Cement and Concrete Composites 104 (2019) 103356

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Cement and Concrete Composites

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The dependence of capillary sorptivity and gas permeability on initial water T

content for unsaturated cement mortars
Fangzhou Rena,b, Chunsheng Zhoua,b,*, Qiang Zengc, Zhu Dingd, Feng Xingd, Wei Wanga,b
a
Key Lab of Structures Dynamic Behavior and Control of the Ministry of Education, Harbin Institute of Technology, Harbin, 150090, China
b
Key Lab of Smart Prevention and Mitigation of Civil Engineering Disasters of the Ministry of Industry and Information Technology, Harbin Institute of Technology, Harbin,
150090, China
c
College of Civil Engineering and Architecture, Zhejiang University, Hangzhou, 310058, China
d
Guangdong Provincial Key Laboratory of Durability for Marine Civil Engineering, College of Civil Engineering, Shenzhen University, Shenzhen, 518060, China

A R T I C LE I N FO A B S T R A C T

Keywords: Capillary sorptivity and gas permeability characterizing the penetration ease of water and gas deserve attention
Mortar in the current attempts to quantify durability performance for cement-based materials. To investigate their
Capillary sorptivity dependences on water content, disk specimens of cement mortars are prepared and thoroughly preconditioned.
Gas permeability At ambient condition, available models could quantify the measured dependence of gas permeability except
Water saturation
capillary sorptivity. Surprisingly, it follows another bilinear law with a transitional saturation degree, beyond
which capillary condensation occurs in gel pores at equilibrium. This extraordinary disagreement is ascribed to
the dynamic structure of C–S–H gel and thus mortars, which are sensitive to water removal and regain.
Physically, it is also responsible to several unexpected anomalous characteristics of water absorption. The un-
saturated flow theory is no longer applicable if ignoring its sensitivity to water, which is the key to approach the
transport mechanisms of water and other deleterious agents in common unsaturated cement-based materials.

1. Introduction Capillary sorptivity represents the velocity of water absorption into

In engineering practice of concrete construction, many physical and
chemical processes are mediated by water [1,2], including of course the
much concerned deterioration of cement-based material under various
environmental actions [3,4]. The durability performance of cement-
based material is mostly determined by the coupled penetration of
various masses. In essence, the water content enforces fundamental
influence on almost all the transport properties of deleterious gases,
ions as well as water itself in cement-based material, and thus de-
termines its durability to a great extent [5]. Since the cement-based
materials under service are rarely saturated by water, it is important to
characterize the dependence of mass transport properties on water
content. Among the widely used indicators quantifying the durability
potential of cement-based material, the relevent capillary sorptivity and
gas permeability are much easy to measure on well-controlled un-
saturated material in laboratory and even in field [6]. Therefore, the
unsaturated capillary sorptivity and gas permeability quantifying the
penetration ease of water and gases deserve much attention in the
current attempts to quantitatively predict the durability performance of
cement-based material.
unsaturated cement-based material under the driving action of capillary
pressure [7]. Based on the Richards equation [8] or unsaturated flow
theory [9], in the one-dimensional absorption into homogeneous
porous medium of uniform water content, the absorbed water volume
per unit area is theoretically proportional to the square root of elapsed
time [2]. The proportional coefficient is clearly defined as the capillary
sorptivity, which is first introduced by Philip in the neighbouring field
of soil physics [10]. When it is directly borrowed to quantify cement-
based material, although the square root of time law still holds, the
strict definition of capillary sorptivity faces several robust challenges
due to several unexpected anomalous behaviors of water absorption
into cement-based material [11–13]. Moreover, although several
models have been established to quantify the dependence of capillary
sorptivity on initial water content [10,14–19], they are mostly devel-
oped from the function of hydraulic diffusivity in terms of saturation
degree, which could be experimentally measured through the Richards
equation [20]. Since the hydraulic diffusivity is intimately linked to
water permeability, cement-based material having anomalously low
water permeability may also have anomalous hydraulic diffusivity [21],
possibly making the models of capillary sorptivity initially proposed for

*
Corresponding author. Key Lab of Structures Dynamic Behavior and Control of the Ministry of Education, Harbin Institute of Technology, Harbin, 150090, China.
E-mail address: zhouchunsheng.HIT@gmail.com (C. Zhou).

https://doi.org/10.1016/j.cemconcomp.2019.103356
Received 26 February 2019; Received in revised form 19 May 2019; Accepted 24 June 2019
Available online 28 June 2019
0958-9465/ © 2019 Elsevier Ltd. All rights reserved.
F. Ren, et al.
soils and rocks unsuitable to cement-based material. Because the fragile
pore structure of cement-based material is extremely sensitive to water
removal and regain during drying preconditioning and following ab-
sorption [21,22], the physical significance of capillary sorptivity and its
dependence on water content are still open questions.
Although transport of gases (CO2, O2, H2O etc.) are seldom driven
by pressure gradient in reality, the measurement of gas permeability is
much easier than water permeability, and could be carried out on at
least partially dried cement-based material. Many experimental data of
unsaturated gas permeability have been reported in literature
[19,23–28]. When describing its dependence on water content, the
available physical or empirical models originally proposed for soils or
rocks [29,30] are usually borrowed to describe cement-based materials,
which have definitely distinct pore structural characteristics from them.
Importantly, these models are all established on the implied assumption
of stationary pore structure, which is not modified by water loss or re-
entry. However, it is well recognized that the micro-structure of ce-
ment-based material is vulnerable to water removal especially at ele-
vated temperature, which is widely adopted in general laboratory ex-
perience to accelerate the preconditioning if required. Not only the
inevitable micro-cracking, the pore structure of cement-based material
is also evolving during the alteration of water content due to the col-
lapse or expansion of C–S–H gel [21,22], which makes its permeability
to water and other fluids totally different by several orders of magni-
tudes. As a consequence, the dependence of unsaturated gas perme-
ability on water content is still far away from current understanding
without detailed considerations on the evolution of pore structure.
In principle, capillary sorptivity and gas permeability of cement-
based material are both physically determined by its current pore
structure and water distribution. To quantify their dependence on water
content, experimental investigation is carried out herein with attention
being paid to the evolving pore structure sensitive to water removal and
regain. In Section 2, the available models for both unsaturated capillary
sorptivity and gas permeability are summarized from literature. In
Section 3, an experimental scheme is thoroughly designed and carried
out to obtain representative results, which are then analyzed in Section
4. Further discussion is made in Section 5 with regard to the essential
water absorption. Finally, several remarks are briefly concluded in
Section 6.
2. Available models in literature
2.1. Definition of saturation degree
As the cement-based materials under service are mostly neither
saturated nor totally dried, numerous efforts have been devoted to in-
vestigate the dependence of capillary sorptivity and gas permeability on
initial water saturation degree. The water content of porous medium
determines the pore space available to water absorption and gas per-
meation, and therefore decides the capillary sorptivity and gas per-
meability together with its pore structure. Before examining the
quantitative dependence of capillary sorptivity and gas permeability on
water content, it is essential to strictly define the water content or water
saturation degree.
Cement-based material is so special that it is ambiguous to define its
totally saturated and dry states [2], so is its water content and water
saturation degree. As a frequently adopted method, the long-established
technique of oven-drying to constant weight at elevated temperature is
generally appreciated. In regular experimental investigation of mass
transport properties, oven-drying at relatively low temperature such as
frequently adopted 60 °C is time-consuming due to its tenacious hold on
water and very low permeability. Moreover, ambient drying at low
relative humidity like that controlled by blue silica gel is also favored
[31]. Besides, although the freeze-drying, vacuum-dry and solvent-ex-
change methods are also recommended when investigating the micro-
structure of cement-based material [32–34], an efficient drying method
2
Cement and Concrete Composites 104 (2019) 103356
without altering its micro-structure does not exist at all [21,22,35].
Furthermore, it is broadly accepted that drying preconditioning will
invariably induce micro-cracking to fragile cement-based material,
which will bias the measured capillary sorptivity and gas permeability
thereafter. Therefore, comprises have to be made. Precisely, the totally
dry state can be practically defined as that having no evaporable water,
which could be operationally and quickly achieved by oven-drying at
105 °C until constant weight with good reproducibility. From these
considerations, the totally dry state without evaporable water is herein
selected as the reference dry state to help define the evaporable water
content. Since micro-cracking damage is inevitably incorporated into
the micro-structure of cement-based material after oven-drying at ele-
vated temperature, the capillary sorptivity and gas permeability ex-
perimentally measured at reference dry state is only nominal, and thus
cannot be directly treated as that actual values in accordance with ideal
totally dry state without incorporation of micro-cracks.
In another aspect, it is also very difficult to achieve complete water
saturation for cement-based material [36]. For relatively large samples
of very low permeability, the time required for liquid to penetrate
throughout them may be surprisingly long and impractical [2]. To
simplify this analysis, the frequently adopted vacuum saturation
method is employed to achieve water saturation state, at which water
content could reach its maximum value under common service condi-
tion. As usual, the water saturation degree Θ (−) is therefore oper-
ationally defined as,
Θ = (Weq − Wdry )/(Wsat − Wdry ) (1)
where W (g) denotes the weight of testing specimen and subscript “eq”,
“dry”, “sat” indicates the operational equilibrium, absolutely dry and
water saturation state, respectively.
To help quantify the dependence of capillary sorptivity S (mm/
min0.5) and gas permeability kg (m2) on water saturation Θ , the relative
capillary sorptivity Sr (−) and relative gas permeability k rg (−) are
usually introduced and defined as,
S (Θ) = S0 × Sr (Θ), kg (Θ) = kg0 × k rg (Θ) (2)
where the subscript “0” denotes the ideal totally dry state with absent
evaporable water and micro-cracks. The totally dry state for cement-
based material is almost impossible to achieve without severe drying at
105 °C. In addition to removing evaporable water, drying at elevated
temperature will undoubtedly generate micro-cracks and thus sig-
nificantly bias the measured gas permeability and capillary sorptivity.
As a result, the experimentally measured gas permeability and capillary
sorptivity at any reference dry state achieved by drying at elevated
temperature cannot be directly regarded as the ideal values kg0 and S0 .
As a matter of fact, it is not realistic to measure the ideal capillary
sorptivity S0 and ideal gas permeability kg0 of cement-based material at
ideal totally dry state due to the unavoidable micro-cracking damage
enforced by drying at elevated temperature. Consequently, they will be
then treated as unknown variables to be determined.
2.2. Modeling relative capillary sorptivity
Theoretically, the capillary sorptivity is intimately correlated to
hydraulic diffusivity and water permeability as all these three water
transport properties can be implemented to quantify the one-dimen-
sional water absorption process into cement-based material [37,38].
Actually, the available theoretical models of capillary sorptivity are
mostly deduced from its relationship with hydraulic diffusivity, which
could be experimentally determined [2]. Originally, a simple empirical
model was proposed by Philip initially for soil materials as [10,14],
Sr (Θ) = 1−Θ (3)
The above Philip model Eq. (3) clearly indicates that relative
sorptivity does not rely on any other physical features of porous
medium but only the water saturation degree Θ .
F. Ren, et al.
Moreover, assuming sharp front for water content profile during
one-dimensional absorption and widely observed exponential hydraulic
diffusivity D (m2/s) with shape parameter n (−),
D (Θ) = D0exp(nΘ)
the simplified Brutsaert model is also suggested as [15,17]
2n
Sr (Θ) = 1− Θ
2n − 1
The Brutsaert model Eq. (5) takes the shape parameter n of the
concerned porous material into consideration, and thus is expected to
have better accuracy. Similarly, another approximate solution from the
Parlange model is yielded as [18],
(2n − 2nΘ − 1/ θ0) exp (nθ0) − (n − nΘ − 1/ θ0)exp(nθ0 Θ)
Sr (Θ) =
(2n − 1/ θ0)exp(nθ0) − n + 1/ θ0
which additionally accounts the volumetric porosity θ0 (−) but in a
more complex expression.
Based on the assumed exponential expression Eq. (4) for hydraulic
diffusivity and its relationship with capillary sorptivity, another ap-
proximate Zhou model for relative capillary sorptivity Sr is also yielded
in terms of saturation degree Θ and shape parameter n as [19],
τ (n)exp(nΘ)
Sr (Θ) = (1 − Θ)
τ [n (1 − Θ)]
where τ is a simple function with a single variable x [19],
τ (x ) = exp( −0. 1153 − 0. 7341x − 0. 0069x 2)
These above models, suggested from either empirical testing results
or the theoretical relationship between capillary sorptivity and ex-
ponential hydraulic diffusivity, are then applied to quantify the de-
pendence of capillary sorptivity on initial water saturation degree.
2.3. Modeling relative gas permeability
2.3.1. Genuchten model
The available models of gas permeability for unsaturated cement-
based material are also borrowed from that initially proposed for soils
and other porous mediums [30,39]. Based on only the water retention
characteristics continuously described by the Van Genutchen model
(VG2) of two fitting parameters α vg (m−1) and βvg (−),
Θ = [1 + (α vg hc ) βvg]−γ with γ = 1 − 1/ βvg
the relative gas permeability can be analytically yielded through the
Mualem's model [30] as,
k rg (Θ) = (1 − Θ)ξ [1 − Θ1/ γ ]2γ (10)
where h c (m) is the capillary pressure head of unsaturated porous
material. The tortuosity factor ξ (−) is found to locate in a wide range
[−1, 3] with an average value about 0.5 for soils [30], although it has
been reported to significantly vary for cement-based materials [24,40].
The coefficient γ (−) enforcing great influence on the modeled relative
gas permeability of cement-based material [25] is proposed to be totally
different from that for soils of distinct pore structure characteristics
[24,27]. Since the relative gas permeability Eq. (10) is derived from the
Van Genutchen model Eq. (9) with two parameters and Mualem model,
it is denoted as VGM2 model below.
2.3.2. Zhou model
Based on the exponential hydraulic diffusivity Eq. (4), the Burdine
model quantifying the link between relative permeabilities to water and
gas phases [29], as well as the Zhou model suggested to quantify water
retention characteristics of cement-based material [38],
Cement and Concrete Composites 104 (2019) 103356
Θ = [1 − βzh + βzh exp(αzh hc )]−1 (11)
the corresponding author C. Zhou has proposed unified models for fluid
permeability and relative molecular diffusivity [19,37,38,41], from
(4) which the relative gas permeability k rg is yielded as,
1
k rg (Θ) = ⎧1 − Θ ⎡Θ + (1 − Θ) ⎤ ⎫ exp(−nΘ)
⎨ ⎢ β ⎥⎬
⎩ ⎣ zh ⎦⎭ (12)
(5) Above Eq. (12) explicitly gives the relative gas permeability as a
function of fitting coefficient βzh and shape parameter n. Since it mainly
comes from the Zhou model [38] and Burdine model [29] together, it
will be named as ZB model below.
Although these above mentioned models for relative capillary
sorptivity and gas permeability have been proposed and validated
through some experimental results, their successful applications to ce-
ment-based materials are still under question since the pore structure
(6) characteristics of fragile cement-based material is absolutely different
from that of soils and rocks, and is rather sensitive to water removal
during drying preconditioning and water absorption [21,22].
3. Experimental scheme
3.1. Materials and specimens
In order to minimize the variance of measured capillary sorptivity
and gas permeability, two mortars of good homogeneity rather than
(7)
concrete materials are prepared with two white Portland cements but
identical W/C= 0.5 and cement to sand ratio of 1:3 by weight. Since the
prominent difference between these two mortars is their cement types,
(8)
they are denoted as M3 and M4 for that mortar using cement of strength
grade 32.5 and 42.5, respectively. In fact, mortars M3 and M4 are ex-
actly the same materials in another low-field Nuclear Magnetic
Resonance investigations we have carried out on their permeability to
various fluids and water vapor adsorption kinetics [21,22]. For more
details about these two white cements and mortars, one may refer to
Refs. [21,22].
According to the designed mix proportions, raw materials are mixed
and casted into prisms of size 100 mm×100 mm×300 mm. After de-
moulding at 24 h, all prisms are cured under controlled temperature
20±1 °C and RH>95%. At the age of 8 months, a number of cylinders of
diameter 50 mm are drilled out from the center of prisms. Neglecting
their ends, 13 disks of 25±2 mm thick are cut from the central part of
cylinders for each mortar material. After sealing their curved surfaces
with epoxy resin and vacuum saturation by water, they are further
(9) submitted to a series of preconditioning and experimental tests, as
shown in Fig. 1 and clarified later with details.
3.2. Preconditioning and testing procedures
From the classical definition of capillary sorptivity [10,42], it
should be measured on at least partially dried specimen with uniform
water content, so is the measurement of gas permeability. How to
fabricate these uniformly and partially dried specimens is a key pro-
blem in the quantification and verification of the influence of water
content on capillary sorptivity and gas permeability, which are rather
sensitive to initial water content and its spatial distribution. In order to
accelerate the preparation of specimens with uniform water contents,
the drying-equilibrating technique rather than natural water vapor
sorption method is generally adopted in experimental investigation of
their gas permeability [19,24,28,43,44] and capillary sorptivity
[45–48] as well. Elevated temperature is sometimes employed to en-
hance the water removal and redistribution, but may brings micro-
cracking damage to fragile structure of cement-based material. More-
over, the long or short equilibrating time for water redistribution is
usually a priori selected. It is hard to ensure uniform distribution of
water since the water transport process and thus the equilibrating time
3
F. Ren, et al.
Fig. 1. The overall experimental testing plan of capillary sorptivity and gas permeability at various conditions.
are closely linked to the transport properties of specific cement-based
material and temperature. One has to be cautious to choose the drying
temperature and equilibrating time span in preparing specimens of
uniform water contents.
The self-scaled drying-equilibrating procedure having been pro-
posed by the corresponding author C. Zhou is also applied herein to
prepare mortar specimens of various uniform water contents [19]. The
equilibrating time for water redistribution in any specimen is judged by
the drying of a reference one of the same material at the same condition
until reaching constant weight. Room temperature is selected to avoid
disfavored micro-cracking damage. Firstly, vacuum-saturated mortar
specimens are dried in a desiccator at room temperature (18–32 °C),
whose RH≈ 0% is controlled by dehydrated CaCl2. Their weights are
monitored at regular intervals. If the weight loss of any specimen is
found to decrease by about 10 percents of its total water content at
vacuum saturation state, it is then sealed by several plastic films and
then adhesive alumina foil to stop water loss and allow redistribution.
These procedures are repeated until the last one (reference specimen)
reaches constant weight (its change in 7 days is less than 0.01 g). At that
time, all those enclosed ones are thought to reach equilibrium with
different uniform water contents. This gentle ambient drying and self-
scaled equilibrating procedure is carefully designed and performed to
prepare partially dried mortar specimens with various uniform water
contents as good as possible. Generally, it takes more than 8 months.
After preparing partially dried mortar specimens of uniform water
contents, gas permeability and capillary sorptivity are measured on
each mortar specimen in sequence. When the first-round tests of gas
permeability and capillary sorptivity are finished, these two reference
specimens in the first round are both sealed to allow newly absorbed
water to redistribute. Meanwhile, all the other specimens are again
dried in the controlled desiccator of RH≈ 0% until they all reaches
constant weight. It takes more than 4 months, which is similar to the
costs of water vapor sorption tests [22]. Thereafter, the gas perme-
ability and capillary sorptivity are measured again on each disk
Fig. 2. Typical fitting of gas permeability and capillary sorptivity for typical specimens of high saturation degrees.
4
Cement and Concrete Composites 104 (2019) 103356
specimen. Through these two rounds of measurements, the gas per-
meability and capillary sorptivity of each specimen are obtained at both
partially dried and constant weight states, which are achieved at gentle
ambient temperature.
In order to quantify the influence of elevated drying temperature on
capillary sorptivity and gas permeability, all mortar specimens are
further subjected to oven-drying at moderate temperature 60 °C and
then severe 105 °C step by step. After reaching constant weight states,
their gas permeability and capillary sorptivity are similarly measured
twice. Through Eq. (1), the totally dry state achieved at 105 °C also
helps determine the evaporable water saturation degree for each spe-
cimen after reaching its equilibrium or other constant weight states at
various conditions.
3.3. Gas permeability measurement
The measurement of gas permeability is carried out through a
Cembureau permeameter [49,50]. Under the intrusion of nitrogen gas
at inlet pressure Pi (Pa), the gas flow rate for each specimen is mon-
itored at the downstream until steady flow rate Q (m3/s) is recorded at
atmospherical pressure Patm (Pa), from which the apparent gas perme-
ability kapp (m2) can be estimated as,
Q 2μg LPatm
kapp =
A Pi2 − Patm
2
(13)
where A (m ) is the sectional area, L (m) is the thickness, and μg (Pa⋅s) is
2
the dynamic viscosity of nitrogen gas. The apparent gas permeability is
repeatedly measured at four inlet pressures (0.2–0.4 MPa). Then the
intrinsic gas permeability kg (m2) independent on both the inlet pres-
sure and gas type can be obtained through linear fitting to Ref. [51].
2b ⎞
kapp = kg ⎛1 +
⎜ ⎟
⎝ Pi + Patm ⎠ (14)
where b (Pa) is a fitting coefficient. Typical measurements of gas
F. Ren, et al.
permeability for two specimens of high water saturation degrees are
shown in Fig. 2a. When talking about the gas permeability, the intrinsic
value kg is always implied without special emphasis.
3.4. Capillary sorptivity measurement
Capillary sorptivity is very easy to measure through gravimetric
method in common laboratory. Each specimen is weighted by an
electronic balance to obtain its initial weight of 0.001 g accuracy, which
in turn helps determine its initial water saturation degree.
Subsequently, it is put in a water tray with only about 3–5 mm im-
mersed in liquid water. At regular intervals of 15 min in the first 2 h and
then 30 min in the later 1 h, disk specimen is moved out and quickly
wiped with dry towel to remove the free water on its surface. After
recording its wet weight at elapsed time t, it is then reset to the water
tray to allow successive absorption of water. Generally, this weighting
operation is finished in 30 s to eliminate the possible error brought by
the temporary interruption of water absorption. The absorbed water
volume per unit area Vw (mm) at time t (min) is further calculated, and
then the capillary sorptivity S (mm/min0.5) is easily yielded through
linear fitting to Ref. [16],
Vw = S t + c
in which c (mm) is a fitting coefficient. In the testing period about 3 h, a
robust linear relationship between Vw and t is always observed with
high correlation coefficient R2 > 0.99. It also support the good effect of
uniform water distribution in mortar specimens prepared through the
self-scaled drying-equilibrating procedure. Representative measure-
ments of capillary sorptivity for two specimens of high water saturation
degree are shown in Fig. 2b.
4. Experimental results
4.1. Porosity and evaporable water content
From the weight of each specimen at initial vacuum saturation and
following constant weight states achieved through various pre-
conditioning procedures, the volumetric porosity θ0 and water satura-
tion degree Θ for mortar M3 and M4 can be easily calculated, as listed
in Table 1. One can see that, mortar M3 of lower strength cement
reasonably has higher porosity θ0 . When reaching constant weight
states through either ambient drying or 60 °C drying technique, the
equilibrium water saturation degree Θ for mortar M3 is lower than M4,
which is attributed to its more porous microstructure. It is noted that,
when reaching constant weight state through ambient drying tech-
nique, although the RH inside the desiccator is controlled to be nearly
0%, a small amount of water still resides in the pore space of mortar
specimens. According to the water vapor adsorption and desorption
isotherms having been reported in Ref. [22], these very low water
contents are already below the monolayer coverage of water molecules
on the inner surface of mortars, which is consistent with water sa-
turation degree Θ ≈ 0. 2. However, due to the strong physi-chemical
bond of C–S–H gel to water molecule, it is too hard to totally remove the
bonded surface water from mortars. If we increase the drying tem-
perature to 60 °C, a little more bonded water will be additionally re-
moved. When the drying temperature reaches 105 °C, all evaporable
Table 1
Porosity and water saturation at constant weight states after various pre-
conditioning.
Mortar Porosity θ0 (−) Evaporable water saturation degree Θ (−)
Ambient dry 60 °C dry 105 °C dry
M3 0.229±0.012 0.115±0.007 0.058± 0.003 0
M4 0.178±0.002 0.191±0.015 0.104± 0.005 0 water saturation. Furthermore, it is easy to judge that the Brutsaert
Cement and Concrete Composites 104 (2019) 103356
water is then lost.
4.2. Water retention characteristics
As mentioned before, the water vapor sorption isotherms for mor-
tars M3 and M4 have been measured and reported in Ref. [22]. Fur-
thermore, their capillary pressure head h c (m) could be deduced from
equilibrium relative humidity RH (−) through the Kelvin equation
[52],
RT
hc = − ln RH
Mw g (16)
in which R (J/mol/K), T (K) and M (g/mol) is the universe gas constant,
absolute temperature and molar mass of water, respectively. The
equilibrium water volume fraction w (mL/g) per unit solid mass at
various RH s, as reported in the original Fig. 3 in Ref. [22], is herein
translated into water saturation degree Θ to give the water vapor
sorption isotherms in terms of Θ (RH ) , as shown in Fig. 3a. Thereafter,
the water retention characteristics h c (Θ) can be further calculated
through Eq. (16) and are shown in Fig. 3b. Since the mortar specimens
for capillary sorptivity and gas permeability measurements are pre-
pared from initially water-saturated state through the controlled am-
(15)
bient drying approach, only the desorption isotherms are translated and
then nonlinearly fitted through both the VG2 model Eq. (9) and Zhou
model Eq. (11). The fitting parameters in Eqs. (9) and (11) are all listed
in Table 2. It is noted that the desorption isotherms for both mortars M3
and M4 are selected from the latest ones measured at desorption for 133
days.
From Fig. 3b, one can easily see that both the VG2 model Eq. (9) and
Zhou model Eq. (11) are of similarly good accuracy to quantify the
water retention characteristics of mortars. The obtained coefficients γ,
αzh and βzh will be used to simulate the dependence of unsaturated gas
permeability on water saturation degree Θ through both the VGM2
model Eq. (10) and ZB model Eq. (12).
4.3. Unsaturated capillary sorptivity
To investigate the dependence of capillary sorptivity on initial water
saturation degree, the gentle self-scaled drying-equilibrating procedure
are carefully designed and carried out at ambient condition to prepare
mortar specimens of uniform water contents, whose capillary sorptivity
and gas permeability can be easily measured together. The experi-
mental capillary sorptivity on mortar specimens of various water con-
tents are shown in Fig. 4a. Due to the impossible task to remove all
evaporable water through ambient drying, the actual capillary sorp-
tivity S0 at ideal totally dry state is still unknown, although the nominal
capillary sorptivity can be measured on specimens totally dried at 105
°C. To help understand the influence of initial water saturation degree
on unsaturated capillary sorptivity, all models summarized in Section
2.2 are also employed to simulate their dependence with a priori as-
sumed shape parameter n and porosity θ0 if needed, as shown in Fig. 4b.
Moreover, roughly adopting actual capillary sorptivity S0 = 0.16 mm/
min0.5 and shape parameter n = 6, the unsaturated sorptivity S (Θ) in
Eq. (2) with Sr (Θ) predicted from the typical Zhou model Eq. (7) is also
shown in Fig. 4a to help analysis these experimental results in com-
parison to all available models.
From Fig. 4, it is very surprised to find that all these models sum-
marized above are obviously incapable to even approximately capture
the dependence of capillary sorptivity on water saturation degree over
the whole range. In Fig. 4a, the dependence of capillary sorptivity from
Zhou model is absolutely and totally different from experimental re-
sults. Considering the Zhou model shown in Fig. 4b behaves rather si-
milar to the Philip model and Parlange model, they are also impossible
to describe the relationship between capillary sorptivity and initial
model cannot capture the features of experimental data too. However,
5
F. Ren, et al. Cement and Concrete Composites 104 (2019) 103356

Fig. 3. The water vapor desorption isotherms and corresponding water retention curves for mortars M3 and M4.

Table 2 become negligible and undetectable at Θ > Θcap . The least-square linear
The fitting parameters in VG2 model and Zhou model for mortars M3 and M4. fitting gives the Θt and Θcap as 0.501 (0.584) and 0.789 (0.852) for
Mortar VG2 model Eq. (9) Zhou model Eq. (11)
mortar M3 (M4), respectively, as shown in Fig. 4a.
The capillary saturation degree Θcap defined from the experimental
−1
αvg (km ) β vg (−) γ = 1 − 1/ β vg αzh (km−1) βzh (−) dependence of capillary sorptivity on initial water saturation degree
agrees well with the free water content identified by the low-field nu-
M3 1.4481 1.5566 0.3576 2.3112E− 5 1.1886E4 clear magnetic resonance (NMR) testing [22], and roughly equals to the
M4 0.5224 1.6677 0.4004 2.9186E− 5 6.4272E3
equilibrium water content at 98% RH. From the multi-exponential fit-
ting to the CPMG relaxation signal from the low-field NMR testing on
the vacuum-saturated specimens of the same mortar materials, it was
the Brutsaert model gives a threshold of capillary saturation degree
reported in Table 2 of [22] that, the 5th exponentially decayed com-
Θcap , beyond which the capillary pressure is too low to absorb liquid
ponent for mortar M3 (M4) takes 20.96% (9.55%) of its total water
water through capillarity. It makes good sense since air voids and
content, which is in good agreement with the free water saturation
coarse pores exert little capillary pressure and thus have little ability to
degree 1 − Θcap = 0. 211 (0.148) defined from the dependence of ca-
absorb liquid water. This feature agrees well with our experimental
pillary sorptivity on initial water content, as shown in Fig. 4a. Since the
findings at high water content near saturation. Nevertheless, all avail-
transverse relaxation time T2 (>1.5 s) of the 5th component is rather
able models in literature are invalid in the quantification of the un-
long, it is definitely free water. The higher Θcap for mortar M3 is ob-
saturated capillary sorptivity for mortar specimens prepared under
viously attributed its coarser microstructure than mortar M4, which
ambient condition. It will be further discussed in Section 5.2 with more
could be seen in their pore size distribution curves already shown in
details.
Figs. 1 and 2 of [21]. Besides, Fig. 3a also indicates that the capillary
When looking at the experimental data shown in Fig. 4a, it seems
saturation degree is roughly equal to the equilibrium water content at
that the capillary sorptivity for mortars M3 and M4 behave in a rather
98% RH. The equilibrium Kelvin diameter of meniscus at 98% RH is a
similar bilinear law with respect to water saturation. In addition to the
little larger than 100 nm at room temperature, which is of negligible
capillary saturation degree Θcap , there is another transitional saturation
capillarity [53].
degree Θt , below which the capillary sorptivity is more sensitive to
In another aspect, the transitional water saturation degree Θt is
water saturation degree. In the two ranges of [0, Θt ] and [Θt , Θcap], ca-
closely linked to the transitional water allocation between gel pores and
pillary sorptivity both linearly depends on water saturation degree Θ
interlayer pores. Together with the water vapor desorption isotherms
but with different proportionality. Moreover, their capillary sorptivity

Fig. 4. The dependence of unsaturated capillary sorptivity on water saturation degree.

6
F. Ren, et al.
shown in Fig. 3a, the transitional saturation degree Θt = 0. 501 (0.584)
for mortar M3 (M4) roughly equals to its equilibrium water volumetric
fraction 0.460 (0.600) at 75% RH, which is also a transitional point
from the view of relative water distribution in interlayer pores and gel
pores, as clearly indicated by Fig. 8 of [22]. It was reported that, al-
though the water content in interlayer pores continuously increases
during water vapor adsorption (see Fig. 7 of [22]), capillary con-
densation will remarkably occur in gel pores when RH is beyond 75%
for mortars M3 and M4 [22]. The Kelvin radius of 3.7 nm in accordance
with critical 75% RH agrees well with the equivalent radius 2.82 (2.89)
nm for the gel pores of mortar M3 (M4) at initial water saturation state
(see Table 2 of [22]). In the case of capillary absorption, it is expected
that, when the mortar specimen of water saturation degree Θ > Θt
contacts with liquid water, although absorbed liquid water is also re-
distributed into interlayer pores and makes them expand, its capillary
sorptivity is primarily determined by the rate of water absorption into
gel pores, inter-hydrates pores and fine capillary pores that are still
empty. When regarding to mortar specimen of Θ < Θt , the interlayer
pores continuous to collapse along with the decrease of its water con-
tent, in turn coarsening its gel pores and inter-hydrates pores that are
almost free of water. As a result, the water absorption rate into am-
plified empty pores gets enhanced by a greater extent. In this sense, the
critical equilibrium state at 75% RH brings the transitional dependence
of capillary sorptivity at initial water saturation degree Θ = Θt . From
these considerations, the transitional water saturation degree Θt is
plausibly linked to the critical equilibrium distribution of water in dy-
namic interlayer pores and gel pores at 75% RH, accounting for the
bilinear dependence of capillary sorptivity on water content.
4.4. Unsaturated gas permeability
To avoid the ambiguous influence of elevated temperature on fra-
gile pore structure of cement-based material, the unsaturated gas per-
meability is measured on specimens with various saturation degrees
that are carefully prepared at ambient condition. Since the action of
elevated temperature is absent, little micro-cracking damage is in-
corporated into those mortar specimens, whose gas permeability are
only affected by the water saturation degree. The experimental data of
their gas permeability kg is shown in Fig. 5 with respect to evaporable
water saturation degree Θ . Although gas permeability is recognized to
be scattering, it seems that the unsaturated gas permeability for both
mortars M3 and M4 obey similar behavior with clear trends. If the
actual gas permeability kg0 at ideal totally dry state is unknown and
Fig. 5. The dependence of unsaturated gas permeability kg on water saturation
degree Θ.
7
Cement and Concrete Composites 104 (2019) 103356
Table 3
The fitting coefficients in the VGM2 and ZB models for unsaturated gas per-
meability of mortars.
Mortar VGM2 model, Eq. (10) ZB model, Eq. (12)
kg0 (10−17 m2) ξ (−) R2 (−) kg0 (10−17 m2) n (−) R2 (−)
M3 1.6134 2.9567 0.8991 1.8356 3.8406 0.8984
M4 1.7883 2.2062 0.8261 2.3152 3.3461 0.8109
thus treated as undetermined parameter, the experimental data of un-
saturated gas pemeability kg for mortars M3 and M4 are both non-
linearly fitted to Eq. (2), in which the relative gas permeability k rg (Θ) is
described by either the VGM2 model Eq. (10) or ZB model Eq. (12), as
shown in Fig. 5. The regressed actual gas permeability kg0 at ideal Θ = 0
and other fitting coefficients are all listed in Table 3. Through com-
paring the predicted kg0 with those gas permeability experimentally
measured on specimens dried at elevated temperature, the effect of
micro-cracking damage induced by drying at elevated temperature
could be approximately evaluated. This will be discussed later.
From Fig. 5, one can easily see that, both the VGM2 and ZB model
could roughly follow the dependence of unsaturated gas permeability
on water saturation degree Θ with similar satisfactory accuracy. All
unsaturated gas permeability predicted from either VGM2 or ZB model
agree well with experimental data, which are measured on mortar M3
(M4) specimens of 0. 141 ≤ Θ ≤ 0. 767 (0. 234 ≤ Θ ≤ 0. 817 ). Within
this range, the VGM2 model and ZB model behave rather similarly in
predicting the dependence of unsaturated gas permeability on evapor-
able water content.
However, when initial water saturation degree Θ < 0. 14 (0.24) for
mortar M3 (M4), the gap between the VGM2 model and ZB model is
obvious, and becomes more remarkable when Θ → 0 , as shown in
Fig. 5. The ZB model Eq. (12) with shape parameter n > 3 always gives
higher gas permeability than the VGM2 model Eq. (10) with tortuosity
coefficient ξ < 3. At the ideal totally dry state, the gas permeability kg0
predicted from the ZB model is 13.8% (29.5%) higher than that from
the VGM2 model for mortar M3 (M4). From Fig. 3a, the water content
Θm ≈ 0. 14 (0.24) for mortar M3 (M4) agrees well with the critical
Θm = 0. 14 (0.20) in accordance with monolayer coverage of water
molecules at about 25% RH from BET theory [53]. If this monolayer of
water is further totally removed, according to the VGM2 model, the gas
permeability will significantly increase by 61.3% (78.8%) for M3 (M4),
from about 1.0× 10−17 m2 to 1.613× 10−17 (1.788× 10−17 ) m2. This sig-
nificant increase of gas permeability comes from the noticeable collapse
of C–S–H gel after removal of surface water, which will obviously
coarsen the pore structure of mortars [21,22].
4.5. Influence of drying temperature
Due to the strong water affinity of cement-based material, it is ra-
ther tough and time-consuming to totally remove its water content
without the action of elevated temperature, which is susceptible to
bring micro-cracking damage. Furthermore, it is widely accepted that
the almost inevitable cracking damage becomes more severe under
more cruel drying condition. Because the gas permeability and capillary
sorptivity are both sensitive to micro-cracking damage, the experi-
mental data measured on nominal dry state achieved at elevated tem-
perature are biased and thus denoted as nominal values. Since the
nominal gas permeability and capillary sorptvity are generally adopted
in laboratory to indicate the transport properties and thus durability
performance of cement-based material, it is necessary to understand the
influence of drying temperature on them before their applications. With
these aims, the nominal gas permeability and capillary sorptivity
measured at three constant weight states achieved at different tem-
peratures are averaged on 13 specimens for each mortar and listed in
F. Ren, et al.
Table 4
Nominal gas permeability and capillary sorptivity measured at various constant weight states.
Mortar Gas permeability kg (× 10−17 m2)
Ambient dry 60 °C dry 105 °C dry
M3 1.484± 0.958 2.915±1.220 5.715± 1.799
M4 1.316± 1.006 2.546±2.435 5.518± 0.798
Table 4.
4.5.1. Nominal gas permeability
Comparing the nominal gas permeability in Table 4 to the predicted
actual values in Table 3, one can obviously see that, the gas perme-
ability of mortar M3 (M4) measured at totally dry state is 3.11 (2.38)
times of that ideal values kg0 predicted through the ZB models, which
gives higher gas permeability than the VGM2 model at Θ = 0 . This
remarkable gap must come from the micro-cracking damage induced by
the action of high temperature. When drying at moderate temperature
60 °C to constant weight, although Θ = 5. 8% (10.4%) for mortar M3
(M4), the measured nominal gas permeability remains obviously higher
than ideal value kg0 predicted from the ZB models by 58.8% (9.9%).
Therefore, the influence of elevated temperature on gas permeability is
unavoidable even at the widely adopted moderate drying temperature
of 60 °C.
When comparing the nominal gas permeability of two mortars, it is
clearly indicated that, the gas permeability for mortar M4 is always
lower than mortar M3 at each constant weight state, but by a rather
small extent about 3.6%–14.5%. However, according to the experi-
mental data reported in Table 2 of [21], the water permeability of
mortar M3 is about 22 times higher than that of mortar M4. Moreover,
if pore water is replaced by isopropanol (IPA), the IPA permeability of
mortar M3 is only a little higher than mortar M4 [21]. It seems con-
fusing but plausible since the pore structure of mortars are definitely
changed by the water removal due to the collapse of interlayer pores of
C–S–H gel [22]. The permeability to either IPA or inert gas for cement-
based material is significantly biased by the inevitable alteration of
pore structure together with the possible micro-cracking damage after
removing pore water especially at elevated temperature. When fluid
permeability is applied to indicate the durability performance of ce-
ment-based material, one must be cautious to choose the permeating
fluid.
4.5.2. Nominal capillary sorptivity
From the experimental data listed in Table 4, it is straightforward to
understand the rising of capillary sorptivity with the increase of drying
temperature for each mortar, since the water content is reduced and
micro-cracking damage is also additionally incorporated. However,
when comparing mortars M3 and M4, it is found that their capillary
sorptivity are fairly similar at identical constant weight state achieved
at 60 °C or 105 °C. Specifically, the averaged capillary sorptivity for
mortar M3 of higher water permeability is definitely higher than mortar
M4 by 7.3% at ambient dry state. In contrast, when it is tested at
constant weight states preconditioned at elevated temperature, the
averaged capillary sorptivity for mortar M4 is inversely higher than
mortar M3 by about 5%, which may be covered by experimental error.
When referring back to Fig. 4a, the capillary sorptivity of mortar M4
does be systematically higher than mortar M3 at any saturation degree
Θ . Although mortar M4 has lower permeability to water, IPA as well as
inert gas, due to the complicated influence of preconditioning tem-
perature, it is ambiguous to say whose nominal capillary sorptivity is
lower. As a consequence, it is tricky to judge the durability performance
of cement-based material by only its nominal capillary sorptivity,
especially when it is measured on samples having underwent high
temperature action. Before testing and applying capillary sorptivity,
8
Cement and Concrete Composites 104 (2019) 103356
Capillary sorptivity S (mm/min0.5)
Ambient dry 60 °C dry 105 °C dry
0.117±0.035 0.161± 0.042 0.223±0.037
0.109±0.032 0.169± 0.033 0.236±0.027
one must be also cautious to select the preconditioning method for
cement-based material.
5. Discussion
5.1. Invalidity of unsaturated flow theory
From the above analysis on the capillary sorptivity measured on
unsaturated mortar specimens, it is surprisingly found that none of
these available models for unsaturated sorptivity is capable to capture
the observed dependence of capillary sorptivity on initial water con-
tent. An earlier investigation the corresponding author C. Zhou has
carried out on three concretes shows somewhat agreement but fairly
rough [19]. Moreover, although good agreements have been reported
on several brick materials [15], another experimental investigation on
concrete materials of various compositions has revealed apparent dis-
agreement between them [47]. Since these models are strictly derived
from the unsaturated flow theory, their disagreement seems pretty
unintelligible and implausible. As a matter of fact, the unanticipated
failure of these models on cement-based materials is reasonably at-
tributed to its strong sensitivity to water only.
It should be kept in mind that, the unsaturated flow theory and
theoretical models for capillary sorptivity are originally developed for
soils and rocks, whose pore structure are treated to be rigid and un-
changed during water removal and regain. However, it is not the case
for cement-based material of distinct pore structure sensitive to water.
During water vapor adsorption, the adsorbed water molecules will enter
the interlayer pores of C–S–H gel with priority, and subsequently makes
C–S–H gel expand [22]. During capillary absorption of liquid water, it is
thus expected that, the absorbed liquid water will rush into interlayer
pores with higher rate than water vapor. This redistribution of absorbed
water into interlayer pores has been observed by a single-sided NMR
testing [54]. Meanwhile, the expansion of C–S–H gel during capillary
absorption will make cement-based material elongate at macroscopic
scale, which has been experimentally validated [55]. It is also the
physical root responsible to the water permeability of cement-based
materials anomalously lower than its permeability to other fluids by
several orders of magnitudes [21]. Similarly, the continuous swelling of
C–S–H gel will gradually slow down the rate of water absorption, then
makes it obviously deviate from the square root of time law, as shown
in the reproduced typical deviation in Fig. 6a [12]. Considering the
dynamic structure of C–S–H gel and thus cement-based material, it is
not surprised to see the disagreement between these available models
and experimentally obtained capillary sorptivity at all. As a result, if the
strong water sensitivity of C–S–H gel is not taken into account, the
unsaturated flow theory is not suitable to quantify the process of ca-
pillary absorption into cement-based material any more.
5.2. Anomalous water absorption
In microscopic scale, capillary absorption is a dynamic process of
water filling into the empty pore space of at least partially dried mortar
specimens, which depends on its current water content and pre-
conditioning history. After preconditioning to a certain water content,
the interlayer pores of mortar specimens will obviously collapse and
coarsen the gel pores and inter-hydrates pores [21,22]. Thereafter, the
F. Ren, et al.
Fig. 6. Two main anomalous characteristics for the water absorption process of cement-based materials.
collapsed interlayer pores of C–S–H gel will continuously absorb liquid
water and progressively swell during capillary absorption. This par-
tially recoverable contraction of interlayer pores during drying pre-
conditioning and their remarkable expansion during water absorption
make the capillary absorption process far more complicated than other
porous medium whose pore structure is almost fixed and insensitive to
water removal and regain.
Based on the unsaturated flow theory, it is strictly yielded that, if
the pore structure of porous medium is inert to the absorbed liquid, its
capillary absorption will obey the square root of time law [2], from
which the capillary sorptivity is defined with clear physical sig-
nificance. Regarding to porous cement-based material, it is broadly
observed that its absorption of many organic liquids complies with this
law very well. However, its capillary absorption of water will re-
markably deviate sooner or later [12,13], as shown in Fig. 6a. In our
opinion, this anomalous deviation is physically brought by the con-
tinuous swelling of C–S–H gel in the wetted part of mortar specimen,
whose water permeability will progressively decrease by several orders
of magnitudes right after contacting with water. Because the absorbed
liquid water has to rush through the wetted zone of decreasing water
permeability, remarkable deviation from the square root of time law is
therefore expected. During water absorption, the progressive expansion
of C–S–H gel that gradually changes the pore structure and water
transport properties of cement-based material is the hidden physical
principle responsible to the extraordinary deviation from the theore-
tical square root of time law. Although it still holds for a short duration
frequently, the physical meaning of capillary sorptivity of water is al-
ready obscured for cement-based materials.
The water sensitivity of C–S–H gel and thus cement-based material
is also the physical root of several other anomalous transport phe-
nomenons. If the liquid absorption is a transport process driven by
purely capillarity, the capillary sorptivity will theoretically scale as
σ / η (see Fig. 6b), where σ (N/m) and η (Pa⋅s) is the surface tension and
dynamic viscosity of the absorbed liquid, respectively [42]. This scaling
does hold for the absorption of many organic liquids but except water
[55–57]. During capillary absorption of water, the water permeability
of the wetted zone of cement-based material is gradually decreasing
and retards the rate of subsequent water absorption. As a consequence,
it is conceivable to see the experimental data of normalized capillary
sorptivity of water beneath those of inert organic liquids, as shown in
Fig. 6b. The observable scattering of experimental data of water ab-
sorption in Fig. 6b is ascribed to different expanding rates of C–S–H gel
of various compositions, which is also dependent on temperature [55].
Thermodynamically, the rate of water entry into the interlayer pores
9
Cement and Concrete Composites 104 (2019) 103356
and thus swelling of C–S–H gel are promoted at higher temperature.
This dependence of C–S–H gel expanding rate on temperature is ad-
ditionally validated from the ending of initial linear phase of water
absorption [13], which occurs earlier at higher operating temperature.
From these above considerations, several other confusing character-
istics of water absorption into cement-based materials are also physi-
cally explained by the specific expansion of C–S–H gel during capillary
absorption of only water.
Considering the complexity of fundamental water transport in ce-
ment-based materials of great sensitive pore structure to water removal
and regain, the penetration processes of deleterious gases, ions and
water itself are still far away from being totally understood. So is the
quantitative modeling of the durability performance for common un-
saturated cement-based materials under service.
6. Concluding remarks
The capillary sorptivity and gas permeability of two mature cement
mortars are carefully measured at various initial water contents and
thoroughly investigated with great emphasis on the water sensitivity of
C–S–H gel. Several concluding remarks could be made with regard to
the quantitative modeling of mass transport and thus durability per-
formance for cement-based materials.
• The dependence of unsaturated gas permeability on water satura-
tion degree could be well quantified through both VGM2 and ZB
models. If drying at ambient condition, the tortuosity factor in these
two models is rather similar but obviously different from that typical
values generally determined on specimens preconditioned at ele-
vated temperature, indicating the elusive sensitivity of pore struc-
ture to preconditioning temperature.
• Because of the remarkable collapse of C–S–H gel and coarsening of
pore structure during required preconditioning, the gas permeability
and capillary sorptivity are both biased especially for drying at
elevated temperature. One must be cautious to apply them to in-
dicate the durability performance of cement-based materials.
• All available models of unsaturated capillary sorptivity in literature
are NOT capable to capture its dependence on initial water content,
which could be well captured by a bilinear law with characteristic
transitional and capillary saturation degrees. This unexpected dis-
agreement between theoretical models and experimental data of
capillary sorptivity measured at ambient condition is ascribed to the
dynamic structure of C–S–H gel and thus cement-based material,
which are definitely rather sensitive to water removal during drying
F. Ren, et al.
preconditioning and water regain in capillary absorption. It makes
the physical significance of capillary sorptivity of water obscure for
cement-based materials.
• The strong sensitivity of C–S–H gel specific to water is physically
responsible to the reported anomalous characteristics of water ab-
sorption in cement-based material. If the strong water sensitivity of
C–S–H gel is neglected, the unsaturated flow theory is NOT capable
to quantify the water transport in cement-based material any more.
Importantly, the modeling of durability performance will face great
challenges in dealing with the complex transport of water itself and
other deleterious agents in common unsaturated cement-based
materials.
Acknowledgment
The financial supports from the National Natural Science
Foundation of China, China (No. 51578194, 51878602) and the
Guangdong Provincial Key Laboratory of Durability for Civil
Engineering (No. GDDCE 17-5), Shenzhen Durability Center for Civil
Engineering, Shenzhen University for the current research work are
gratefully acknowledged.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cemconcomp.2019.103356.
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