑, Ruiqiang Bai a,b, Yinghong Qin c
a
State Key Laboratory of Frozen Soil Engineering, Northwest Institute of Eco-Environment and Resources, Chinese Academy of Sciences, Lanzhou, Gansu 730000, China
b
University of Chinese Academy of Sciences, Beijing 100049, China
c
College of Civil Engineering and Architecture, Guangxi University, Guangxi 530000, China

h i g h l i g h t s

Collision probabilistic factor of the formation of gypsum was calculated.

Reaction-rate constant calculation formula of gypsum is proposed.

Formulae of the volume fractions of mirabilite and gypsum in the pore were proposed.

Damage node of concrete under sulfate wetting–drying cycles was well predicted.

Concrete was in a dynamic damaging-filling state under wetting–drying cycles.

a r t i c l e i n f o a b s t r a c t

Article history: This study aims to investigate the damage mechanism and predict the failure time of concrete subjected
Received 20 November 2019 to wetting and drying (WD) cycles in a sodium sulfate solution. To explore the growth rules and the
Received in revised form 4 July 2020 growth rates of gypsum, the reaction-rate constant calculation formula of gypsum is proposed based
Accepted 10 August 2020
on theories of chemical reaction kinetics. Subsequently, the formulae of the volume fractions of mirabilite
and gypsum in the pore under each WD cycle are proposed and used to calculate the macroscopical ten-
sile stress to determine the WD cycle number that the concrete can sustain. Finally, the reliability of the
Keywords:
proposed model is verified by an indoor experiment. In addition, a new damage type of concrete, induced
Wetting–drying cycle
Sodium sulfate
by filling-damaging cycles, is also found during the experiment. These findings can be used for evaluating
Gypsum the damage of concrete that is subjected to cyclic WD in sodium sulfate solution.
Crystal growth Ó 2020 Elsevier Ltd. All rights reserved.
Crystallization pressure
Durability

1. Introduction Sodium sulfate physically attacks plain concrete by precipitat-

Concrete is widely used in many construction fields, such as
pavement, bridge and building due to its low cost, simple prepara-
tion process and high performance. However, concrete will be seri-
ously damaged when it is exposed to marine environments, acid
rain and saline soil. In these harsh conditions, the durability of con-
crete is influenced by inorganic salts, including the chlorine salt
and sulfate [1,2]. The chlorine salt is the most harmful salt to rein-
forced concrete, and the sulfate is the most harmful salt to the
plain concrete [3,4]. Sodium sulfate attacks plain concrete physi-
cally and chemically.
⇑ Corresponding author at: State Key Laboratory of Frozen Soil Engineering,
Northwest Institute of Eco-Environment and Resources, Chinese Academy of
Sciences, Lanzhou, Gansu 730000, China.
E-mail address: ymlai@lzb.ac.cn (Y. Lai).
ing mirabilite in the pore of concrete when the surrounding tem-
perature and relative humidity change [5]. At an environment
with cyclic wetting and drying (WD), the thenardite deposites in
the pore during the drying process, increases the concentration
of the solution in the pore in the subsequent wetting cycle and
even precipitates mirabilite in the pore. The mirabilite cumulates
in the pore progressively as the increase of the WD cycle index,
crystallization pressure is generated, and the concrete is damaged
[6]. The physical damage has already been widely accepted [7–9]
and the failure mechanism of the mirabilite has been studied. Car-
los et al. [10] investigated the transformation rule between differ-
ent crystal phases of sodium sulfate and found that both thenardite
and mirabilite can precipitate directly from a saturated sodium
sulfate solution at room temperature (20 °C). The crystallization
pressure of sodium sulfate in the pore of rock was analyzed and
calculated at different times of WD cycles [11].

https://doi.org/10.1016/j.conbuildmat.2020.120525
0950-0618/Ó 2020 Elsevier Ltd. All rights reserved.
2 J. Ren et al. / Construction and Building Materials 264 (2020) 120525

Nomenclature

SM,i Volume fraction of mirabilite after i WD cycles

Symbols
SG,i Volume fraction of gypsum after i WD cycles
ae Ionic activity of e
SM Total volume fraction of mirabilite
b’ Biot coefficient
SG Total volume fraction of gypsum
cNa2 SO4 Concentration of sodium sulfate mol/L
Sm Volume fraction of the crystal after m = n + i + 1 WD cy-
c’ Concentration of the solution mol/L
cles
cCa2þ Concentration of calcium ion mol/L
Sn Volume fraction of the crystal after n WD cycles
cs Saturation concentration of sodium sulfate mol/L
t Any time during the reaction
c’s Concentration of the saturated solution mol/L
t0 The wetting duration for each WD cycle
cSO2 Concentration of sulfate ion
4 T Temperature in Kelvin K
c0SO2 Concentration of sulfate ion in initial state mol/L
sat4
cSO2 Concentration of sulfate ion in saturated sodium sulfate
vc Molar volume of any crystal L/mol
4
solution mol/L
v reac
e Stoichiometric coefficient of ion e
cðCa2þ SO2 Þ Concentration of the particle pair of ðCa2þ SO2
v CaðOHÞ Molar volume of calcium hydroxide L/mol
4 Þ mol=L
vG
2
4 Molar volume of gypsum L/mol
DSO2 Diffusion coefficient of sulfate ion m2/s
e
4
Any ion
vM Molar volume of mirabilite L/mol
f Surface tension N/m
vT Molar volume of thenardite L/mol
Vc,i Total volume of the crystals after i WD cycles L
ISO2 Flux of SO2
4 at the spherical area around the Ca
2þ
mol/s
4 Vc,i+1 Total volume of the crystals after i + 1 WD cycles L
J SO2 the flux of SO2
4 in per unit time per unit area mol/(sm )
2
4 VG Volume of gypsum L
kB Boltzmann constant J/K
VG,i Volume of gypsum after i WD cycles L
kG Reaction-rate constant of gypsum
VG,i+1 Volume of gypsum after i + 1 WD cycles L
k1D Diffusion-rate constant of reaction particle
VG,n Volume of gypsum after n WD cycles L
k-1D Separation-rate constant of the particle pair
VM,i Volume of mirabilite after i WD cycles L
k2 Reaction-rate constant of the particle pair
VM,i+1 Volume of mirabilite after i + 1 WD cycles L
KG dissolution equilibrium constant of gypsum
Vi+1
M Volume of the mirabilite produced during i + 1 WD cycle
K MN1 X N2 N3 H2 O Dissolution equilibrium constant ofMN1 X N2  N 3 H2 O
L
Kreac Equilibrium constant of the chemical reaction
Vp Volume of the pore L
KSP,M Thermodynamic solubility product of mirabilite
V 0p Initial volume of the pore L
KSP,T Thermodynamic solubility product of thenardite
V np Volume of the pore after n WD cycles L
MG Molar mass of gypsum g/mol
VQ Volume in the pore that the solution can invade L
NA Avogadro’s constant mol1
VRi Volume in the pore that available for solution invading L
NG Particle number of gypsum mol
Vs Volume of the solid dissolved in the pore solution L
N0G Particle number of gypsum at the initial condition mol
VT,i Volume of thenardite after i WD cycles L
NiG Particle number of gypsum after i WD cycles mol
V DG The volume increment from the formation of gypsum L
NnG Particle number of gypsum after n WD cycles mol
cCa2þ Reaction rate of calcium ion mol/s
NSO2 Particle number of sulfate ion mol
4 cG Formation rate of gypsum mol/(Ls)
p Osmotic pressure Pa
e Poisson’s ratio
Ps Saturated osmotic pressure Pa
n Reaction degree mol
P Probabilistic factor for the molecule collision
h Contacting angel between the crystal liquid interface
Pc Crystallization pressure MPa
and the pore wall
PG Crystallization pressure of gypsum MPa
PM Crystallization pressure of mirabilite MPa
lHCa2þ Standard chemical potential of calcium ion J/mol
Qreac Ionic activity product
lHG Standard chemical potential of gypsum J/mol
le Chemical potential of e
QG Ionic activity product of gypsum
rp Radius of the pore m
lHe Standard chemical potential of e J/mol
r Ca2þ Radius of calcium ion pm
lHSO2 Standard chemical potential of sulfate ion J/mol
r* 4
Macroscopic tensile stress
r SO2 Radius of sulfate ion pm
4
r Ca2þ SO2 Radius of calcium ion plus sulfate ion pm
rc Critical tensile stress
r
4
Distance between Ca2+ and SO2
rG Macroscopic tensile stress of gypsum
4 pm
R Molar gas constant J/(molK)
rM Macroscopic tensile stress of mirabilite
rr Radial compressive stress
RHsat,T Deliquescence relative humidity of thenardite
rT Tensile strength of the concrete
S1 Volume fraction of the crystal after one WD cycles
Sc Volume fraction of the crystal in the pore
p Circular constant
qG Density of gypsum
Si Volume fraction of the crystal after i WD cycles
gw Viscosity of water
Si+1 Volume fraction of the crystal after i + 1 WD cycles

Sodium sulfate chemically attacks plain concrete by reacting
with the hydrated calcium silicates (C-S-H) [12]. Sodium sulfate
also reacts with the calcium hydroxide in the plain concrete, pro-
duces expansion crystal and causes damages in the concrete [13].
Studies on the chemical damage are still controversial.
One argument is whether the formation of gypsum expands the
concrete. Hansen [14,15] believed that the precipitation of gypsum
is expansion-free. If the gypsum can cause expansion, the volume
of plain concrete increases during the reaction of calcium ion and
sulfate ion. The gypsum should form in situ or on the surface of cal-
cium hydroxide particle. Supporting the viewpoint of Hansen,
Mather [16] thought that the formation of gypsum cannot create
expansion and pointed out that gypsum was primarily formed
from the reaction of sulfate ions and calcium ions by a through-
solution mechanism. On contrary, most researchers thought that
the formation of gypsum can cause expansion [17–20]. By studying
gypsum in the interfacial zone of a plain concrete, Bonen and
Sarkar [21] found that a thick layer of gypsum up to 50 lm width
 J. Ren et al. / Construction and Building Materials 264 (2020) 120525
precipitates by a through-solution mechanism. This crystallization
of gypsum causes tensile stress and expansion in the concrete. The
results are effectively contradicted to the opinion of Hansen. Yong
et al. [22] also investigated the damage process of the interfacial
zone under the sulfate attack. They got the same viewpoint as
Bonen and Sarkar, and thought that sulfate ion can react with cal-
cium hydroxide and monosulfate (AFm) and lead to expansion and
cracking. Wang [23] observed the products at different depths in a
cement paste under sulfate attack by X-ray diffraction. The inves-
tigation result found that the formation of gypsum causes more
damage than the formation of ettringite does. Ping and Beaudion
[24,25] suggested a theory model based on the principles of chem-
ical thermodynamics and pointed out that the crystal induced
pressure needs to additional conditions. One is that the solid pro-
duct should form and grow in a confined space, and the other is
that the activity product of the reactants in the pore solution
should be larger than the solubility product of the solid products
under atmospheric pressure. Tian and Cohen [26] carried out the
sulfate attack experiments and demonstrated that the damage in
the concrete is caused simultaneously by the expansions of ettrin-
gite and gypsum. However, the crystal type varies with sulfate con-
centration and this thus results in the different failure mechanism
in the concrete. Hence, a new argument was generated on the fail-
ure mechanism between the laboratory test and the site condition.
Gallop and Taylor [27,28] found that the sulfate concentration used
is usually 30 g/l in the laboratory and the main corrosion product is
gypsum. The gypsum forms veins and layers in the first 2 mm
beneath the surface of the mortar bars. Bellmann et al. [29] demon-
strated the result according to the investigation on the product in
the concrete under different concentrations of the sodium sulfate
solution. When the concentration of sodium sulfate solution is
low, the main reaction product is ettringite and the main reaction
product is gypsum under high concentration sodium sulfate
solution.
After the damage of concrete under sulfate attack is understood,
the research emphasis has been shifted to the crystallization pres-
sure, which usually includes the pressure caused by the formation
of mirabilite, gypsum and ettringite. The crystallization pressure
caused by mirabilite has already been studied on the basis of the
principles of thermodynamics and physical chemistry. Tsui et al.
[30] analyzed the phase transformation and crystallization pres-
sure of sodium sulfate, and found a threshold of salt content
beyond which damage increases substantially. Scherer [31,32]
found that the crystallization pressure in the pore comes from
the repulsive force between the crystal and the pore wall, and
the maximum pressure is determined by the separating force on
the surface of the crystal. The crystallization pressure caused by
mirabilite is larger than that caused by other salts, and at most
of the time the concrete and rock materials fail to resist the max-
imum crystallization pressure [33]. On the basis of the crystalliza-
tion pressure equation [34], Rijniers et al. [35,36] investigated the
crystallization pressure of mirabilite and heptehydrated phase by
nuclear magnetic resonance. The result indicated that the heptehy-
drated phase cannot cause crystallization pressure and damages
but the mirabilite in the pore can. After investigating the deforma-
tion and crystallization pressure in the pore, Coussy [37] correlated
the crystallization pressure with the macroscopic tensile stress, a
correlation that can forecast the damage time via the critical stress
was proposed. However, most of these studies focused on the
supersaturation of sodium sulfate solution only, but not on the
influence of relative humidity on the crystallization pressure. Stei-
ger and Asmussen [38] proposed a crystallization-pressure equa-
tion that considered the influences of both thermodynamic
solubility and the relative humidity. This equation has been widely
used by the subsequent researchers. Different from the crystalliza-
tion of mirabilite, the formations of gypsum and ettringite in the
3
pore belong to ionic reaction [24]. Both gypsum and ettringite
are formed with the reaction of ions by a through-solution mech-
anism [39]. The reaction solution belongs to multicomponent
dielectric solution, the crystallization pressure correlates with the
ion activity product in the solution. On the basis of the crystalliza-
tion pressure equation of supersaturated solution, Scherer et al.
[9,40,41] proposed an ionic-reaction crystallization pressure equa-
tion that can be used to calculate the crystallization pressure of
gypsum and ettringite in the pore solution. Based on this new
equation, Flatt and Scherer [42] analyzed the thermodynamics of
crystallization stress when the ettringite formation is delayed
(DEF). They calculated the lowest content, the storage temperature
and the limited space of ettringite crystal that cause damages in
the pore. In addition, on the basis of the ionic-reaction crystalliza-
tion pressure equation, Yu et al. [43] calculated the crystallization
pressure of ettringite in the pore of the concrete under the sulfate
attack and the failure mechanism in the plain concrete.
Most of the studies centered on the pore crystallization pres-
sure which belongs to microscopic force. However, the concrete
failure always results from the macroscopic tensile stress, which
can be caused by crystallization pressure. When the macroscopic
tensile stress exceeds the critical tensile strength of the concrete,
the concrete is damaged. Hence, a bridge is needed from the micro-
scopic crystallization pressure to the macroscopic tensile stress for
forecasting the life of the concrete. Coussy [37] derived the equa-
tion between the macroscopic stress and the crystallization pres-
sure on the basis of the thermodynamic and physical chemistry.
Coussy pointed out that the macroscopic stress is a function of
crystallization pressure, of Biot coefficient and of the volume frac-
tion of the pore space filled with crystals. However, Coussy’s equa-
tion has rarely been used to forecast the damaging time of the
concrete under sulfate attack, because the volume fraction is hard
to calculate precisely. On one hand, the solid volume is composed
of several kinds of crystals such as mirabilite, gypsum and ettrin-
gite. On the other hand, the volumes of gypsum and ettringite vary
not only with the soak time in the solution but also with the reac-
tion rate of ions in the solution. In addition, calculation of the
reaction-rate of ionic reaction needs to understand the molecular
dynamics theory.
The calculation is more complicated when the concrete is sub-
jected to WD cycles, because the volumes of the crystals accumu-
late in the pore with the increase of the cycle time. So far, the
stability and the crystallization pressure of the crystal are studied
on the basis of the thermodynamics [44–47]. Limited studies are
centered on the reaction rate of gypsum and on the volume frac-
tions of both mirabilite and gypsum in the pore space. However,
the research of mirabilite and gypsum in the pore of plain concrete
is critical to understand the failure mechanism of concrete and
forecast its damage time. Such studies are important for the engi-
neering application of the concrete and are also meaningful to
understand the destruction process of the concrete subjected to
the WD cycles of sodium sulfate solution.
Formulae about the crystallization pressure and the volume
fraction in the pores are always used to forecast and analyze the
damage of concrete under WD cycle test. Due to the complexity
of the in-situ environment, the formulae are usually used in the
indoor test. For the indoor WD cycle test, the test conditions vary
from person to person [48–50]. However, most of the tests are con-
ducted according to the relevant test standards [48–49]. Based on
the standard, the concentration of the sodium sulfate solution is
5 wt%, the cycle period is 24 h, the total cycle number is 150 times
and so on. During the test, the compressive strength, the mass and
the ultrasonic velocity of plain concrete samples were usually
tested to analyze the durability of concrete subjected to WD cycles.
Among which, the mass change is an important index for the dura-
bility of the concrete and can reflect the damage mode in the
4 J. Ren et al. / Construction and Building Materials 264 (2020) 120525
concrete. The previous studies found that the mass of the concrete
increases with the increase of WD times. However, these studies
have a limit. Because their test span are usually ten, fifteen, or
thirty cycles [51–53], the test results just can reflect the change
trend of the mass but fail to represent the specific variation of
the mass during the experimental process. The specific variation
of the mass can bring a further understanding for the damage in
the concrete. Therefore, a high frequency testing during the WD
cycles is needed. In addition, a further study on the damage mode
of the concrete is needed.
Here the damage of the concrete subjected to WD cycles using
the sodium sulfate as the solution was studied. The interaction
between the sodium sulfate solution and the hydration products
in the pore was investigated. The growth rule, growth rate and
the volume of the crystals on the basis of the molecular dynamics
and physical chemistry were also studied. Through these studies,
formulae for the volume fraction of mirabilite and gypsum at dif-
ferent WD cycles were proposed. With the volume fraction and
the crystallization pressure of the crystals, the macroscopical ten-
sile stress developed in a plain concrete can be calculated. By com-
paring the macroscopical tensile stress during each WD cycle with
the critical tensile stress of the concrete, the damage of the con-
crete under WD cycle can be forecasted. Then, the reliability of
the formulae is verified by our laboratory WD test results. The
WD cycles were conducted according to the relevant test stan-
dards. During the test, a high frequency testing method was used
to explore the specific variation of concrete. The new damage mode
of concrete under WD cycles was found. On the basis of these tests
and the theoretical formulae, the life and the damaging process of
the plain concrete, attacked by cyclic wetting and drying, can be
forecasted and understood.
2. Growth of crystals under WD cycles
2.1. Properties of the crystals
Several kinds of crystals are generated in concrete during WD
cycles. One is mirabilite formed by the supersaturation of sodium
sulfate solution; the other two are ettringite and gypsum which
are produced by the reaction between hydration products and
sodium sulfate. These crystals change with the temperature, the
humidity and the concentration of sodium sulfate solution. Hence,
it is necessary to study the stability and changing rule of the crys-
tals at different conditions in order to analyze the failure mecha-
nism of concrete under WD cycles.
2.1.1. Sodium sulfate
Sodium sulfate belongs to monoclinic and has at least eight
crystal phases [11]. Phase I and phase II can only exist at the tem-
perature above 270 °C and 225 °C. Phase II have a narrow stability
zone [54]. The crystalline phase Na2SO48H2O is formed only under
high pressure condition [55–58]. Only phases III, IV, V, sodium sul-
fate heptahydrate, and mirabilite can exist at room temperature
(20 °C), of which phases III, IV and sodium sulfate heptahydrate
are unstable [54,59]. Therefore, only phase V and mirabilite can
stably exist at room temperature.
Na2SO4 usually has three possible crystal phases in the pore
solution: an anhydrous phase (thenardite), a decahydrated phase
(mirabilite), and a metastabel heptahydrated phase. The crystal-
lization pressure in the pore is often calculated by Eq. (1) [21]
based on thermodynamics. The crystallization pressure can also
be calculated by Eq. (2) [60] in which the crystallization pressure
is a function of the contact angel between the crystal liquid
interface and the pore wall. The contact angel is usually larger than
90° (Fig. 1). Rijniers et al. [35,36] found that sodium sulfate
heptahydrate has a contact angel of about 90° and cannot cause
significant stress in a porous medium. Hence, only the crystalliza-
tion pressures of thenardite and mirabilite at room temperature
are considered.


nRT cNa2 SO4
Pc ¼ ln ð1Þ
vc cs
2f cosh
Pc ¼ ð2Þ
rp
where Pc is the crystal pressure in the pore (MPa), n is the number
of ions in the salt, R is the molar gas constant (J/(mol∙k)), T is the
temperature in Kelvin (K), vc is the molar volume of the salt
(L/mol), cNa2 SO4 is the saturation concentration of sodium sulfate in
the pore (mol/L), cs is the saturation concentration of sodium sulfate
(mol/L), f is the surface tension (N/m), h is the contact angel
between the crystal liquid interface and the pore wall (°) and rp is
the radius of the pore (m) (assuming that the pore is a cylindrical
shape).
The transformation between thenardite and mirabilite is influ-
enced by temperature and relative humidity. The correlation
between the sodium sulfate solution and temperature is shown
in Fig. 2 [61]. There are two important bifurcations. One bifurcation
temperature is 32.38 °C, above which the supersaturation sodium
sulfate solution precipitates as thenardite and below which, as
mirabilite. The crystal phase can also be changed by relative
humidity (Fig. 3) [60]. Above 32.38 °C, the sodium sulfate directly
precipitates as thenardite at any relative humidity [62,63]. Below
32.38 °C, the sodium sulfate precipitates firstly as mirabilite and
then as thenardite with the decrease of the humidity [63,64].
2.1.2. Ettringite and gypsum
The ettringite has a volume that is about 2.27 times of the vol-
ume of solid reactant. The crystallization of ettringite thus causes
expansion, spalling, and cracking in the concrete [65]. Ettringite
is formed by ion reactions in the solution, because the solid–solid
conversion is kinetically difficult at room temperature and more
likely to occur at high temperature or in very low porosity system
[66]. Ettringite begins to lose free water when the temperature
above 40 °C [44,67,68]. On the contrary, gypsum has a good ther-
mostability. Above 104 °C, gypsum begins to lose free water.
Hence, the gypsum is stable during the WD cycles as the common
drying has a temperature up to 75 °C [69], at which the phase of
ettringite has changed.
When the concrete immerses in a sodium sulfate solution, the
gydration product calcium hydroxide can react with sodium sul-
fate and produce gypsum (Eqs. (3) and (4)). After that, the gypsum
can react with the hydrated calcium aluminate and produce ettrin-
gite (Eq. (5)). The main product is determined by the concentration
of the sulfate ion [70], with the product as ettringite at low concen-
tration but gypsum at high concentration [28,71,72].
2C 2 S þ 4H2 O ! C 3 S2 H3 þ CaðOHÞ2 ð3Þ
Fig. 1. The crystal grows in the pore.
 J. Ren et al. / Construction and Building Materials 264 (2020) 120525 5

mirabilite in the pore if the concentration of sodium sulfate solu-

tion in the pore is known. However, the growth rate of gypsum
depends on the reaction rate of the ions, the concentration of the
sodium sulfate solution and the wetting duration. The reaction rate
also correlates with the reaction type. It is necessary to investigate
the reaction type and the reaction rate of the production of
gypsum.

2.2.1. Reaction type and rate

Fig. 2. The diagram of the crystal phase changes with the temperature [61].
Fig. 3. The diagram of sodium sulfate solution changes with the relative humidity
[60].
CaðOHÞ2 þ Na2 SO4 þ 2H2 O ! CaSO4  2H2 O þ 2NaOH ð4Þ
The gypsum forms during the reaction of calcium hydroxide,
sodium sulfate and water in the pore solution. As strong elec-
trolytes, both calcium hydroxide and sodium sulfate can be fully
ionized in the solution as calcium ion, hydroxide ion, sodium ion
and sulfate ion. Hence, the formation of gypsum belongs to liquid
phase ionic reaction [73]. The calcium ion in the pore solution orig-
inates from the dissolution of solid hydration product calcium
hydroxide. The solubility of calcium hydroxide is small and
decreases with the increase of temperature [74,75]. Calcium
hydroxide in pore of concrete is sufficient and can furthest dissolve
in the pore solution at the test temperature. Hence, it can be
assumed that the concentration of calcium ion is equal to the sol-
ubility of calcium hydroxide at the experimental temperature.
There are three stages during the generation of gypsum. In the
first stage, calcium hydroxide and sodium sulfate are ionized in the
solution. In the second stage, the ions diffuse in the solution and
form particle pairs when ions are meeting. In the last stage, the
particle pairs react and produce the gypsum. During the second
stage, there are a mass of water molecules around the reaction
ions. The reaction ions need constantly extrude the water mole-
cules and enter into the same cage to meet and react with each
other [76] (Fig. 4).
The crystal of gypsum is composed of calcium ion, sulfate ion
and water molecule. Because the reaction takes place in water, it
can be considered that water has no effect on the reaction rate.
Hence, the reaction rate depends on the concentration and diffu-
sion rate of calcium ion and sulfate ion. The reaction equation
can be written as:
k1D
  k
Ca2þ þ SO2
4 $ Ca  SO2 ! CaSO4  2H2 O ð6Þ
2þ 2
4
k1D H2 O

where (Ca2þ  SO2 4 ) is the particle pair, k1D is the diffusion-rate con-
3ðCaSO4  2H2 OÞ þ 3CaO  Al2 O3  12H2 O þ 14H2 O stant of reaction particle, k-1D is the separation-rate constant of the
! 3CaO  Al2 O3  3CaSO4  32H2 O ð5Þ particle pair, k2 is the reaction-rate constant of the particle pair. For
some time later, the concentration of the particle pair reaches the
The concentration of sodium sulfate solution used in the labora- stabilization state:
tory is always much larger than that in site. However, the WD
interface of the concrete in site always suffers cyclic WD. Hence, dcðCa2þ SO2 Þ
the concentration of sodium sulfate at the WD interface is also
4
¼ k1D  cCa2þ  cSO4 2  k1D cðCa2þ SO2 Þ  k2 cðCa2þ SO2 Þ ¼ 0
dt 4 4

much larger than that under site condition, comparable to the con- ð7Þ
centration used in laboratory. Therefore, the WD interface is pref-
erentially damaged. In addition, the damage generated by the where cðCa2þ SO2 Þ is the concentration of the particle pair
4

expansion crystal is mainly induced by gypsum instead of ettrin- (Ca 

2þ
SO2
4 )
(mol/L), cCa2þ is the concentration of calcium ion (mol/
gite. Hence, the growth rate of gypsum was considered, while the L), cSO2 is the concentration of sulfate ion (mol/L). From Eq. (7),
4
influence of ettringite was neglected. The plain concrete samples
the concentration of the particle pair at the stabilization state can
are damaged rapidly under WD cycles, during which the influence
be obtained:
of sodium sulfate on the gel materials in the concrete is negligibly.
Hence, only the damage caused by the crystallization of mirabilite k1D  cCa2þ  cSO2
and gypsum was studied. cðCa2þ SO2 Þ ¼ 4
ð8Þ
4 k1D þ k2
The reaction rate can be calculated by:
2.2. Growth rate of the crystal
k2 k1D
cG ¼ k2 cðCa2þ SO2
4 Þ
¼ c 2þ  cSO2 ¼ kG  cCa2þ  cSO2 ð9Þ
The crystallization pressure is determined by the volume of k1D þ k2 Ca 4 4

expansion crystal in the pore. The volume is always determined

by the growth rate of crystal in the pore. The volume of sodium sul-
fate in the pore depends on the concentration of the sodium sulfate
solution and on WD times. It is feasible to calculate the volume of
where cG is the formation rate of gypsum (mol/(Ls)), kG is the
k2 k1D
reaction-rate constant of gypsum andkG ¼ k1D þk2
. When k-1Dk2,
the diffusion rate of the ions is much quicker than the reaction rate
6 J. Ren et al. / Construction and Building Materials 264 (2020) 120525

Fig. 4. The particles react in the solution.

 2
of the particle pair and kG ¼ kk21D
k1D
. The reaction rate of gypsum cCa2þ ¼ 4p rCa2þ þ rSO2 DSO2 cSO2 ð12Þ
4 4 4
mainly depends on the reaction rate of the particle pair. When
k2k-1D, the particle pair reacts in a rate that is faster than the dif- where ISO2 is the flux of sulfate ion at the spherical area around the
4
fusion rate of the ions. Hence, kG = k1D, the reaction rate of gypsum calcium ion (mol/s),r Ca2þ is the radius of Ca2+ (pm), and r SO2 is the
4
mainly depends on the diffusion rate of the ions in the solution [77]. radius of SO2
4 (pm).
As the reactive activation energy of gypsum in the water solution is
Because both Ca2+ and SO2 4 are diffusing in the solution, the dif-
very small, the reaction rate of gypsum depends on the diffusion fusion coefficient DSO2 in Eq. (12) should beDCa2þ þ DSO2 . Also, the
rates of the ions. Hence, the formation of gypsum is a diffusion- 4 4

number of Ca2+ ions is more than one. Hence, the reaction rate
controlled reaction and the reaction rate should be calculated by
should be
the molecular kinetic theory [78,79].
  
According to reaction kinetics in the diffusion zone, it is cG ¼ 4p DCa2þ þ DSO2 r Ca2þ þ r SO2 cCa2þ  cSO2  NA ð13Þ
assumed that a Ca2+ cannot move, and SO2 4 reacts with Ca2+ if 4 4 4

the SO4 diffuses into the spherical zone around the Ca2+ with a
2 1
where NA is the Avogadro’s constant (mol ). According to Eq. (13),
rCa2þ SO2 radius (Fig. 5). r Ca2þ SO2 is the radius of Ca2+ plus SO2
4 the diffusion rate constant
4 4
  
(pm). There is a concentration gradient of SO2 4 around the Ca2+ iskG ¼ 4p DCa2þ þ DSO2 r Ca2þ þ rSO2 N A . From Stokes-Einstein dif-
[77,80]. The concentration of SO24 decreases with closing to Ca2+. 4 4

fusion coefficient equation, it can be got

The reaction rate is equivalent to the flux at the spherical area
around the Ca2+ with a r Ca2þ SO2 radius. According to Fick’s first
4 kB T
law of diffusion, the flux of SO2 2
4 (J SO2 mol/(sm )) per unit time
DSO2 ¼ ð14Þ
4 4 6pgw rSO2
4
per unit area is proportional to the concentration gradient:
dcSO2 kB T
J SO2 ¼ DSO2 : ð10Þ DCa2þ ¼ ð15Þ
6pgw rCa2þ
4
4 4 dr
where DSO2 is the diffusion coefficient of SO2 2
4 (m /s), r is the dis-
4 where kB is Boltzmann constant, kB = 1.38  1023(J/K); g is the vis-
dcSO2
tance between Ca and 2+
SO2
(pm), and dr4 is the concentration cosity of the solvent (Pas). Substituting Eqs. (14) and (15) into kG
4
gradient of SO2 2+ leads to
4 . Hence, the reactive particle number of Ca
(cCa2þ ) in unit time can be written as:  2
 2 2kB T r Ca2þ þ r SO2
kG ¼ 4
NA ð16Þ
cCa2þ ¼ ISO2 ¼ 4p r Ca2þ þ r SO2 J SO2 ð11Þ 3gw rCa2þ r SO2
4 4 4 4

Substituting Eq. (10) into Eq. (11) gets In fact, not all of the particles effectively collide with each other.
For the effective collision, the particles must have enough energy,
collide in the specific direction, collide for enough time, and exist
in the external of the molecule structure. Hence, the calculative
result of the diffusion rate constant is always much larger than
the practical value. The probabilistic factor P for the molecule col-
lision is added to Eq. (16), and the diffusion rate constant is
 2
2kB T r Ca2þ þ r SO2
kG ¼ 4
NA  P ð17Þ
3gw rCa2þ r SO2
4

The radius of the ion is always dependent on the charge number

and the charge distribution. The radii of calcium ion and the sulfate
ion are 99 pm and 258 pm, respectively. At the temperature of
298.15 K, the value of gw is 0.8937  103 Pas. It can be calculated
that kG = 9.222  109P(Lmol1min1). The reaction rate of calcium
ion and the sulfate ion at the temperature of 298.15 K was tested
and the value of the reaction-rate constant is 0.058 Lmol1min1
(Appendix 1). Using this value, the probabilistic factor is found to
be 1.048  1013. Based on the value of the probabilistic factor,
Eq. (17) can be expressed as
 2
Fig. 5. Schematic diagram of Ca2+ surrounded by SO2
4 ions. - 13 2kB T r Ca2þ þ r SO2
kG ¼ 1:048  10   4
 NA ð18Þ
3gw r Ca2þ r SO2
4
 J. Ren et al. / Construction and Building Materials 264 (2020) 120525 7

From Eq. (18), the reaction rate of the calcium ion and the sul- 2.2.3. The volume of thenardite
fate ion at any temperature can be obtained. After saturated, sodium sulfate solution in the pore is supersat-
urated and mirabilite precipitates under the following WD cycles.
2.2.2. The volume of gypsum During the drying process, the mirabilite transforms to thenardite
For the concrete under WD cycles, the calcium ion, the sulfate and the volume of the thenardite after i WD times can be written
ion and the water molecule react in the pore solution and form as
gypsum. As solvent, water has no influence on the reaction rate vT
V T;i ¼ V M;i ð29Þ
of gypsum. For the reaction vM
Ca2þ þ SO2
4 þ 2H2 O ! CaSO4  2H2 O ð19Þ where VM,i is the volume of mirablite after after i WD times (L), VT,i is
its reaction rate can be expressed as the volume of thenardite after i WD times (L), vT is the molar vol-
ume of thenardite (L/mol) and vM is the molar volume of mirabilite
1 dn (L/mol).
cG ¼ ð20Þ
V p dt
2.2.4. The volume fraction of the crystal in the pore.
where n is the reaction degree (mol), t is the reaction time (s), and
The accumulation of crystals in the pore can be divided into two
Vp is the volume of the pore (L). According to law of mass
stages under WD cycles. Before the saturation of sodium sulfate
actioncG ¼ kG  cCa2þ  cSO2 , integrating cG from the original state
4 solution, only gypsum is generated in the pore. After the saturation
(t = 0) to the current state (t0), one gets: of sodium sulfate, mirabilite and gypsum are generated at the same
n ¼ kG  cCa2þ  cSO2  V p  t 0 ð21Þ time. The following investigates these two stages sequentially.
4

The particle number of the reaction product is: (1) The sodium sulfate solution is not saturation
NG ¼ N0G þn ð22Þ
At this stage the pore volume that the solution can invade to
where NG is the particle number of gypsum (mol), N 0G is the particle during each WD cycle was assumed to remain unchanged. If the
number of gypsum at the initial condition (mol). Substituting Eq. sodium sulfate solution is saturated after n WD cycles, the volume
(21) into Eq. (22) gets: of gypsum in the pore can be expressed as
nðn þ 1Þ
NG ¼ N0G þ kG  cCa2þ  cSO2  V p  t0 ð23Þ V G;n ¼  kG  V 0p  t 0  v G  c0SO2  cCa2þ ð30Þ
4
2 4

Due to no gypsum under the initial condition, the particle num- where V0p is the initial volume of the pore (L).
ber of gypsum isN 0G ¼ 0. The particle number of gypsum at the time As vG is a function of the density of gypsum (qG = 2.32  103 g/
of t0 can be written as L), and of the molar mass of gypsum (MG = 172 g/mol), the molar
NG ¼ kG  cCa2þ  cSO2  V p  t 0 ð24Þ volume of gypsum can be calculated by:
4
MG
Assuming that the wetting duration for each WD cycle is t0 and vG ¼ ¼ 74:53  10 - 3
L=mol ð31Þ
qG
the sodium sulfate solution is saturated after n WD cycles. Before
the sodium sulfate solution reaching saturation, it can be assumed Similar to Eq. (31), one can obtain that the molar volume of cal-
that the concentration of the sodium sulfate solution in the pore of cium hydroxide (v CaðOHÞ2 ) is 33.4  103 L/mol. As one molar calcium
concrete is an arithmetic progression whose common difference is hydroxide reacts with one molar sodium sulfate and produces one
the initial concentration of the sodium sulfate solution. Neglecting molar of gypsum, this would result in
the influence of the gypsum on the pore volume, the particle num-
V DG ¼ 0:55V G ð32Þ
ber of gypsum after n cycles of WD (N nG (mol)) can be obtained:
where VDG is the solid volume increment from the formation of
nðn þ 1Þ
NnG ¼  kG  V p  t 0  c0SO2  cCa2þ ð25Þ gypsum (L), VG is the volume of gypsum (L). Hence, the volume frac-
2 4
tion of the pore space filled with crystals after n WD cycles (Sn) can
where c0SO2 is the initial concentration of the sodium sulfate be expressed as
4

(mol/L). The volume of gypsum after n times of WD cycle 0:55V G;n nðn þ 1Þ 
Sn ¼ ¼ 0:55  kG  t 0  v G  c0SO2  cCa2þ ð33Þ
(VG,n (L)) can be expressed by V 0p 2 4

nðn þ 1Þ
V G;n ¼  kG  V p  t 0  v G  c0SO2  cCa2þ ð26Þ The volume of the pore space after n times of WD cycles (Vnp (L))
2 4
is
where vG is the molar volume of gypsum (L/mol).
With the increase of WD cycle, the concentration of sodium sul- V np ¼ V 0p  0:55V G;n ð34Þ
fate reaches saturation and keeps unchanged in the following
cycles. After i WD cycles, the particles number of gypsum
(N iG mol) can be expressed as (2) The sodium sulfate solution is saturation
1) Assuming that the sodium sulfate solution is saturated after
NiG ¼ i  kG  V p  t 0  csat
SO2
 cCa2þ ð27Þ
4 n WD cycles, the solution supersaturates and produces mir-
where csat is the saturation concentration of sodium sulfate abilite in the following cycles. After n + i + 1 WD cycles, the
SO2 4 volume in the pore, which can be used for the solution to
(mol/L). Hence, the volume of gypsum after i WD cycles invade (VQ (L)), is
(VG,i (L)) is
vT
V G;i ¼ NiG  v G ¼ i  kG  V p  t0  v G  csat  cCa2þ ð28Þ V Q ¼ V np  V M;i þV V ð35Þ
SO24 v M S G;i
8 J. Ren et al. / Construction and Building Materials 264 (2020) 120525

where V S is the volume of the solid dissolved in the pore solution As the forming rate of gypsum is much slower than that of mir-
(L). From Eq. (32), it can be written by abilite [11,43] and as the expansion volume is only about half of
the gypsum, it can be assumed that
V S - V G;i ¼ - 0:55V G;i ð36Þ
!
Substituting Eq. (36) into Eq. (35), one gets the volume in the V M;i V M;i V G;i
 þ 0:55 n ¼ Si ð48Þ
pore that can be used for the solution to invade after i + 1 WD V np V np Vp
cycles:
Based on Eq. (48), Eq. (47) can be written as
vT
V Q ¼ V np  V M;i
vM
 0:55V G;i ð37Þ vT
V Q =V np ¼ 1 - Si  ð49Þ
vM
2) From Eq. (37), the volume of the mirabilite produced during In Eq. (45), assuming A = ðv M þ 0:55kG  t0  v G  cCa2þ Þcsat
SO2
and
the i + 1 wetting process (Vi+1
M (L)) can be calculated by:
4

substituting Eq. (49) into Eq. (45), one gets



vT vT
V iþ1
M ¼ V np  V M;i  0:55V G;i csat  vM ð38Þ Siþ1 ¼ Si 1  A  þA ð50Þ
vM SO2 4 vM
3) The volume of mirabilite in the pore after i + 1 times of WD It can also be assumed that
cycles can be expressed as vT
A ¼q

 vM
vT
V M;iþ1 ¼ V M;i þ V np  V M;i  0:55V G;i csat  vM ð39Þ then, Eq. (50) can be simplified as
vM SO2 4

Siþ1 ¼ Si ð1  qÞ þ A ð51Þ
Similarly, the volume of gypsum in the pore after i + 1 WD
cycles (VM,i+1 (L)) can be expressed as It can be seen that this is a geometric progression whose com-
 mon ratio is (1-q). The volume fraction of the crystals in the pore
V G;iþ1 ¼ V G;i þ kG  V Q  t0  v G  csat
SO2
 cCa2þ ð40Þ after one WD cycle (S1) can be calculated by
4

The volume increment produced by the formation of gypsum is V np  csat

SO2
 v M þ 0:55V G;1
S1 ¼ 4
ð52Þ
0:55V G;iþ1 ¼ 0:55V G;i þ 0:55  kG  V Q  t 0  v G  csat
SO2
 cCa2þ ð41Þ V np
4

where VG,i+1 is the volume of gypsum after i + 1 WD cycles. With Eqs. (51) and (52), the volume fraction of the crystals in
the pore after i times of WD cycles can be obtained by:



4) From Eqs. (39) and (41), the volume fraction of crystals in vM v T ði1Þ v M
Si ¼ A   1A þ ð53Þ
the pore after i + 1 WD cycles (Si+1) can be obtained by
vT vM vT
V C;iþ1 Eq. (53) can be simplified as
Siþ1 ¼ "
V np
i #

 vM vT
vT Si ¼
vT
1 1A
vM
ð54Þ
¼ ðV M;i þ V np  V M;i  0:55V G;i csat  v M Þ=V np
vM SO2 4

þ 0:55V G;iþ1 =V np ð42Þ where A = ðv M þ 0:55kG  t 0  v G  cCa2þ Þcsat

SO2
and is defined as the coef-
4

ficient which influences the growth rate of the crystal in the pore.
where VC,i+1 is the volume of the crystal in the pore after i + 1 WD
cycles (L). Eq. (42) can be simplified as
! (3) The total volume fraction of crystals in the pore
V M;i V G;i VQ
Siþ1 ¼ þ 0:55  n þ n  csat2 According to the volume fraction of crystals in the pore at the
V np Vp V p SO4
first and the second stages, the total volume fraction after m
 ðv M þ 0:55kG  t 0  v G  cCa2þ Þ ð43Þ (m = n + i) WD cycles (Sm) can be obtained by
As the volume fraction of crystals in the pore after i WD cycles 0:55V G;n þ Si  V np
(Si) is Sm ¼ ð55Þ
V 0p
V M;i V G;i
Si ¼ þ 0:55  n ð44Þ where V0p is the initial volume of the pore (L). Eq. (55) can be simpli-
V np Vp
fied as
Substituting Eq. (44) into Eq. (43) gets the volume fraction of
the crystals in the pore after i + 1 WD cycles Sm ¼ Sn þ Si ð1  Sn Þ ð56Þ

Siþ1 ¼ Si þ V Q =V np  csat
SO2
 ðv M þ 0:55kG  t 0  v G  cCa2þ Þ ð45Þ
4 Eq. (56) can be used to calculate the volume fraction of crystals
in the pore.
where


vT (4) The volume fraction of mirabilite and gypsum in the pore
V Q =V np ¼ V np  V M;i  0:55V G;i =V np ð46Þ
vM
After the sodium sulfate solution reaching saturation, the vol-
It also can be expressed as
! ume in the pore that is available for the invading solution is VRi


V M;i V G;i V M;i vT (L) at the number i WD cycle, where i = 1,2,3i. From Eqs. (39)
V Q =V np ¼1 þ 0:55 n þ 1 ð47Þ
V np Vp Vpn
vM and (41), after i WD cycles, the volume of mirabilite and gypsum
can be obtained by
 J. Ren et al. / Construction and Building Materials 264 (2020) 120525 9

  i 
V M;i ¼ csat v V þ csat v V þ    þ csat v V vM
2  v T
so2 M R1 so2 M R2 so2 M Ri Si ¼ 1  1  csat ð68Þ
4 4 4
vT SO
v ðV R1 þ V R2 þ    þ V Ri Þ
4
¼ csat
so2 M
ð57Þ
4
This result is consistent with the result proposed by Flatt et al.
    [11], verifying that the Eq. (56) is reasonable and reliable.
V G;i ¼ 0:55kG t0 csat
so2
cCa2þ v G V R1 þ 0:55kG t 0 csat
so2
cCa2þ v G V R2
 
4 4

þ 0:55kG t0 csatso2
cCa2þ v G V Ri 3. Crystallization pressure and the failure of materials
 
4

¼ 0:55kG t0 csat c
so2 Ca2þ G
v ðV R1 þ V R2 þ    þ V Ri Þ
4
ð58Þ 3.1. Crystallization pressure in the pore

According to Eqs. (57) and (58), the total volume of the crystals In 1939 Correns and Steinborn [81] proposed an equation for
in the pore after i WD cycles (VC,i (L)) can be expressed as crystallization pressure of one molar substance on the basis of
ideal solution and single molecule crystallization:
V C;i ¼ V M;i þ V G;i
0
  RT c
¼ csat v þ 0:55kG t0 csat
so2 M 4
c v ðV R1 þ V R2 þ    þ V Ri Þ
so2 Ca2þ G 4
Pc ¼
vc
ln 0
cs
ð69Þ

¼ AðV R1 þ V R2 þ    þ V Ri Þ where c’ is the concentration of the solution, and cs’ is the concen-
ð59Þ tration of the saturated solution. The equation is only valid for ideal
solutions of molecular solutes. Correns also put forward another
During the WD test with saturated sodium sulfate, the volume
equation for the crystallization pressure. One is the osmotic pres-
ratio of mirabilite and gypsum in the total volume after i WD cycles
sure [34]
can be obtained by:
Pc v c ¼ RTlnðp=ps Þ ð70Þ
V M;i csat
so2
vM csat
so2
vM
¼ sat 4
¼ 4
ð60Þ
V C;i cso2 v M þ 0:55kG t 0 csat c
so2 Ca
2þ v G A where p is the osmotic pressure (Pa) and ps is the saturated osmotic
4 4 pressure (Pa). The other is the saturation pressure

0:55kG t 0 csat cCa2þ v G 0:55kG t 0 csat cCa2þ v G Pc v c ¼ RTlnðcNa2 SO4 =cs Þ ð71Þ
V G;i so2 so2
¼ sat 4
¼ 4
ð61Þ
V C;i cso2 v M þ 0:55kG t 0 csat c 2þ v G
so2 Ca
A Based on the equations proposed by Correns, Steiger and
4 4
Asmussen [38] put forward the crystallization pressure of the sat-
Hence, the volume fraction of mirabilite (SM,i) and gypsum (SG,i) urated sodium sulfate solution
in the pore at the second stage can be expressed as:


RT RHsat;T

" # Pc ¼ lnK SP;T  lnK SP;M þ 10ln ð72Þ
V M;i v M vT i
V M;i vc 100
SM;i ¼ Si ¼ 1 1A ð62Þ
V C;i vT vM V C;i where RHsat,T is the deliquescence relative humidity of thenardite
" and is determined by the water activity in a non-ideal solution cal-

#
V G;i v M vT i culation using Pitzer coefficients suited for a solution with particu-
V G;i
SG;i ¼ Si ¼ 1 1A ð63Þ
V C;i v T vM V C;i larly high concentrations. KSP,T and KSP,M are the thermodynamic
solubility products of thenardite and mirabilite, respectively.
From Eqs. (62) and (63), the volume fractions of mirabilite (SM) Gypsum is formed by ion reaction in the solution, and the crys-
and gypsum (SG) in the pore after the two stages are tallization pressure of gypsum is different from that of sodium sul-
fate. Based on the crystallization pressure equation proposed by
SM;i  V np
SM ¼ ð64Þ Correns, one can have the crystallization pressure for ion reaction
V 0p [24,39,42,82]:


0:55V G;n þ SG;i  V np RT Q
Pc ¼ ln reac ð73Þ
SG ¼
V 0p
ð65Þ vc K reac

According to Eqs. (33) and (34), Eqs. (64) and (65) are simplified where Qreac is the ionic activity product defined by
Y v reac
as Q reac ¼ ae e ð74Þ
SM ¼ SM;i ð1  Sn Þ ð66Þ e

where Kreact is the equilibrium constant of the chemical reaction, ae

SG ¼ Sn þ SG;i ð1  Sn Þ ð67Þ and v e
ðreacÞ
are the activity and the stoichiometric coefficient of ion e
in the solution, respectively.
For any salt M N1 X N2  N 3 H2 O, its electrolytic type can be
(5) The volume fraction of crystals in the pore under other expressed as
conditions M N 1 X N2  N 3 H2 O $ N 1 M þ N 2 X þ N 3 H 2 O ð75Þ

For some other materials, such as rock, only mirabilite is gener- At the dissolution equilibrium state, one has
ated in the pore during WD cycles with sodium sulfate solution.
N1 lMv þ þ N2 lXv  þ N 3 lW  lMN X N N 3 H2 O ¼0 ð76Þ
There is no calcium hydroxide which can react with the sodium 1 2

sulfate and produce gypsum. In Eq. (56), letting Sn ! 0, that is to

  According to the electrolyte balance theory, one has that
say kG  t 0  v G  csat
SO2
 cCa2þ ! 0, it can be obtained that Sm = Si
4
le ¼ lHe þ RTlnae ð77Þ
and A ¼ v M  csat
SO2
. Eq. (54) was simplified as
4
10 J. Ren et al. / Construction and Building Materials 264 (2020) 120525

where le and lH e are the chemical potential and the standard chem-
ical potential, respectively, at a given temperature and pressure; ai
is the ionic activity. Substituting Eq. (77) into Eq. (76) yields
lHMN1 XN2 N3 H2 O  N1 lHMv þ  N2 lHXv   N3 lHW
K MN1 X N2 N3 H2 O ¼ exp
RT
where K MN1 XN2 N3 H2 O is the dissolution equilibrium constant of
MN1 X N2  N 3 H2 O. Harvie and Wear used Pitzer’s formula to calculate
the dissolution equilibrium constants of 12 kinds of ions, 55 kinds
of salts and water, at the temperature of 25 °C and the pressure
of 101.325 KPa [83]. They have also given the standard chemical
potential of the ions, salts and water. Hence, the dissolution equilib-
rium constant of gypsum (KG) at the temperature of 25 °C and the
pressure of 101.325 KPa can be calculated by:
lG  lCa2þ  lSO2
H H H
3.3. Critical tensile stress of concrete
From Eqs. (66), (67), (72), (73) and (82), the macroscopic tensile
stress caused by the crystallization pressure in the pore can be cal-
culated. Then, it can be used to forecast the damage of the concrete.
ð78Þ The critical tensile stress of concrete is [86]
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
rc ¼ rT = 3ð1  2eÞ ð85Þ
where rc is the critical tensile stress (MPa), rT is the tensile strength
of the concrete (MPa) and e is the Poisson’s ratio. For concrete, the
Poisson’s ratio is usually 0.24–0.25 [85–87] and typically e = 0.25 is
adopted. If the macroscopic tensile stress exceeds the critical stress,
the sample will be damaged.
4. Experiments

K G ¼ exp 4
¼ 2:627  10 - 5
ð79Þ To validate the equation used to forecast the damage of con-
RT crete, the compressive strength, the mass and the ultrasonic veloc-
where lHG , lHCa2þ and lHSO2 are the standard chemical potential of ity of plain concrete samples subjected to WD cycles are tested
4
according to Chinese standard GB/T50082-2009. The damage time
gypsum, calcium ion, sulfate ion, respectively. The crystallization
of the samples was worked out.
pressure in the pore of concrete composes of the crystallization of
mirabilite and gypsum and can be expressed as



 4.1. Materials
RT RHsat;T RT Q
PC ¼ lnK SP;T  lnK SP;M þ 10ln þ ln reac ð80Þ
vM 100 v G K reac The cement, used in this study, was 42.5 R Qilianshan cement in
accordance with the relevant Chinese standard. The specific sur-
The crystallization pressure in the pore of rock under WD cycles
face area was 320 m2/kg, the standard consistency was 25%. The
with a sodium sulfate solution mainly comes from the crystalliza-
chemical compositions of the cement were given in Table 1. The
tion of mirabilite and can be calculated by Eq. (72).
sand used was natural river sand which was taken from Liujiaxia
in Gansu province. The fineness modulus of the sand used is
3.2. The macroscopic tensile stress
2.37. The apparent density and water content of the sand are
1.47 kg/cm3 and 1.16%, respectively. The apparent density and
The crystallization pressure in the pore is the microscopic force
water content of the aggregate are 2.96 kg/cm3 and 0.59%, respec-
and only can be felt at the pore scale. A macroscopic tensile stress
tively. The aggregate is basalt with silt content 0.01% and a contin-
must be calculated to assess possible damage to the porous host
uous gradation of 5–20 mm. The water reducer used was
[37,42]. For this, a poromechanic approach is used [37], assuming
polycarboxylate superplasticizer with a water reduction up to
that mirabilite and gypsum are homogeneously distributed through-
25%. The water used to make the samples was tap water and that
out the sample. Averaging the stress over a representative volume
used for sodium sulfate solution is deionized water.
element yields the macroscopic tensile stress (r* (MPa)) [37]:

r  ¼ r r b 0 Sc ð81Þ 4.2. Samples and curing

where b’ is the Biot coefficient; Sc is the volume fraction of the crys-
The concrete used in the test was ordinary plain concrete and
tals in the pore and rr is the radial compressive stress (MPa) which
its composition was given in Table 2. The w/c stands for water
can approximatively equal to the crystallization pressure in the
cement ratio. These materials in Table 2 were mixed and molded
pore (rrDP). Zhang et al. [84] investigated the correlation between
into cubes with a side length of 100 mm. There are three samples
Biot coefficient and hydration degree, and found that the Biot coef-
in one group and there are thirteen groups in total. Eleven groups
ficient of concrete is generally about 0.20–0.40. Ulm et al. [85]
are used for the test and the other two are spare samples. Some
found that the Biot coefficient of concrete is 0.23 ± 0.1. This study
other mixtures were sieved by the sieve No. 4.75 mm and then
then takes the value of the Biot coefficient as 0.23.
pure into the mould (40  40  160 mm3) to make the cement
As the crystallization pressure in the pore of the concrete comes
mortar samples. Three cement mortar samples were prepared.
from mirabilite and gypsum, the macroscopic tensile stress can be
All of the samples were vibrated compactly on the shaking table
expressed as
and then cured in the molds for 24 hours. 24 hours later, the sam-
r ¼ rG þ rM ¼ b0 ðPG SG þ PM SM Þ ð82Þ ples were pulled out and cured in a standard condition for 28 days
with an ambient temperature of 20 ± 2 °C and a relative humidity
where PG (MPa) and rG (MPa) are the crystallization pressure and
over 95%. After that, the samples were dried for 48 hours at the
the macroscopic tensile stress caused by gypsum, respectively; PM
temperature of 75 °C, and then the samples were used for the
(MPa) and rM (MPa) are the crystallization pressure and the macro-
WD cycle test.
scopic tensile stress caused by mirabilite, respectively.
If there is only mirabilite or gypsum crystal in the pore, the
4.3. Test methods
macroscopic tensile stress is

(1) WD cycle test

r ¼ rM ¼ b0 PM SM ð83Þ
The WD cycle test was conducted on samples after 28 day cur-
or ing according to Chinese GB/T50082-2009. The schematic of WD
cycle was illustrated in Fig. 6. During the wetting procedure, the
r ¼ rG ¼ b0 PG SG

ð84Þ solution in the liquid storage tank got into the space where the
 J. Ren et al. / Construction and Building Materials 264 (2020) 120525 11

Table 1
The chemical compositions of the cement (wt.%).

SiO2 Al2O3 Fe2O3 CaO MgO SO3

21.78 5.25 3.31 66.32 1.12 0.41

samples stayed in. The concentration of the sodium sulfate solu-

tion used was 5 wt%. The solution was renewed after 15 WD cycles
in order to maintain the concentration of the solution in the
required values. The stainless steel grids were used to make sure
that the samples were in full contact with the solution. During
the drying procedure, the solution was discharged into the storage
tank and the samples were dried by the heating tube. The drying
temperatures were controlled by control panel on the control
box. The test time was 24 hours for one cycle, among which
15 hours were used for wetting the samples and 9 hours drying
the samples. The drying procedure was further divided into four
stages: 2 hours for air drying, 5 h for drying with high temperature,
one and a half hours for air cooling and half an hour for refrigera-
tion. The high drying temperature and the cooling temperature Fig. 6. The schematic of the WD cycle.
were 75 °C and 25 °C, respectively. The airing drying and the air
cooling temperatures were the ambient temperature (The temper-
ature of the room where we conducted the experiment was about 30 WD cycles. To ensure the test effect, cement mortars chosen
20 ± 3 °C). were natural flatness. The cement mortar samples were explored
at different magnifications using a German MERLIN Compact
(2) Compressive strength device. The crystals at the surface of the cement mortar were
observed.
The compressive strength was measured according to Chinese
standard of JTG E30-2005. The compressive strength of one group (6) Energy Dispersive Spectrometer (EDS)
of samples after 28 day curing was tested to detect the initial
strength. During the WD cycles, the compressive strength was After the sample was observed by SEM at different magnifica-
measured on each 3 samples after each three cycles and the load- tion, crystals at the surface of the sample were analyzed by EDS.
ing rate is 0.5 MPa/s. The mean value of the three samples was In the EDS figure, different X coordinates correspond to different
taken as test result, if the differences between the maximum, min- elements. Hence, the element composition of the crystal can be
imum values and the median value were within 15% of the median obtained.
value, respectively. If one of the difference values is not within 15%
of the median value, the median value was used as the test result. If (7) Mercury Intrusion Porosimetry (MIP)
both of the differences were not within 15% of the median value,
the compressive strength should be tested again. Cylindrical samples, with height of 10 mm and diameter of
10 mm, were drilled from the cement mortar. The pore character-
(3) The test of the mass change istics of the samples were tested after suffering 0, 15 and 30 WD
cycles, respectively. The samples were put into absolute ethanol
The three samples, which were used for the compressive
to stop the hydration reaction until they were used for the test.
strength test after 30 cycles, were also used for the mass change
Before the test, the samples were taken out and dried at ambient
test. Their masses were tested after each WD cycle and recorded.
temperature. The MIP (Auto Pore IV 9500 type) with a maximum
pressure of 413.8 MPa was used to evaluate the porosity and
(4) The test of ultrasonic velocity
pore-size distribution of the samples. The density, contact angle
and the surface tensile of mercury were taken as 13.5335 g/ml,
The three samples used for the mass change testing were also
130° and 485 dynes/cm, respectively. The equilibrium time of both
used for the ultrasonic velocity test. The longitudinal wave veloci-
high pressure and low pressure were 10 s.
ties were tested on two fixed opposite surfaces of the samples. The
test was conducted after every three cycles and each sample was
tested for three times. The mean values were chosen as the test
4.4. Results and discussion
results.
To investigate the macro changes of the samples under WD
(5) Scanning Electron Microscope (SEM)
cycle, the compressive strength, the mass change and the ultra-
sonic velocity of the samples were tested during the experiment,
The cement mortar used for SEM was collected from the sample
because the compressive strength directly reflects the deteriora-
which was conducted by compressive strength test after suffering
tion of the sample, the mass change reflects the accumulation of

Table 2
The composition of 1 m3 concrete.

Cement (kg) Sand (kg) Aggregate (kg) Water reducer (kg) w/c
450 673 1097 4 0.4
12 J. Ren et al. / Construction and Building Materials 264 (2020) 120525
Fig. 7. The relationship between compressive strength and WD cycles.
expansive crystals in the pores and the spalling of mortar around
the sample, and the ultrasonic velocity reflects the compactness
of the concrete. After that, the SEM and MIP were conducted to
investigate the microcosmic changes in the samples. The crystal
type can be known by SEM, and the pore characteristics can be
understood by MIP.
4.4.1. Compressive strength
Fig. 7 shows the results of the compressive strength test. The
compressive strength has a slight decreasing at the first 6 cycles.
The reason may be that the sodium sulfate solution with the con-
centration 5 wt% is not saturated until the end of the fifth cycle
(Fig. 2). Until the sixth cycle, mirabilite precipitates and starts fill-
ing the pores in the concrete. Hence, the damage in the concrete
before the sixth cycle comes mainly from the corrosion function
of sodium sulfate (Eqs. (3) and (4)) and the shrinkage in concrete
during the drying stage. However, the corrosion reaction rate is
too slow and the volume of expansion crystal is insufficient to
damage the concrete. Therefore, it can be determined that the
decrease of compressive strength is mainly caused by the shrink-
age of the concrete. The compressive strength reaches the maxi-
mum at the ninth WD cycle. After that, the compressive strength
declines in a wave with the increase of cycle number, because mir-
abitite forms and then fills the pores and microfracture caused by
the shrinkage. The compressive strength is enhanced with the
gradually dense structure and reaches the maximum at the ninth
cycle. With the increase of the volumes of mirabilite and gypsum
in the pore, the crystallization pressure increases. When the crys-
tallization pressure exceeds the critical tensile stress of the con-
crete, the sample is damaged and the compressive strength
decreases with the increase of WD cycles.
4.4.2. Mass change
The masses of the samples after each cycle were tested and
shown in Fig. 8. It can be seen that the change rule has some differ-
ence with the previous studies [51–53]. In the previous studies, the
mass of the sample was tested every 15 or 30 cycles. The mass
always decreases firstly and then increases during the WD cycle.
With high frequency detection, more information can be obtained
from the results (Fig. 8). The mass has a little or no change at the
first eight cycles and has a relatively evident decrease at the ninth
cycle. This trend indicates that the concrete is damaged for the first
time during the ninth WD cycle. Some of the mortars are peeled off
from the sample and decrease the mass of the sample. Before the
first damage, the initial state of the sample is fine, so the damage
is not serious. The mass subsequently has an increasing trend after
the ninth cycle. The reason is that new crystals form and fill the
cracks from the first damage, and thus increase the mass of the
sample. With the continuous increase of cycle index, the cracks
from the first damage will fully be filled again and this causes
the second damage. It can be seen that the mass of the sample
declines significantly after the fifteenth cycle. Because the sample
has been damaged before, the second damage is more serious than
the first time (Fig. 7). After that, the samples are damaged for the
third time and then repeat the cycle again. Besides, the increment
of the mass is larger than the previous one, inferring that the dam-
age is more and more serious. Although the mass curves of the
samples fluctuate locally, the overall trends of the masses decrease
firstly and increase finally. These overall trends are same as the
results of the previous studies [51–53]. Based on the change rule
of the mass, it can be considered that damage is generated again
and again in the sample during the WD cycle. Hence, it can be rede-
fined that the concrete is in a dynamic damaging-filling state dur-
ing the WD cycle.
4.4.3. Ultrasonic velocity
Fig. 9 shows the ultrasonic velocity of concrete samples, which
reflects the compactness of the concrete. The ultrasonic velocity
increases at the first nine cycles and reaches the maximum at
the ninth cycle. This trend illustrates that the concrete is not dam-
aged before the ninth cycle and that the structure of concrete is
being denser. This finding is consistent with the change rule of
compressive strength. After the ninth cycle, the ultrasonic velocity
decreases. This decreasing trend indicates the structure of the con-
crete is damaged by the excessively crystallization pressure.
Although the crystals can fill the pores and cracks again after the
damage, the ultrasonic velocity still decreases. The reason is that
the aggregate and the mortar in the concrete are closely bonded
before damaging. After damage, the bonds are broken and the
structure is divided into mortar-crystal-aggregate state. There is
a layer of air between the different phases. The ultrasonic velocity
in the air is much lower than that in the aggregate and the mortar.
The interface between different phases greatly influences the ultra-
sonic velocity.
4.4.4. Microstructure analysis
The SEM was conducted on the cement mortar of the concrete
after 30 WD cycles. The image of the cement mortar is shown in
Fig. 10(a). There are many prismatic crystals in the pores. The ele-
mentary composition of the crystals was analyzed by the energy
spectrum (Fig. 10(b)). The main elements are calcium, oxygen
and sulfur. This indicates that gypsum is the main product during
Fig. 8. The relationship between the mass and the WD cycles.
 J. Ren et al. / Construction and Building Materials 264 (2020) 120525 13

the WD cycles and fills the pores in the concrete. Some cracks also
can be seen in the cement mortar and this indicates that concrete is
damaged during the WD cycles duo to the generation of expansion
crystal. After that the structure of the cement mortar was observed
at a larger magnification. It can be seen that there are some form-
less crystals in the pore which was filled with gypsum (Fig. 10(c)).
The main elements of the crystals are sodium, oxygen and sulfur
(Fig. 10(d)). These formless crystals should be sodium sulfate crys-
tal. This indicates that the pore solution saturates and sodium sul-
fate precipitates in the pore.
The MIP was employed to explain the influence of WD cycles on
pore characteristics. The tests were conducted on the cement mor-
tar samples after 0, 15 and 30 WD cycles. The pore diameter distri-
butions of the samples are shown in Fig. 11. Pores in the samples
include gel micro-pores (<10 nm), capillary pores (10–5000 nm)
and macro-pores (>5000 nm) [88]. Only one peak can be found
for the samples without WD attack. The most probable aperture
is about 77 nm. However, two peaks can be observed for the sam-
ples after 15 and 30 WD cycles. The peaks move to the two sides
compared with the sample without WD attack. The peaks of the
sample after 15 WD cycles are 70 nm and 151 nm. The peaks of
the sample after 30 WD cycles are 40 nm and 183 nm. The varia-
tion of the most probable aperture indicates that some of the pores
in the concrete are filled with the expansive crystals and the crys-
tallization pressure of these expansive crystals results in more
large pores in the concrete. With the increasing of WD cycle times,
this trend is more and more obvious and aggravates the damage of
concrete. In addition, the volumes of the pores, which are smaller
than 5 nm and larger than 6000 nm, also decrease with the increas-
ing of WD cycle times. This indicates that some gel micro-pores are
fully filled by the expansive crystals and then burst to capillary
pores. The macro-pores are absolutely filled and also change to
capillary pores.
The critical apertures of the samples are then analyzed in
Fig. 12. The critical aperture refers to the through pore size in the
concrete and is very important for the concrete. It can be seen that
the critical aperture is increased after WD cycles. The critical aper-
tures after 15 and 30 cycles are about 1000–2000 nm, and the crit-
ical aperture is only about 500 nm before the WD cycle. This
indicates that the concrete is more easily damaged after WD cycle.
This is consistent with the test result of compressive strength.
The proportions of gel micro-pores, capillary pores and macro-
pores in the samples are shown in Fig. 13. It can be seen that the
volume of capillary pores increases with the increase of WD cycles.
The volumes of micro-pores and macro-pores decrease with the
increase of WD cycles. Besides, it also can be seen that the porosity
increases after WD cycles, and it has a little change during the first
15 cycles and increases obviously during the latter 15 cycles. These
results also indicate that some micro-pores and macro-pores are
changed into capillary pores by the generation of expansive crys-
tals. When the volume of the expansive crystals is large enough,
the pore wall is damaged by the crystallization pressure and more
pores are formed in the samples. Therefore, the porosity of the
sample increases with the increase of WD times.
5. Model verification and discussion
To verify the volume fraction formula proposed in this paper,
the formula was used to calculate the damage time of the concrete
samples subjected to WD cycles.
5.1. Damage of concrete under WD cycles
The conditions in the WD cycles were used to calculate the
damage time of the concrete. The experimental conditions include
a wetting temperature of 298.15 K and a concentration of the
sodium sulfate solution of 0.352 mol/L (50 g/L). Before the sodium
sulfate solution was saturated, it is assumed that the concentration
of the solution in the pore was an arithmetic progress with the
increase of WD cycles. The solution in the pore was saturated at
the fifth cycle, because the maximum concentration of the sodium
sulfate solution at the temperature of 298.15 K was 1.75 mol/L.
From the sixth cycle, the concentration of the solution in the pore
was 1.75 mol/L and not changed at all. The concentrations of the
sodium sulfate solution in the pore at the first five cycles were
given in Table 3.
From Eq. (18), the reaction rate constant can be calculated by
 2
r 2þ þ r
2kB T Ca SO 2
kG ¼ 1:048  10 - 13   4
 NA
3gw r Ca2þ r SO2
4
1
1
¼ 0:058Lmol min ð86Þ
where the molar volume of thenardite is vT = 53.3  10 L/mol, the 3
molar volume of mirabilite is vM = 217.7  103 L /mol, and the
molar volume of gypsum is vG = 74.53  103 L /mol. The concen-
tration of calcium hydroxide was assumed equal to its solubility
at the temperature of 298.15 K. Hence, the concentration of the cal-
cium hydroxide in the pore solution should be 2.146  103 mol/L.
For one WD cycle, the wetting time is 15 hours, i.e., 900 min. For
A = 0.3885, from Eqs. (60) and (61), the volume fractions can be
obtained by
vM
sat
V M;i cso2
¼ 4 ¼ 0:0979 ð87Þ
V C;i A

cCa2þ v G
sat
V G;i 0:55kG t 0 cso2
¼ 4
¼ 0:021 ð88Þ
V C;i A
V M;i V
Substituting the values of A, V C;i
; V G;i into Eqs. (62) and (63), the
C;i

volume fractions of mirabilite and gypsum in the pore at the sixth

Fig. 9. The correlation between the ultrasonic velocity and the WD cycles.
to tenth WD cycles (as n = 5, i = 1,2,3,4,5) can be calculated and
were given in Table 4. After that, the volume fractions of gypsum
in the first five cycles (n = 1,2,3,4,5) can be calculated by Eq. (33)
and were given in Table 5. Finally, the total volume fractions of
mirabilite and gypsum can be calculated by Eqs. (66) and (67)
(Table 6).
The crystallization pressures of mirabilite and gypsum can be
calculated by Eqs. (72) and (73), respectively. At the wetting stage
of the WD cycles, once the solution arrives at the pore, the thenar-
dite in the pore will dissolve in the solution, even make the
14 J. Ren et al. / Construction and Building Materials 264 (2020) 120525

Fig. 10. The test of SEM: (a) The SEM image of the cement mortar at X1000 magnification; (b) The energy spectrum of gypsum; (c) The SEM image of the cement mortar at
X1780 magnification, (d) The energy spectrum of the sodium sulfate.

Fig. 11. The pore size distributions of the cement mortar samples.

solution supersaturate and precipitate as mirabilite. Assuming that
the generation of mirabilite is completed, the solution is pure.
Hence, KSP,T and KSP,M can be calculated by the Pitzer formula for
single component electrolyte (Appendix 2) [89]. Substituting the
values of KSP,T and KSP,M into Eq. (72), one obtains the crystallization
pressure of mirabilite. The calculated result is 9.3055 MPa. After
that, with the continuous wetting of concrete, the calcium hydrox-
ide dissolves in the solution, reacts with sodium sulfate and gener-
ates gypsum. The solubility of calcium hydroxide is assumed as a
constant. If the sodium sulfate consumes the calcium hydroxide
in the solution, new calcium hydroxide will dissolve and make sure
that the concentration of calcium hydroxide is a constant. Hence,
 J. Ren et al. / Construction and Building Materials 264 (2020) 120525 15

the concentration of calcium hydroxide can be considered as a con-

stant during the wetting. During the generation of gypsum, it can
be assumed that there are only sodium sulfate and calcium
hydroxide in the solution. Because the contents of the other ions
are very low, their influence on the activities of the reaction ions
can be neglected. Therefore, the ionic activity product of gypsum
(QG) can be calculated by the Pitzer formula for mixed electrolyte
which proposed by Harvie and Wear (Appendix 3) [90]. As the
sodium sulfate solution in the pore is saturated after five cycles,
the ionic activity products of gypsum in the following cycles are
equal to those in the fifth cycle. Therefore, the ionic activity pro-
duct of gypsum in the first five WD cycles (Table 7) was only cal-
culated. From the results in Table 6, the crystallization pressure
of gypsum in the first WD cycles can be obtained (Table 8).
Because the ionic activity product of gypsum is a constant after
the fifth cycle, the crystallization pressure of gypsum after the fifth
cycle is a constant as well. The total macroscopic tensile stress that
Fig. 12. The pore size distribution of the cement mortar under cumulative
originates from the macroscopic tensile stress of mirabilite and
intrusion.
gypsum can be calculated (Table 9).
The tensile stress of C40 ordinary concrete is usually 3.9 ± 0.1
MPa [91–93]. The critical tensile stress can be obtained by Eq. (85):
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
rc ¼ rT = 3ð1  2eÞ ¼ 3:184MPa ð89Þ

Table 6
The total volume fraction of mirabilite and gypsum in the pore.

Cycle number SM SG
1 0.000 1.616  103
2 0.000 4.847  103
3 0.000 9.694  103
4 0.000 0.016
5 0.000 0.024
6 0.371 0.032
7 0.707 0.040
8 1.010 0.045
9 1.284 0.051
10 1.533 0.056
Fig. 13. Porosities of the cement mortar after 0, 15 and 30WD cycles.

Table 3
The concentration of sodium sulfate solution in the pore.

Cycle number 1 2 3 4 5
Concentration of sodium sulfate solution (mol/L) 0.352 0.704 1.056 1.408 1.750

Table 4
The value of SM,i and SG,i from the sixth to tenth WD cycle.

Cycle number 6 7 8 9 10
SM,i 0.380 0.724 1.035 1.316 1.571
SG,i 8.148  103 0.016 0.022 0.028 0.033

Table 5
The volume fraction of gypsum in the pore at the first five WD cycles.

Cycle number 1 2 3 4 5
Sn 1.616  103 4.847  103 9.694  103 0.016 0.024
16 J. Ren et al. / Construction and Building Materials 264 (2020) 120525

Table 7
The ion activity product of gypsum.

Cycle number 1 2 3 4 5
6
Ion activity product (10 ) 7.47855 6.89370 6.30605 5.80789 5.38438

Table 8
The crystallization pressure of gypsum.

Cycle number 1 2 3 4 5
Crystallization pressure (MPa) 24.321113 26.49749 28.088335 29.33512 30.379922

After calculating the crystallization pressure, the macroscopic

Table 9
tensile stress can be calculated using the values of the crystalliza-
The macroscopic tensile stress.
tion pressure and volume fraction of mirabilite in the pore by
Cycle Tensile stress of Tensile stress of Total tensile Eq. (81). The values of macroscopic tensile stress under different
number mirabilite (MPa) gypsum (MPa) stress (MPa)
WD cycles were given in Table 11.
1 0 0.009040 0.009040 The critical tensile stress was calculated by Eq. (85) and the
2 0 0.029540 0.029540
value is
3 0 0.062626 0.062626
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
4 0 0.107953 0.107953 rc ¼ rT = 3ð1  2eÞ ¼ 2:25MPa ð91Þ
5 0 0.167697 0.167697
6 0.794038 0.223596 1.017635 where the value of Poisson’s ratio is 0.26 [11] and the tensile
7 1.513167 0.279495 1.792663
stress is 2.7 MPa for the rock. It can be seen that the rock was dam-
8 2.161668 0.314432 2.476100
9 2.748100 0.356356 3.104457 aged after the fourth cycle and this is consistent with the test result
10 3.281026 0.391293 3.672320 of Flatt et al. [11]. Therefore, the volume fraction model, proposed
by this paper, is not only useful for the concrete but also useful for
the noncorrosive materials, such as rock.

Comparing the calculated result with the macroscopic tensile
stress in Table 8, it is found that the macroscopic tensile stress
was close to the critical tensile stress in the ninth cycle and
exceeded the critical tensile stress in the tenth cycle. The concrete
was damaged after the tenth cycle. This variation regularity is con-
sistent with that of experimental result in which the compressive
strength and the ultrasonic velocity of the concrete decreased after
the ninth cycle. Although the mass of the concrete decreased after
the eighth cycle, the deviation is within the range of error. The pro-
posed models, in this paper, were thus reliable to forecast the dam-
age of the concrete.
5.2. The damage in corrosion-free material under WD cycles
If there is no reaction in the material under WD cycles, only
mirabilite generates in the pore of the material. The rock studied
by Flatt et al. [11] was calculated as an instance to verify the pro-
posed model in this paper. The volume fraction of mirabilite in the
pore was calculated by Eq. (68) at the temperature of 298.15 K. The
results were given in Table 10 (i = 1,2,3,4,5).
From Eq. (72), the crystallization pressure of mirabilite can be
calculated by



RT RHsat;T
Pc ¼ K SP;T  K SP;M þ 10ln ¼ - 9:3055MPa
vM 100
6. Conclusions
To investigate the damage process and mechanism of concrete
under WD cycles, the crystal growth and the crystallization pres-
sure were calculated and the WD cycles that the plain concrete
can sustain was forecasted. The following conclusions can be
made:
(1) The damage in the concrete composes of physical damage
caused by the crystallization of mirabilite, and the physico-
chemical damage which refers to the losing function of gel
material and the generation of expansion crystal in the cor-
rosion reaction. The type and content of the expansive crys-
tal change with the concentration of sodium sulfate solution.
A high concentration leads to gypsum precipitation, while a
low one, ettringite formation. However, there always gener-
ate gypsum at the wet-dry interface of concrete in field and
in the pore of the concrete in the laboratory.
(2) The reaction of the generation of gypsum is diffusion-
controlled liquid ionic reaction. The reaction-rate constant
formula was derived based on the diffusion controlled reac-
tion theory. The formula for collision probabilistic factor was
worked out and then the reaction rate constant at any tem-
perature can be calculated by the formula.
(3) Based on the chemical reaction dynamics and phase transi-
ð90Þ
tion laws, the volume formulae of gypsum and mirabilite
in the pore at any WD cycles were proposed. The total vol-

Table 10
Volume fraction of the crystals in the pore.

Cycle number 1 2 3 4 5
Volume fraction 0.0932 0.1844 0.2730 0.3603 0.4453
 J. Ren et al. / Construction and Building Materials 264 (2020) 120525
ume fraction formula and the volume fraction formulae of
mirabilite and gypsum in the pore were derived for the con-
crete samples under WD cycles, in the conditions that the
sodium sulfate solution saturates or not saturate.
(4) By testing the compressive strength, mass change and the
ultrasonic velocity of the concrete in laboratory, the number
of WD cycle that the concrete can sustain under the experi-
mental condition was determined. Under the experimental
condition, the macroscopic tensile tress was calculated using
the volume fraction in the pore and the crystallization pres-
sure in the pore. By comparing the macroscopic tensile tress
with the critical tensile stress of the concrete, the cycle num-
ber that the concrete can sustain was obtained. The theoret-
ical result is consistent with the experimental result. The
proposed formulae were also used to calculate the damage
time of the rock which does not react with sodium sulfate.
The result is also consistent with Flatt’s experimental result,
verifying the reliability of the formulas.
(5) Most of the current studies thought that the mass simply
increases with the increase of WD times. By measuring the
mass of the test concrete after each cycle, a different change
rule was found. The mass has few changes at the initial
cycles and then presents an increasing in wave. Hence, the
concrete is not straightly damaged but in a dynamic
damaging-filling state under the WD cycles.
CRediT authorship contribution statement
Jingge Ren: Conceptualization, Data curation, Validation, Inves-
tigation, Writing - original draft, Writing - review & editing. Yuan-
ming Lai: Conceptualization, Writing - review & editing,
Resources, Supervision, Funding acquisition. Ruiqiang Bai: Writing
- review & editing. Yinghong Qin: Writing - review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
This research was supported by National Key Research and
Development Program of China [grant number
2018YFC0809605], Key Research Program of Frontier Sciences of
Chinese Academy of Sciences [grant number QYZDY-SSW-
DQC015], National key Basic Research Program of China [973 pro-
gram number 2012CB026102], National Natural Science Founda-
tion of China [grant numbers 41230630].
Appendix 1. Measure of the reaction rate constant of calcium
ion and the sulfate ion
A1.1. Material
The testing reagents include sodium sulfate, calcium chloride,
and distilled water. The instrument includes cylinders, beakers,
weighing papers, droppers, a balance with the precision 0.001 g,
a conductivity meter (DDS-307), and constant temperature baths.
A1.2. Test method and experiment
A1.2.1. Test method
The reaction of calcium and sulfate ions in the solution can be
written as
17
SO2
4 þ Ca
2þ
þ 2H2 O ! CaSO4  2H2 O: ðA1:1Þ
As water is the solvent, the reaction rate mainly depends on the
concentrations of calcium and sulfate ions and on the temperature
of the solution. The reaction rate constant is mainly dependent on
the temperature. Under the condition that the wetting tempera-
ture in the WD cycle testing was 298.15 K, the reaction rate con-
stant was measured at the temperature of 298.15 K. Here the
electric conductivity rate instrument was used to test the reaction
rate.
During the WD cycles, the reaction of calcium hydroxide and
the sodium sulfate forms gypsum. Hence, reactants used for testing
the reaction rate constant should be calcium hydroxide and
sodium sulfate. However, the calcium hydroxide solution also
reacts with the carbon dioxide and generates calcium carbonate
(Eq. (A1.2)). Moreover, the solubility of calcium carbonate is smal-
ler than that of calcium sulfate. Hence, if the calcium hydroxide is
chosen as the reactant, the reaction product is more likely to be
calcium carbonate rather than the calcium sulfate. Therefore, the
calcium chloride was chosen to replace the calcium hydroxide.
Because the calcium chloride is also strong electrolytes and can
provide equal numbers of calcium ion in the solution. This replace-
ment will not influence the reaction rate and it is reasonable.
Ca2þ þ 2OH1 þ CO2 ! CaCO3 þ H2 O ðA1:2Þ
A1.2.2. Experiment
0.1 mol/L sodium sulfate solution and 0.1 mol/L calcium chlo-
ride solution were prepared and poured into the beakers. Before
the experiment, the two solutions in the beakers were placed in
the water bath with the temperature of 298.15 K. After 10 min,
the solution were taken out if their temperatures reached to
298.15 K. Equal volumes of these two solutions were taken out
and mixed in a beaker which was also put in the water bath with
the temperature of 298.15 K. At the same time, the computing time
was started. The conductivity of the mixed solution was detected
and recorded each 10 min for four times, then the conductivity
of the mixed solution was detected and recorded each 20 min for
another four times. The test was completed after the eight values
were got. After that, the conductivities of 0.05 mol/L sodium sulfate
solution and calcium chloride solution at the temperature of
298.15 K were tested and recorded.
A1.3. Results and calculation
As the reaction between calcium and sulfate ions is the second
order reaction, when the reaction lasts for a time of t, the reaction
rate can be expressed as
dx  
¼ kG  c0SO2  x  c0Ca2þ  x : ðA1:3Þ
dt 4
where x (mol) is the variation of the reactant at the time of t (min),
c0SO2 (mol/L) and c0Ca2þ (mol/L) are the initial concentration of cal-
4
cium ion and sulfate ion and kG is the reaction rate constant of
the formation of gypsum. If the initial concentration of sulfate ion
equals to that of calcium ion, Eq. (A1.3) can be simplified as
 2
dx
¼ kG  c0SO2  x : ðA1:4Þ
dt 4
Integrating Eq. (A1.4) yields
1 x
kG ¼  : ðA1:5Þ
tc0SO2 c0SO2  x
4 4
18 J. Ren et al. / Construction and Building Materials 264 (2020) 120525

Table 11
Macroscopic tensile stress.

Cycle number 1 2 3 4 5
Tensile stress (MPa) 0.6071 1.2698 1.8799 2.4811 3.0644

However, the concentration of the ions in the solution cannot be

measured directly. Hence, the reaction rate was reflected by the
conductivity of the solution. The conductivity of the solution
always depends on the concentration of metal ions and the tem-
perature of the solution. It can be known that the concentration
of the mixed solution is 0.05 mol/L as the concentrations of both
sulfate and calcium ions are 0.1 mol/L. If the conductivities of
0.05 mol/L calcium chloride solution and 0.05 mol/L sodium sulfate
solution are LCa2þ and LSO2 , respectively, the conductivity of the
4

mixed solution (L0), which is composed of the same volume of

0.1 mol/L calcium chloride solution and 0.1 mol/L sodium sulfate
solution, is equal to LCa2þ þ LSO2 . Hence, at the time of t, the con-
4

ductivity of the mixed solution is Lt. Eq. (A1.5) can be written as

1 L0  Lt
kG ¼  : ðA1:6Þ
tc0SO2 Lt
4
L0 Lt
Fig. A1. The correlation between t
and Lt.
Eq. (A1.6) can also be expressed as
1 L0  Lt
Lt ¼  : ðA1:7Þ
kG c0SO2 t Table A2
4 The fitting equation and coefficients.

There is a linear correlation between L0 L

t
t
and Lt as the reaction Equation R2 Slope (p) Intercept (q)
1
is a second order reaction. The slope of the correlation line is k 0 . y = px + q 0.9183 343.00 11,384
Gc
SO2
4

Hence, the reaction rate constant can be calculated by the slope.

The test results were given in Table A1. The conductivities of
0.05 mol/L sodium sulfate solution and calcium chloride solution This equation neglects the other force except for Coulombic
were tested and they were 15.02 ms and 16.76 ms, respectively. force between the ions and it is only useful for the solution whose
According to the results in Table A1, the correlation between L0 L
t
t
concentration is smaller than 0.1 mol/L. Based on Debye-Hückel’s
and Lt can be analyzed (Fig A1). equation, Pitzer (1973) proposed formulae to calculate the average
L0 Lt
t
and Lt follows a linear correlation, with a R2 is 0.9183 activity coefficient of the electrolyte and the permeability
(Table A2). From Eq. (A1.7) we can obtain: coefficient of the solution. It is available for the high concentration
solution with a concentration up to 6 mol/L. Hence, the formulae of
1
kG c0SO2 ¼ 343 min : ðA1:8Þ Pitzer were used to calculate the average activity coefficient of the
4
electrolyte and the permeability coefficient of the solution.
kG = 0.058Lmol1min1 can be obtained from Eq. (A1.8). For the electrolyte MX whose molar concentration is m, the for-
mulae to calculate the average activity coefficient (c±MX) and the
Appendix 2. The calculation of the equilibrium constants of permeability coefficient (u) are expressed as [88]
thenardite and mirabilite 2dM dX c 2ðdM dX Þ
3=2
c
lnc MX ¼ jZ M Z X jf þ m BMX þ m2 C cMX ðA2:2Þ
d d
A2.1. The formulae of Pitzer
3=2
2dM dX u 2ðdM dX Þ
In the electrolyte solution, the calculation of equilibrium con- u  1 ¼ jZ M Z X jf u þ m BMX þ m2 Cu
MX : ðA2:3Þ
d d
stant of the electrolyte is crucial to calculate the ionic activity.
Debye-Hückel firstly proposed the model to calculate the ionic where M, X are the cation and the anion, dM, dX are the number of
activity of the electrolyte: the cation and the anion, and Z M ; Z X are the charge number of the
cation and the anion, respectively. d = dM + dX is the total ion num-
pffiffi c u
Ajzþ z j I ber within the electrolyte. f ; f ; BcMX and Bu
MX are all the functions of
lgc ¼ pffiffi : ðA2:1Þ the ionic strength (I) and they are defined as:
1 þ aB I

Table A1
The conductivity of the mixed solution.

t(min) 10 20 30 40 60 80 100 120

Lt(ms/cm) 15,760 15,640 15,530 15,430 15,240 15,050 14,860 14,680
 J. Ren et al. / Construction and Building Materials 264 (2020) 120525 19

" #
c I1=2 2   The dissolution equilibrium constant of thenardite is
f ¼ Au þ ln 1 þ bI1=2 ðA2:4Þ
1 þ bI1=2 b
w ¼ mNaþ cNaþ mSO2 cSO2 aw :
K Na2 SO4 ¼ ðaNaþ Þ2 aSO2 a10 ðA2:15Þ
2 2 10
4 4 4
!
u I1=2 The water activity (aw) equation is
f ¼ Au 1=2
ðA2:5Þ X
1 þ bI lnaw ¼ u ðme =55:508Þ: ðA2:16Þ
   
where me (mol/kg) is the molar concentration of the ion (e). The
BcMX ¼ 2bMX þ bMX g a1 I1=2 þ bMX g a2 I1=2
ð0 Þ ð1 Þ ð2Þ
ðA2:6Þ
value of water activity at the temperature of 298.15 K is 0.9428.
From Eqs. (A2.14) and (A2.15), the ratio of K Na2 SO4 to K Na2 SO4 10H2 O
ð0 Þ ð1 Þ ð2 Þ
B/MX ¼ bMX þ bMX ea1 I
1=2 1=2
þ bMX ea2 I ðA2:7Þ can be calculated by

3 u K Na2 SO4
C cMX ¼ C : ðA2:8Þ ¼ a10
w : ðA2:17Þ
2 MX K Na2 SO4 10H2 O

where b(0), b(1), b(2), and C u are the Pitzer parameters of the elec- After that, the ratio of K Na2 SO4 to K Na2 SO4 10H2 O can be calculated by
trolyte; b = 1.2 kg1/2/mol1/2 is an empirical constant; Au is the per- the value of water activity.
meability coefficient of Debye-Hückel which is determined by the
property of the solution and the temperature. It is defined as: Appendix 3. The calculation of the ionic activity and

1=2
2 3=2 permeability coefficient in the mixed solution of sodium sulfate
1 2p N 0 q W ee
Au ¼ : ðA2:9Þ and calcium hydroxide
3 1000 DkB T
where N0 is the Avogadro constant; kB is the Boltzmann constant; ec A3.1. Calculation formulae
is the charge of the electron; qw is the density of the solvent at the
temperature of T; D is the dielectric constant of the solvent. The During the wetting stage of the WD cycles, the hydration pro-
value of Au is 0.3915 kg1/2/mol1/2 at the temperature of 298.15 K. duct calcium hydroxide dissolves in the sodium sulfate solution
ð2Þ on the pore. The solution in the pore is a mixed electrolyte solu-
For non-2-2 electrolyte, the value 0f bMX is zero in Eqs. (A2.6) and
tion. Pitzer formulae were arranged by Harvie and Wear; the for-
(A2.7). The value of a1 is 2 kg1/2/mol1/2. For 2-2 electrolyte, the val-
mulae used for calculating the ionic activity in the mixed
ues of a1 and a2 are 1.4 kg1/2/mol1/2 and 12 kg1/2/mol1/2, respec-
solution were obtained. The calculation formulae are [92]
tively. The I in Eqs (A2.6) and (A2.7) is the ionic strength and
 
N Na

defined as:
Ri mi ðu  1Þ ¼ 2½Au I3=2 = 1 þ 1:2I1=2 þ
c
R R mc ma Buca þ ZC ca
1X

c¼1 a¼1
I¼ mi Z 2i : ðA2:10Þ N c 1 Nc Na N a 1 Na
2 þ R R mc mc0 Uucc0 þ R ma wcc0 a þ R R ma ma0
c¼1 c0 ¼cþ1 a¼1 a¼1 a0 ¼aþ1
The expression of g ðxÞ is

Nc Na Na Nn Nc


  Uuaa0 þ R mc waa0 c þ R R mn ma knc þ R R mn mc knc
1 c¼1 n¼1 a¼1 n¼1 a¼1
g ðxÞ ¼ 2 1  1 þ x  x2 ex =x2 ðA2:11Þ
2 ðA3:1Þ

Na
A2.2. The calculation of the equilibrium constants of thenardite and lncM ¼ z2M F þ R ma ð2BMa þ ZC Ma Þ
a¼1
mirabilite
 N 1
Nc Na a
þ R mc 2UMc þ R ma wMca þ R
Sodium sulfate is 2–1 electrolyte. The average ionic activity of c¼1 a¼1 a¼1

sodium sulfate and the permeability coefficient of the solution Na Nc Na

can be obtained by:  R ma ma0 waa0 M þ jzM j R R mc ma C ca

a0 ¼aþ1 c¼1 a¼1

4 c 25=2 2 c Nn
lnc MX ¼ 2f þ mBcMX þ m C MX ðA2:12Þ þ R mn ð2knM Þ ðA3:2Þ
3 3 n¼1

4 25=2 2 u Nc
u  1 ¼ 2f u þ mBuMX þ m C MX : ðA2:13Þ lncX ¼ z2X F þ R mc ð2BcX þ ZC cX Þ
3 3 c¼1

 N 1
The Pitzer parameters of sodium sulfate are: b(0) = 0.0196, Na Nc c Nc
þ R ma 2UXa þ R mc wXac þ R R mc mc0 wcc0 X
b = 1.113 and C u ¼ 0:00497. The concentration of the saturated
(1) a¼1 c¼1 c¼1 c0 ¼cþ1

sodium sulfate solution is 1.75 mol/kg. Hence, the values of Nc Na Nn

c u
f ; f ; BcMX and Bu
MX can be calculated by Eqs (A2.3-A2.6). Substitut-
ing the results into Eqs (A2.12) and (A2.13), one can obtain that the
value of the average ionic activity of sodium sulfate is 0.1638 and
the value of the permeability coefficient of the solution is 0.6225 at
the temperature of 298.15 K. According to the principle of chemical
equilibrium, when a salt reaches the dissolution equilibrium in
solution at constant temperature and pressure, the dissolution
equilibrium constant of the salt is a constant. Therefore, the disso-
lution equilibrium constant of thenardite is
 1
K Na2 SO4 ¼ ðaNaþ Þ2 aSO2 ¼ m2Naþ c2Naþ mSO2 cSO2 :
4 4
þ jzX j R R mc ma C ca þ R mn ð2knX Þ ðA3:3Þ
c¼1 a¼1 n¼1
where M, c and c0 are the cations; X, a and a0 are the anions; Nc, Na
and Nn are the number of the cation, anion and neutral molecule,
respectively; cM, ZM and mc are the activity coefficient, ionic
valence and the molality of the cation; cX, ZX and ma are the activity
coefficient, ionic valence and the molality of the anion; and cn, mn,
knc and kna are the activity coefficient of the neutral molecule, the
molality of the neutral molecule, the interaction coefficient
between the cation and the neutral molecule and the interaction
ðA2:14Þ coefficient between the anion and the neutral molecule,
4
respectively.
20 J. Ren et al. / Construction and Building Materials 264 (2020) 120525

F, C, Z, Bu and B are defined as: Table A3

h    i Nc Pitzer parameters.
F ¼ Au I1=2 = 1 þ 1:2I1=2 þ 2=1:2ln 1 þ 1:2I1=2 þ R Electrolyte bð0Þ bð1Þ bð2Þ Cu
c¼1
Na N c1 Nc N a1 Na2 SO4 0.04604 0.93350 – 0.00483
 R mc ma B0ca þ R R mc mc0 U0cc0 þ R CaðOHÞ2 0.1747 0.2303 5.72 –
a¼1 c¼1 c0 ¼cþ1 a¼1
NaOH 0.17067 0.08411 – 0.00342
Na
CaSO4 0.2 3.7762 58.388 –
 R ma ma0 U0aa0 ðA3:4Þ
a0 ¼aþ1
 
C MX ¼ C u
MX = 2jzM zX j
1=2
ðA3:5Þ
Table A4
Z ¼ Ri¼1 jzi jmi ðA3:6Þ The interaction parameters of the ions.

    hNa,Ca wNa,Ca,SO4 wNa,Ca,OH hSO4,OH wSO4,OH,Na wSO4,OH,Ca

Bu
ð0Þ ð1Þ 1=2 ð2Þ
CA ¼ bCA þ bCA exp a1 I þ bCA exp a2 I1=2 ðA3:7Þ 0.07 0.055 0 0.013 0.009 0

   
ð0Þ ð1Þ ð2Þ
BCA ¼ bCA þ bCA g a1 I1=2 þ bCA g a2 I1=2 ðA3:8Þ

h    i Hence, the values of Ehij and Eh0ij can be calculated by Eqs.

ð1Þ ð2Þ
B0CA ¼ bCA g 0 a1 I1=2 þ bCA g 0 a2 I1=2 =I ðA3:9Þ (A3.15-A3.19). Substituting the results to Eqs. (A3.12-A3.14), one
gets the values of Uu 0
ij ; Uij and Uij . Finally, the ionic activity of the
where Au is the permeability coefficient of Debye-Hückel and the
ions and the permeability coefficient of the mixed solution can
value of Au is 0.3915 kg1/2/mol1/2 at the temperature of 298.15 K;
be obtained.
w is the interaction parameter of three different ions (two cations
and one anion or two anions and one cation); Bu and B are the sec-
A3.2. The calculation of ionic activity and permeability coefficient
ond virial coefficients; B0 is the differentiation of B about ionic
ð0Þ ð1Þ ð2Þ
strength. bCA ;
and bCA bCA
in Eqs. ((A3-7)-(A3-9)) are the Pitzer
Assuming that there are only sodium sulfate and calcium
parameters of the electrolyte. For non-2-2 electrolyte, the values hydroxide in the pore solution, the formulae arranged by Harvie
ð2Þ
of bCA and a2 equal to zero, and a1 is 2 kg1/2/mol1/2. For 2-2 elec- and Wear were used to calculate the ionic activity and the perme-
trolyte, the values of a1 and a2 are 1.4 kg1/2/mol1/2 and 12 kg1/2/- ability coefficient. Pitzer parameters of sodium sulfate, calcium
mol1/2, respectively. hydroxide, calcium sulfate and sodium hydroxide were given in
g and g0 are defined as: Table A3. The interaction parameters of the ions were given in
Table A3.
g ðxÞ ¼ 2½1  ð1 þ xÞexpðxÞ =x2 ðA3:10Þ
Based on the values in Tables A3 and A4, the activity coefficients
of the ions in the mixed solution at different concentration can be
g 0 ðxÞ ¼ 2 1  1 þ x þ x2 =2 expðxÞ =x2 ðA3:11Þ
calculated.
Uuij ; Uij and U0ij are also the second virial coefficients; they corre-
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