Construction and Building Materials 244 (2020) 118298

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Construction and Building Materials

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

Computed permeability for cement paste subject to freeze-thaw cycles

at early ages
Ya Wei a,⇑, Weiqiang Guo b, Zehong Wu b, Xiang Gao b
a
Key Laboratory of Civil Engineering Safety and Durability of China Education Ministry, Department of Civil Engineering, Tsinghua University, Beijing 100084, China
b
Department of Civil Engineering, Tsinghua University, Beijing 100084, China

h i g h l i g h t s

The pore parameters are measured from MIP, BSE, and X-ray CT scanning techniques.

The pore characteristics of cement pastes subject to freeze-thaw cycles are assessed.

The intrinsic permeability of cement paste is obtained by three different methods.

The GEM method is a more suitable tool for cementitious materials with low porosity.

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

Article history: Assessing the permeability of concrete subject to unexpected freeze-thaw cycles at early age is critical to
Received 28 November 2018 ensure the durability and service life of concrete structures. However, measuring permeability of con-
Received in revised form 15 January 2020 crete and cement paste has been a challenge. In this study, the intrinsic permeability of cement paste
Accepted 27 January 2020
is calculated by using Katz-Thompson equation, general effective media (GEM) method, and Navier-
Stokes method based on the pore parameters measured from the mercury intrusion porosimetry
(MIP), the backscattered electron (BSE) imaging, and the X-ray computed tomography (CT) techniques.
Keywords:
The pastes are subject to freeze-thaw cycles at the age of 1 and 7 days followed by sealed curing until
Early-age concrete
Freeze-thaw cycles
the age of 40 days. The water-to-cement (w/c) ratios of paste are 0.3 and 0.5, representing the high-
Image processing and low-strength concrete, respectively. The measured pore characteristics and the calculated intrinsic
Pore characteristics permeability are then compared to that of the control samples. The measurable pore size range of each
X-ray CT scanning technique is quantified, and the applicability of each computing method for permeability is discussed.
The results of this study provide the insight into the feasibility of different measuring techniques for pore
parameters and the predicting methods for permeability, particularly for cementitious materials subject
to freeze-thaw cycles.
Ó 2020 Elsevier Ltd. All rights reserved.

1. Introduction constructed in this area must meet the requirement of freeze-

The engineering structures are normally challenged by the
severe environment conditions including climate and geography.
Particularly in the regions with high attitude, the climate is charac-
terized by frequently dramatic temperature change during a day.
The temperature can drop from above 15 °C at summer-like noon
to below 0 °C from the sudden snow storm, which renders the con-
crete structures several freeze-thaw cycles during a day. This is
particularly detrimental for concrete at very early-ages when the
microstructure of paste is still vulnerable. Cement concrete
⇑ Corresponding author.
E-mail address: yawei@tsinghua.edu.cn (Y. Wei).
thaw resistance.
Permeability is typically used as one of the key indicators for
the durability of concrete [1–3]. Permeability of concrete is directly
affected by the pore characteristics, such as the total porosity, the
pore size distribution, and the critical pore diameter of the paste
phase in concrete. Freeze-thaw cycles can inhibit and even stop
the further hydration of cement paste, and thus hinders the forma-
tion of dense microstructure of concrete. This will further increase
the permeability of concrete. The significant increase of concrete
permeability was found in high water/cement ratio (w/c) of 0.65
concrete after subject to freeze-thaw cycles [4]. Soroushian and
Elzafraney [5] also found that the permeability of concrete was
increased to twice of the control sample by the freeze-thaw cycles.

https://doi.org/10.1016/j.conbuildmat.2020.118298
0950-0618/Ó 2020 Elsevier Ltd. All rights reserved.
2 Y. Wei et al. / Construction and Building Materials 244 (2020) 118298
Laboratory-based tests have been conducted for many years to
measure the permeability of concrete and paste. It is widely recog-
nized that direct experimental measurement of water permeability
usually encounters practical difficulties for modern dense concrete
due to its low permeability and the complicated testing conditions.
Given the limitations of experimental test, the prediction of per-
meability of cementitious materials is quite helpful to assess the
durability of concrete efficiently, either with analytical or numeri-
cal models. Researchers developed analytical models for perme-
ability prediction from the microstructure information obtained
from the mercury intrusion porosimetry (MIP) and the backscat-
tered electron (BSE) images. These models are established based
on the fact that the permeability is controlled by pore distribution
and the percolation of pore network. In these models, Katz-
Thompson equation established the relationship between the per-
meability and the critical pore diameter of concrete [6]. It is
accepted that the Katz-Thompson equation is more applicable to
cementitious materials with higher w/c ratios [7–9]. Halamickova
and Detwiler [8] concluded that Katz-Thompson equation might
work better for systems with interconnected capillary pore net-
works than for systems with gel pores dominating the transport.
By using the effective porosity and the pore threshold diameter
derived from MIP results, a modified Katz–Thompson model is pro-
posed by Ma et al. [10] to predict the water permeability of paste
containing alkali activated fly ash.
Unlike other porous materials, the solid phase of the cement
paste contains gel pores. This means that even if the capillary
porosity is less than the percolation threshold, the diffusion can
still occur [11]. Based on Bruggeman’s effective media theory and
the percolation theory, McLachlan et al. [12] proposed a general
effective media (GEM) model to describe the effective macroscopic
properties, such as the electrical resistivity and the permeability of
cement paste which is considered as a bicomposite material with
one high-permeable phase made of capillary pores and one low-
permeable phase consisting of C-S-H gel, CH, and the unhydrated
cement particles. These two phases change with the hydration pro-
cess, and the permeability of cement paste depends strongly on the
amount of porosity present in the microstructure. Therefore, the
volume fraction and the permeability of each phase determine
the overall permeability. This two-phase system has been
employed successfully in the previous study for computing the
electrical conductivity and the permeability of concrete and
cement paste [11,13,14]. By identifying and defining the intrinsic
permeability of concrete from GEM model, Wimalasiri et al. [15]
proposed a new methodology to investigate the permeability of
stressed concrete.
With the advance of X-ray CT technique, non-destructively
measuring the microstructure of cementitious materials at the
lm scale becomes possible [16]. Models are often developed to cal-
culate the permeability of cement-based materials from the
microstructure information detected by the X-ray CT technique.
Bentz and Martys [17] proposed the methodology of calculating
permeability of cement paste by using finite element method from
the X-ray CT scanned results. This method is capable of taking into
account the effect of porosity, pore size distribution and percola-
tion of pore network. It has been used for predicting permeability
of cementitious materials in recent years [18–22]. Zhang [22] pre-
dicted the water permeability and the gas permeability by using
the lattice Boltzmann model based the 3D microstructure of
cement paste obtained by using the high-resolution X-ray micro-
CT. By using a 3D Stokes permeability solver for porous media,
Pieralisi et al. [23] suggested that it is possible to account for the
important influence of the compaction in the assessment of the
permeability without the need of resorting to experimental stud-
ies. With improved technologies in image acquisition, processing,
and analysis, we can take advantage of the 3D information
provided by X-ray CT, not only to visualize, but also to quantify
more accurately the pore system, cracks, and other properties to
assess the durability of cement-based materials against the
freeze-thaw action [24].
In this study, the pastes are subjected to freeze-thaw cycles at
early-ages to simulate the severe conditions that concrete
experienced in the high-attitude and cold regions. The pore charac-
teristics of pastes subject to early-age freeze-thaw cycles are
assessed by using different techniques, and the predicted intrinsic
permeability based on the measured microstructure parameters
are compared to the experimental results. The applicability of dif-
ferent techniques and modeling methods is discussed. The results
of this study can provide an alternative way of quantifying
freeze-thaw resistance and the insight into the feasibility of
measuring techniques and the predicting method, particularly for
permeability of cementitious materials.
2. Review of computational methods for permeability
2.1. Katz-Thompson equation
Katz and Thompson derived an equation relating the permeabil-
ity of porous media to the microstructural parameters by using
percolation concepts in terms of conductivity (1987) [6]. The
intrinsic permeability (k in m2) is determined by the connectivity
of pore (denoted by r=r0 and often called the conductivity forma-
tion factor) and the pertinent length scale (Lc ):
1 r 2
k¼ L ð1Þ
226 r0 c
where, r is the electrical conductivity of the saturated porous mate-
rials; r0 is the conductivity of the solution in the pores; Lc is the
critical pore diameter, which corresponds to the pore diameter at
the inflection point on a cumulative volume versus pressure dia-
gram measured from MIP [9]. Under the condition of pore diameter
greater than Lc, a connected path can form spanning the sample. The
smaller the critical pore size, the finer the pore structure. This equa-
tion was originally developed to predict the intrinsic permeability
of the sedimentary rock from the MIP data.
It was experimentally proven by measuring the electrical resis-
tance of the sample that the inflection point of the rapidly rising
portion on the cumulative intrusion curve marks the threshold of
the formation of a continuous pathway and consequently electrical
continuity through the sample. Katz and Thompson [6] proposed
an expression for the conductivity formation factor which can be
calculated from MIP data as:
r Lmax
¼ /SðLmax Þ ð2Þ
r0 Lc
where, Lmax is the electrical conductivity characteristic dimension
that produces maximum conductance, which is defined from the
mercury injection curve. Lmax = 0.34 lm for a very broad pore size
distribution in rocks [6], in this study Lmax will be calculated from
the measured pore characteristics for cement paste, which is
detailed in Section 5.1, / is the total porosity, S is the fractional
volume of the connected pore space involving pore diameter of Lmax
and larger. The intrinsic permeability k and the conductivity forma-
tion factor can be predicted from the same mercury intrusion mea-
surements with no adjustable parameters [6].
The Katz-Thompson equation performed well for rocks [6].
Christensen et al. [7]directly measured r=r0 by the electrical tech-
nique and found that the calculated permeability of cement paste
tracked well with the experimental data, the difference between
the experimental and the calculated permeabilities is within 1.5
order of the magnitude. Garboczi [25] found that the prediction
 Y. Wei et al. / Construction and Building Materials 244 (2020) 118298 3

from Katz-Thompson equation agrees with the measured perme- 0:32ð1  aÞ

ability of cement paste, and expected that the equation should still
work for concrete. However, Ei-Dieb and Hooton [26] concluded
that Katz-Thompson equation does not apply to concrete, he calcu-
lated r=r0 from the MIP data instead of measuring it.
By combining Eqs. (1) and (2), the intrinsic permeability of the
porous materials can be expressed as a function of porosity (/), the
critical pore diameter (Lc), the pore size that produces maximum
electrical conductance ðLmax Þ, and the fractional volume of the con-
nected pores with size greater than Lmax ðSðLmax ÞÞ:


1 2 Lmax
k¼ Lmax /SðLmax Þ
89 Lc
The Katz-Thompson equation as shown by Eq. (3) is an analyt-
ical method to calculate the intrinsic permeability of porous media
from its pore characteristics. The parameters in Eq. (3) for predict-
ing permeability can be obtained by different measuring tech-
niques, such as MIP and BSE which will be used in this study for
pore structure measurement.
V Unhydrated ¼ ð7Þ
ðw=cÞ þ 0:32
where, w/c is the water-cement ratio; a is the hydration degree,
which can also be calculated from Power’s model:
ð1  /Þðw=cÞ  0:32/
a¼ ð8Þ
0:36
The ratio of volume fraction of C-S-H and CH can be calculated
from stoichiometry. In this study, VC-S-H/VCH = 1.66:0.63 is selected
for cement paste.
It can be seen from Eq. (4) that the value of overall permeability
ð3Þ (k) is always between kl and kh. The main path of transport in
cement paste is known to be the capillary pore space, whereas,
the gel pores play a minor role in transport, except at very low cap-
illary porosity. Also note that the model itself contains time-
dependent hydration effect, which is revealed by the microstruc-
tural changes in cement paste specimens. The GEM theory is
shown to apply to both low- and high-permeable cement paste
[7,9].

2.2. GEM theory-based method 2.3. Navier-Stokes method

With doubt of that the Katz-Thompson equation cannot directly The flow condition within the paste microstructure was
apply to predict the water permeability of cementitious materials, assumed to be incompressible slow flow. That means that the den-
because it was developed based on rocks in which gel pore does sity (q) and the viscosity of the fluid are constant. The equation of
not exist, the general effective media (GEM) theory-based model continuity can be written as:
was proposed considering the contributions of both capillary pores
@q
and the gel pores in the cementitious materials to predict the per- þ r  ðqv Þ ¼ 0 ð9Þ
meability of OPC paste [9]. In this method, cement paste is consid- @t
ered as a two-phase material. One phase is the high-permeable where, v is the local velocity of the fluid, qv is the mass flux. In this
capillary pore and the other one is the low-permeable phase con- equation, since the density of the fluid is constant, @@tq ¼ 0, Eq. (9) can
sisting of C-S-H gel, CH, and the unhydrated particles. The overall be simplified as:
permeability (k) of the cement paste can be calculated based on
the volume fraction and the permeability of each phase [27,28]: rv ¼0 ð10Þ
   
1=t 1=t 1=t 1=t By incorporating a time derivative of pressure term with a so-
ð1  /Þ kl  k / kh  k
þ ¼0 ð4Þ called artificial compressibility parameter into the continuity
1=t 1=t 1=t 1=t
kl þ Ak kh þ Ak equation, the entire set of governing equations can be transformed
into a time-dependent and hyperbolic-parabolic-type equation.
where, k (in m2) is the intrinsic permeability of the cement paste, Under this circumstance, Eq. (9) can be expressed as:
which is independent of the fluid used to measure it; / is the cap-
@p
illary porosity; /c ¼ 0:18 is the critical capillary porosity for perco- þ c2 r  v ¼ 0 ð11Þ
2 @t
lation; A ¼ ð1  /c Þ=/c ; kh ¼ L 2 ð1:8Þð1
 /c Þ is the permeability
1
226 c
of the high-permeable phase, which only depends on the critical where, c2 is an arbitrary constant. At the same time, the equation of
pore diameter Lc and the critical capillary porosity /c ; t is the crit- motion can be written into substantial derivative with the Navier-
ical exponent for the permeability. Christensen et al. [29] pointed Stokes equation as:
out that the t exponent of the GEM equation could be termed as Dv
‘‘shape factor”. t = 2 can be regarded as a theoretical value in cement q ¼ rp þ ur2 v þ f ð12Þ
Dt
2
paste [30] kl ¼ kC - S - H ð1  ð1  /C - S - H Þ=ð1  /0 c ÞÞ is the perme-
where, u is the viscosity of fluid; f is body force, which is neglected
ability of the low-permeable phase; /0c is the critical volume frac-
since the sample is in microscale. Because the Reynolds number is
tion of C-S-H, which is 0.17 according to[32], kC - S - H is the
extremely small for the creeping flow, the acceleration term
permeability of C-S-H gel, which is 7  1023 m2 [31]; /C - S - H is
q DDtv ¼ 0. Therefore, Eq. (12) is further simplified to obtain the linear
the volume fraction of C-S-H in solid phase which includes C-S-H
Stokes equation as:
gel, CH, and the unhydrated components, and can be calculated
by using Eq. (5): ur2 v ¼ rp ð13Þ
VC - S - H The boundary conditions include the fluid velocity vanishing at
/C - S - H ¼ ð5Þ
V Unhydrated þ V CH þ V C - S - H all fluid-solid interfaces and an applied pressure gradient across
two of the faces comprising the three-dimensional microstructure
The volume fraction of the hydration products (V C - S - H and [17]. To numerically solve the Stokes equations, a finite-difference
V CH ) and the unhydrated cement particles V Unhydrated can be calcu- scheme in conjunction with the artificial compressibility relaxation
lated by using Power’s model [31] for ordinary Portland cement algorithm is employed. The discretized and non-dimensionalized
paste (Eqs. (6) and (7)), respectively: approximation of Eqs. (11) and (13) can be written as:
!
0:68a 1  nþ1  @ v nþ1 @ v nþ1 @ v nþ1
V C - S - H þ V CH ¼ ð6Þ p  pn þ c2 x
þ
y
þ z ¼0 ð14Þ
ðw=cÞ þ 0:32 Dt @x @y @z
4 Y. Wei et al. / Construction and Building Materials 244 (2020) 118298

!
1  nþ1  @pn @ 2 v nx @ 2 v nx @ 2 v nx 3.2. Freeze-thaw test
v x  v nx þ ¼ ur2 v nx ¼ u þ þ ð15Þ
Dt @x @x2 @y2 @z2
This study aims to investigate the permeability of concrete
! exposed to freeze-thaw cycles shortly after construction. More-
1  nþ1  @pn @ 2 v ny @ 2 v ny @ 2 v ny over, the high-altitude cold region is normally dry, and most of
v y  v ny þ ¼ ur2 v ny ¼ u þ þ ð16Þ the structures such as bridges and roads are not directly exposed
Dt @y @x2 @y2 @z2
to water. Therefore, an air freeze-thaw cycling condition was
adopted in this study. The temperature varied at a constant rate
!
1  nþ1  @pn @ 2 v nz @ 2 v nz @ 2 v nz between 20 and 20 °C, and each cycle was finished within
v  v nz þ ¼ ur2 v nz ¼ u þ þ ð17Þ 6 hrs. The freeze-thaw cycles were initiated on pastes at the age
Dt z @z @x2 @y2 @z2
of 1, and 7 days, simulating the early-age frozen condition. The
freeze-thaw cycling period last for 12 days for each specimen,
where, n is the time step, and the lattice spacing is considered as
and thus total 48 freeze-thaw cycles were applied to each sample.
one. The discretized forms in Eqs. (15)–(17) have 6 forms depending
After the freeze-thaw test was completed, the sample was sealed
on where the nearest solid voxels are located. The velocity compo-
cured in the temperature-controlled room until the age of 40 days.
nents at different locations will be determined when the following
A control sample which was not subject to freeze-thaw cycles and
condition will be met:
cured in a sealed condition in the tube was also tested for compar-

 ison. The curing scheme is shown in Fig. 1 for better illustration. All
1  nþ1 
max v i  v ni  < e ð18Þ the paste samples were tested at the age of 40 days for pore size
Dt characterization by using the techniques of MIP, BSE, and Micro-
CT for further permeability prediction.
where, e is a sufficiently small value.
To calculate the permeability, a finite difference scheme for the
3.3. MIP measurement
combined Navier-Stokes/Darcy flows is adopted on the basis of
microstructure reconstruction from CT images for cement paste.
The pore size distribution of the paste subject to freeze-thaw
The water permeability of cement paste is determined by simulat-
cycling at the age of 1 and 7 days and the paste under the sealed
ing a steady flow through a saturated sample under a hydrostatic
curing was measured by Mercury Intrusion Porosimetry (MIP).
pressure gradient, that is, upscaling the Navier–Stokes equation
The MIP technique was selected to measure the smaller pore size
to Darcy’s law (estimating the macroscale fluid flow). Once the
ranging from few nanometers to 1 lm which is difficult to be cap-
finite difference solution converges sufficiently, the permeability
tured by techniques such as BSE and the X-ray CT. The principle of
k can be calculated by volume averaging the local fluid velocity
MIP measurement is based on an assumption that the pore volume
(in the direction of the flow) and applying the Darcy equation:
equals to the intruded volume of mercury into a porous medium.
The intruded volume of mercury depends on the applied pressure.
k DP
hv i ¼  ð19Þ By assuming the pore geometry in the cementitious material to be
u L
cylindrical, the relationship between the pore diameter, d, and the
where, hv i is the average fluid velocity in the direction of the flow external applied pressure, P, known as Washburn equation [33]
for the porous paste, L is the length of the sample across which was established. The sample used for the MIP measurement was
there is an applied pressure difference of DP, and u is the fluid taken from the bulk sample and weighed about 2~3 g. The samples
viscosity. were pre-dried by heating at the temperature of 50 °C prior to the
MIP measurement.

3. Experimental methods 3.4. BSE imaging

3.1. Materials and samples
In this study, cement pastes with water-to-cement (w/c) ratio of
0.3 and 0.5 were investigated, which represent high and low
strength paste, denoted as 3P and 5P, respectively. The cement
used was ordinary Portland cement, the chemical composition
and the physical properties are listed in Table 1. After mixing,
the fresh paste was cast into a plastic tube with U = 10 mm for
BSE and MIP measurements and a tube with U = 5 mm for X-ray
CT scanning. Rotation was done by hand frequently after casting
to avoid excessive bleeding, particularly for paste with high w/c
ratio of 0.5. After setting, the plastic tubes filled with the hardening
paste were sealed and placed in a curing room with constant tem-
perature of 23 °C and the relative humidity of 50% until the age for
testing.
The pore size was also measured by using FEI QUANTA 200
scanning electron microscopy (SEM) with backscattered electron
(BSE) which aims for the large pore measurement. The sample size
is U10 mm  10 mm, which was cut from the bulk cylindrical
specimen. The sample was grinded and polished to obtain a flat
surface prior to the BSE observation. The images were obtained
at a high vacuum with an accelerating voltage of 15 kV, the work-
ing distance was 10~15 mm, and the field size was about
277 lm  208 lm.
3.5. X-ray CT
A Skyscan 1172 X-ray CT was used to scan the paste sample for
pore size distribution. The size of sample is U5 mm  10 mm. A
power setting of 100 kV and 50 lA was used for a full cone-

Table 1
Chemical composition and physical properties of cement.

Materials Mass fraction/% Specific gravity Specific surface area/(m2 kg1)

SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O K2O LOI
Cement 20.55 4.59 3.27 62.59 2.61 2.93 0.53 0.83 1.77 3.14 350
 Y. Wei et al. / Construction and Building Materials 244 (2020) 118298 5

Freeze-Thaw cycling Sealed curing sample, that includes both scanning and reconstructing time, was
about two hours.
Control
3.6. Permeability measurement

7d-FT Considering the difficulties of conducting water permeability on

1d-FT
0 10 20 30 40
Age (days)
Fig. 1. Duration of sealed curing and freeze-thaw cycling prior to the measurement
of pore size distribution and permeability at the age of 40 days.
beam scan with 1284 projection views for each sample. The reso-
lution is 2.97 lm. Each scan was made every 2.97 lm along the
height of the cylindrical sample. A 2D microstructure image can
be pictured per scan based on the X-ray absorption value that cor-
relates to the density of different phase, from which a 3D digital
image is reconstructed (Fig. 2). The cubic volume of interest
(VOI) of 3373 voxels was extracted from the middle of the cylindri-
cal sample, because there is abnormal increase in the grey level
close to the boundary of the sample due to the ray attenuation,
scattering and noise which can cause misinterpretation of the
scanned image [34]. Considering the characteristic length of
the individual phase in the hardened cement paste is about
106 m~105 m [35], the reconstructed cubic volume with size
of 1001  1001  1001 lm can represent the homogeneous
property of the sample tested. The image acquisition time for each
paste specimens, concrete specimens were selected for permeabil-
ity measurement, which have the same w/c ratio and the curing
regime as that of the paste samples for pore measurement. The vol-
ume fraction of aggregate in such concrete is 50%. Natural sand
was used as fine aggregate, and the limestone with maximum size
of 12.5 mm was used as coarse aggregate. The permeability of con-
crete can be evaluated by the conductivity of concrete saturated
with the concentrated slat solution by using the Nernst-Einstein-
Lu (NEL) method [36]. The NEL method is a rapid test which deter-
mines the electrical conductivity of the salt saturated concrete
[37]. If concrete is considered as a solid electrolyte, the diffusion
coefficient of the charged species (Di) in concrete is related to its
partial conductivity ri, and this relation is called the Nest-
Einstein equation,
RT ri
Di ¼ ð20Þ
Zi 2 F 2 C i
where, Di is the diffusion coefficient of species i (cm2/s); R is the gas
constant (8.314 J/mol.K); T is the absolute temperature (K); ri is the
partial conductivity of species i (S/cm); Zi is the charge of species i; F
is Faraday’s constant (96,500 Coul/mol); Ci is the concentration of
the species i (mol/cm3). Noted that,
ri ¼ ti r ð21Þ
where, r is the conductivity of concrete; ti is the transference num-
ber of species i.

Micro-CT Specimen

Scanned
length Slice
3.7mm

Diameter 5mm

Series of Slices
Extracted Cube
250

200

150

100

50
0

Fig. 2. X-ray CT scanning on paste sample and imaging processing.

6 Y. Wei et al. / Construction and Building Materials 244 (2020) 118298
Di can thus be calculated as:
RT rti
Di ¼ ð22Þ
Zi 2 F 2 C i
In NEL test, the concrete specimens are treated by vacuum salt
saturation, which means that t i  1:0 and Ci is the chloride concen-
tration in the pore solution used in vacuum salt saturation. At this
time, the diffusion coefficient Di can be calculated based on
Eq. (22).
The NEL test device is shown in Fig. 3. After the designed curing
period, the concrete specimens with a size of U100  50 mm were
treated by the vacuum salt saturation, as shown in Fig. 3a. Sodium
chloride solution with a concentration of 4 mol/L was used. There-
fore, Ci in Eq. (22) is equal to 4.0. After the vacuum salt saturation,
the specimen was placed between the two copper electrodes
(Fig. 3b). The electrodes were connected to a DC power supply of
5 V. The test last for 5 min, and the amount of charges passed
through the specimen was recorded. It should be noted that the
diffusivity of chloride is measured on concrete specimen with the
same w/c ratio as the paste specimen, the measured results should
be comparable to the computed permeability on paste specimen
since they have the same w/c ratio and the curing method.
4. Pore characteristics quantified from different techniques
4.1. Pore characteristics from MIP measurement
The pore size distribution measured at the age of 40 days by
MIP for the 3P and 5P pastes under the conditions of sealed curing
and the condition of subject to freeze-thaw freeze-thaw cycles at
the age of 1 and 7 days is shown in Table 2. It is clear that the
MIP measures pores with size greater than 3 nm and less than
1 lm, which includes both gel pore (<5nm) and capillary pore
(>5nm). Ref. [38] found through NMR measurement that the gel
pore is not affected by the freeze-thaw cycles, because of the very
low freezing point of the gel water. For 3P paste with low w/c
ratio = 0.3, the porosity of the sample froze at the age of 1 day
(porosity = 22%) is similar to that of the sample frozen at the age
of 7 days (porosity = 24%). And their porosities are slightly greater
than that of the control sample (22%). The above values suggest
that the low w/c ratio paste is not sensitive to the early-age
freeze-thaw cycling, and the porosity at later age is not affected
very much by the early-age frozen compared to the control sample
(Table 3).
On the contrary to 3P sample, the freeze-thaw cycles impose
greater damage to the high w/c ratio paste of 5P in terms of poros-
ity within the range of 3 nm~1 lm (Table 2). The porosity varies
Fig. 3. NEL test (a) vacuum salt saturation, and (d) measuring diffusion coefficient
of chloride in concrete.
significantly between the paste under the sealed curing condition
and the paste subject to freeze-thaw cycles at the age of 1 and
7 days. The porosity can reach 37% for 5P frozen at the age of
1 day compared to that of the control sample of 23%. The earlier
the age when frozen starts, the greater the porosity at later age.
By differentiating the intruded volume, the characteristics of
pore size distribution can be clearly seen in Fig. 4. For 3P mixture,
the pore size distributions of the frozen and the unfrozen samples
are similar, with one single peak within the pore size range of
30~40 nm. This indicates that frozen does not alter the pore size
distribution for low w/c ratio 3P paste. The pore size corresponding
to the peak of curves in the log differential intrusion volume vs.
equivalent pore diameter is known as the critical pore diameter
(Lc ), which relates to the pore diameter at the inflection point on
a cumulative volume versus pressure diagram measured from
the MIP test [9].
For high w/c ratio paste 5P, multiple peaks were found for both
pastes with and without frozen because of the greater pore size
distribution and porosity in such high w/c ratio = 0.5 paste. The
critical pore diameter (Lc ) corresponds to the highest peak in the
curve. As shown in Fig. 4d, the paste frozen at the age of 1 day
shows most significant large size pore with the Lc ranging between
600~800 nm. It is 90 nm for the paste frozen at the age of 7 days,
and 60 nm for the control sample.
4.2. Pore characteristics from BSE imaging
The MIP is not able to measure the volume of pores with size
greater than 1 lm. As a supplementary method, BSE image analysis
was frequently used to quantify the fraction of pores in the hard-
ened paste since Lange and Jennings [39]. The pore size distribu-
tion was quantified from the BSE image analysis (Fig. 5) based on
the principle of stereology which assumes that the volume fraction
in the 3D space can be represented by the area fraction on the 2D
image [39]. The pore fraction on the 2D image was identified and
calculated by using Image pro plus software. In the BSE measure-
ment, the detectable pore size depends on the preset resolution
and the field size of the BSE images. For the pixel size of 0.27 lm
 0.27 lm achieved in this study, the lower limit of the detectable
pore size is about 0.86 lm by using the Image pro plus software.
The pore size measured by BSE is just connected to the pore size
measured by MIP.
The pore size distribution quantified by the BSE image analysis
is shown in Table 2 for the control pastes and the pastes subject to
early-age freeze-thaw cycles. It is seen that the pore size ranging
between 1~30 lm is measured by the BSE technique. The size of
the majority pores captured by BSE ranges between 1~20 lm. Sim-
ilar to the MIP results, the pore size of paste with w/c ratio = 0.3
(3P) sample is not affected too much by the early-age freeze-
thaw cycles, the samples subject to the early-age freeze-thaw
cycles show slightly greater porosity than the control sample.
However, the 5P sample shows greater porosity within pore size
range of 1~20 lm after subject to the early-age freeze-thaw cycles
compared to the control sample.
4.3. Pore characteristics from X-ray CT scanning
X-ray CT scanning is a nondestructive technique to obtain the
microstructure information of the cementitious materials com-
pared to the MIP and the BSE techniques, because the delicate dry-
ing or grinding and polishing processes are not required for
preparing sample for X-ray CT scanning, the original microstruc-
ture of the sample can be preserved without disturbance.
However, it is critical to separate the pore phase from the solid
phases in the X-ray CT scanned images for quantifying the pore
space. Segmentation or image thresholding is to convert the
 Y. Wei et al. / Construction and Building Materials 244 (2020) 118298 7

Table 2
Range of pore size, porosity (/), the critical pore size (Lc ), the pore size at which the electrical conductivity reaches maximum (Lmax), and the fraction (SðLmax Þ) of connected pores
with size  Lmax, measured by the three techniques (MIP, BSE, and X-ray CT) for 3P (w/c = 0.3) and 5P (w/c = 0.5) pastes under the conditions of sealed curing and subject to freeze-
thaw (FT) cycles at the age of 1 (1d-FT) and 7 (7d-FT) days.

Technique Range of pore size 3P-1d-FT 3P-7d-FT 3P-control

/ Lc Lmax SðLmax Þ / Lc Lmax SðLmax Þ / Lc Lmax SðLmax Þ
MIP 3 nm~1 lm 22% 40.30 nm 32.40 nm 0.64 24% 40.30 nm 32.40 nm 0.74 22% 45.30 nm 36.35 nm 0.74
BSE 1 lm~30 lm 24% 2.00 lm 1.60 lm 0.51 21% 2.15 lm 1.65 lm 0.47 20% 2.15 lm 1.65 lm 0.47
X-ray CT >10 lm 10% 16.50 lm 13.00 lm 0.19 9% 16.50 lm 13.00 lm 0.21 9% 16.50 lm 13.00 lm 0.21
Technique Range of pore size 5P-1d-FT 5P-7d-FT 5P-control
/ Lc Lmax SðLmax Þ / Lc Lmax SðLmax Þ / Lc Lmax SðLmax Þ
MIP 3 nm~1 lm 37% 678.75 nm 554.70 nm 0.85 31% 62.50 nm 50.35 nm 0.83 23% 40.30 nm 32.40 nm 0.83
BSE 1 lm~30 lm 41% 2.00 lm 1.60 lm 0.57 33% 2.35 lm 1.85 lm 0.51 27% 2.15um 1.65 lm 0.44
X-ray CT >10 lm 34% 26.00 lm 19.50 lm 0.47 27% 26.00 lm 19.50 lm 0.47 18% 16.00um 12.50 lm 0.16

Table 3
Calculated intrinsic permeability (m2) by different computing methods based on the pore characteristics measured by different techniques.

Mixture Computing method Pore measuring technique

MIP BSE X-ray CT
3P-1d K-T equation 1.33E18 2.80E15 2.64E14
GEM method 4.24E19 1.57E15 –
Navier-Stokes – – 1.96E16
3P-7d K-T equation 1.69E18 2.27E15 2.75E14
GEM method 6.36E19 9.05E16 –
Navier-Stokes – – 4.76E16
3P-control K-T equation 1.94E18 2.20E15 2.80E14
GEM method 5.36E19 9.05E16 –
Navier-Stokes – – 1.98E16
5P-1d K-T equation 8.85E16 5.36E15 5.00E13
GEM method 5.72E16 6.01E15 –
Navier-Stokes – – 1.17E13
5P-7d K-T equation 5.93E16 5.07E15 4.08E13
GEM method 3.32E18 2.72E15 –
Navier-Stokes – – 1.25E13
5P-control K-T equation 1.82E18 2.84E15 4.06E14
GEM method 5.30E19 5.41E15 –
Navier-Stokes – – 6.27E15

(a) 0.4 3P-1d-FT (b) 0.4 5P-1d-FT

3P-7d-FT 5P-7d-FT
0.3 3P-control 0.3 5P-control
Porosity
Porosity

0.2 0.2

0.1 0.1

0 0
100 101 102 103 100 101 102 103

(c) 0.3 (d) 0.3

dV/dlogD (mL/g)

dV/dlogD (mL/g)

Lc range： Lc(5P-7d-FT): 90nm

0.2 30 ~ 40nm 0.2
Lc(5P-1d-FT):
Lc(5P-control):60nm
800nm
0.1 0.1

0 0
100 101 102 103 100 101 102 103
Pore diameter (nm) Pore diameter (nm)

Fig. 4. Measured pore size distribution by MIP and determination of critical pore size (Lc) in 3P and 5P pastes at the age of 40 days after sealed curing and subject to freeze-
thaw cycles at the age of 1 and 7 days.
8 Y. Wei et al. / Construction and Building Materials 244 (2020) 118298

(a) (b) (c)

50μm 50μm 50μm

(d) (e) 2.5 Pore C-S-H Clinker

2.0

Number (×10^3)
1.5
1.0
0.5

50μm 0
0 50 100 150 200 250
Greyscale

Fig. 5. (a) BSE image; (b) binary image after segmentation of pore; (c) binary image after segmentation of CSH; (d) binary image after segmentation of clinker; (e) distribution
of greyscale of pore, CSH, and clinker phases of 5P paste.

greyscale-based CT image to a binary image by identifying the pore
and the solid matrix based on their voxel intensity values. The
porosity is calculated through dividing the number of pore voxels
by the total number of voxels in the volume of interest.
The first step of obtaining the porosity is to determine the grey-
scale thresholds of the pore and the clinker phases. As illustrated in
Fig. 6a, typical pore phase and the clinker phase are selected from
the original X-ray CT scanned image, a line was drawn across the
pore (with green line) and the clinker (with red line) phase, respec-
tively. And then the greyscale along the line was plotted as a grey-
scale histogram shown in Fig. 6b. There is an obvious valley with
lower greyscale value located in the middle of the histogram curve
of the line drawn across the pore phase. The values in the valley
represent the greyscale of the pore phase. The greyscale of the
upper bound of the valley is taken as the upper threshold of the
pore phase. And any greyscale less than this threshold is taken as
pore phase. In this study, the threshold of greyscale value for pore
phase is 30 as illustrated in Fig. 6b. Similarly, the threshold of the
clinker is determined as a greyscale value above which represents
the clinker phase. In this study, the greyscale threshold of the clin-
ker is determined as 80 as illustrated in Fig. 6b. These threshold
values were determined based on over 30 locations for each phase,
which intends to represent the average greyscale of each phase.
Thresholds were then used to convert the greyscale images to
the binary black and white images as shown in Fig. 6c, which is
used to determine the pore size distribution.
The quantified pore size distribution from the scanned 2D
images by using X-ray CT for different paste samples is shown in
Table 2. It is seen that the size of the majority pores ranges
between 20~60 lm. It should be noted that the lower limit of
the detectable pore size by the X-ray CT used in this study is
2.97 lm. Therefore, there is overlapping of pore size measured
by BSE and X-ray CT.
Compared to the pore size distribution quantified from the BSE
image analysis, the pore size distribution based on the X-ray CT
scanning is greater, which can reveal the distribution of pores with
size greater than 30 lm. From Fig. 7, the best range of pore size
that BSE can capture might be below 20 lm, whereas, X-ray CT
can capture pore with size below 200 lm (Fig. 7). For high w/c ratio
paste subject to freeze-thaw cycles at early-age, X-ray CT is recom-
mended for pore size quantification due to its capability of captur-
ing large pores.
It should be mentioned that the pore size distribution quanti-
fied from the X-ray CT scanning is based on the analysis of the
2D images rather than the reconstructed 3D microstructure of
the paste. This is because that the commercial software (such as
Mimics) quantifies the characteristics of pores from the recon-
structed 3D microstructure in which the pores are assumed to be

140

120
clinker
114μm
100
Greyscale

80 80

60 hydration
product
225μm 40
30
20
pore
0
0 40 80 120 160 200 240
Distance (μm ) (c) Segmented image where black represents
pore, grey represents hydration product, and
(a) Original image scanned from CT
white represents clinker
(b) Determination of threshold greyscale of each phase

Fig. 6. Determination of greyscale threshold of each phase and the image segmentation of X-ray CT scanned image.
 Y. Wei et al. / Construction and Building Materials 244 (2020) 118298
Six columns within one tick represent 3P-1d, 3P-7d, 3P, 5P-1d, 5P-7d, 5P from left to right,
25% measured by MIP, BSE and
<0.86μm
Captured by MIP
20%
15%
Porosity
10%
5%
0%
Fig. 7. Comparison of pore size distribution measured by MIP, BSE, and X-ray CT for 3P and 5P pastes under sealed curing and subject to freeze-thaw cycles at the age of 1 and
7 days.
spheres filling the pore space, which normally leads to an unreal-
istic pore size distribution compared to the real pore size distribu-
tion. The pore size distribution quantified directly from the Mimics
software gives significantly higher content of smaller pores.
5. Computing permeability from measured pore characteristics
5.1. Determination of Lc and Lmax
For analytical calculation of intrinsic permeability by using
either Katz-Thompson method or GEM method, the parameters,
such as porosity (/), the critical pore diameter (Lc ), and the pore
diameter (Lmax) which produces the maximum conductance of
concrete are necessary to be determined first. By differentiating
the intruded volume, Lc can be clearly seen in Fig. 4. The pore diam-
eter producing the maximum conductance of concrete (Lmax) was
determined from the mercury injection curve as the diameter cor-
responding to the peak of the pore volume times square pore diam-
eter vs. the pore diameter curve, as shown in Fig. 8 for the data
obtained from the MIP, BSE, and the X-ray CT scanning. The calcu-
lated Lmax for the 3O and 5O pastes subject to the sealed curing and
the early-age freeze-thaw cycles are summarized in Table 2. It is
seen that the significant difference exists between Lmax quantified
from the three pore measuring techniques for the same mixture. In
general, Lmax is in nm obtained from the MIP measurement, it is in
lm from both the BSE and the X-ray CT measurements. The signif-
icant difference is due to the resolution of different techniques
used in measuring the pore characteristics other than the differ-
ence of microstructure itself. From Table 2, Lmax = 0.34 lm for a
very broad pore size distribution in rocks [6] is not held in cemen-
titious materials.
9
X-ray CT.
0.86μm~3μm 3μm~12μm >12μm
Captured Captured Captured
by MIP and by CT and by CT
BSE BSE
Minimum detectable pore diameter
Minimum detectable pore diameter
in BSE image (0.86μm)
in CT image (3μm)
Pore diameter
5.2. Calculated permeability based on Katz-Thompson equation
Utilizing Katz-Thompson equation to calculate the intrinsic per-
meability of paste requires the pore parameters which can be
quantified from MIP measurement, BSE image analysis, and the
X-ray CT scanned image. The measured pore parameters are sum-
marized in Table 2 for different pastes and curing methods. The
calculated intrinsic permeability by using Katz-Thompson equa-
tion is plotted in Fig. 9.
Due to the significant difference of the pore parameters mea-
sured by using the three techniques, the predicted permeability
shows difference in magnitude, as shown in Fig. 9. The predicted
permeability ranges 1018~1016 m2 based on the MIP measure-
ment, it is about 1015 m2 based on the BSE measurement, and
1014~1013 m2 based on the X-ray CT measurement. The MIP-
based permeability is about three to five orders of magnitude
lower than that computed from the X-ray CT-based permeability.
This is not surprising considering the much smaller pore size
accessed by the MIP compared to the BSE and the X-ray CT scan-
ning. The magnitude of the computed permeability corresponds
well with the pore size accessed by different techniques.
The effect of w/c ratio and the early-age freeze-thaw cycles on
the permeability is revealed very well by the predicted permeabil-
ity from the MIP measurement. Whereas, the predicted permeabil-
ity based on the pore parameters obtained from the BSE and the X-
ray CT techniques does not show the effects of the w/c ratio and the
early-age freeze-thaw cycles that the pastes were subjected to.
This might suggest that the pore parameters obtained from the
MIP measurement is more applicable than the BSE and the X-ray
CT measurement, when Katz-Thompson equation is used for the
permeability prediction. The Katz-Thompson equation performs
well for pore size below 1 lm.
10 Y. Wei et al. / Construction and Building Materials 244 (2020) 118298

6.E+02
4.E+10
4.E+02 Lmax(MIP)=32nm

2.E+02

3.E+10
0.E+00
0 20 40 60
Porosity x Diameter3

5.E+07
2.E+10
4.E+07
3.E+07
2.E+07
1.E+07
1.E+10 0.E+00
0 1000 2000 3000

Lmax(CT)=13000nm
Lmax(BSE)=1600nm
0.E+00
0 2000 4000 6000 8000 10000 12000 14000 16000 18000
Pore diameter (nm)

Fig. 8. Determination of Lmax based on pore size distribution measured from MIP, BSE, and X-ray CT.

1.E-11 1.E-11
MIP-KT
1.E-12 MIP BSE CT 1.E-12
MIP-GEM
Intrinsic permebility (m2)

1.E-13 BSE-KT
Intrinsic permebility (m2)

1.E-13
BSE-GEM
1.E-14
1.E-14
1.E-15
1.E-15
1.E-16
1.E-16
1.E-17

1.E-17 1.E-18

1.E-18 1.E-19
3P-1d 3P-7d 3P 5P-1d 5P-7d 5P 3P-1d 3P-7d 3P 5P-1d 5P-7d 5P

Fig. 9. Comparison of calculated intrinsic permeability by using Katz-Thompson Fig. 10. Comparison of calculated intrinsic permeability by using Katz-Thompson
equation from measured pore size distribution by MIP, BSE, and X-ray CT (KT) equation and GEM method from measured pore parameters by MIP and BSE
techniques. techniques.

Katz-Thompson equation for the low w/c ratio pastes of 3O, this
5.3. Calculated permeability based on GEM method paste is less porous than other pastes, and the predicted perme-
ability by GEM method is expected to be closer to the real perme-
The calculated intrinsic permeability based on the GEM method ability. Again, the MIP measurement on the pore characteristics is
as well as the Katz-Thompson equation was also plotted in Fig. 10. more suitable for permeability prediction by using Katz-Thompson
Pore parameters from the MIP and BSE measurements were used and GEM methods, as the effects of both w/c ratio and the early-age
as inputs. It is apparent that the computed permeability by the freeze-thaw cycles are revealed by the computed permeability.
GEM method shows similar trend to the permeability computed
by the Katz-Thompson equation for the same pore measuring
technique. 5.4. Computed permeability based on Navier-Stokes method
In general, based on the same pore measuring technique, the
computed permeability from the GEM method is less than that Navier-Stokes is a numerical method which computes perme-
from the Katz-Thompson method. The reason might contribute to ability based on the digitalized microstructure information from
that the GEM method applies well for less porous media such as the X-ray CT scanned image. Therefore, the homogeneity of the
the cementitious materials with both gel pore and capillary pore computing volume is important to ensure that a representative
network dominating transport, whereas the Katz-Thompson equa- permeability is computed. To evaluate the effect of the heteroge-
tion applies to more porous media with capillary pore network neous nature of the cementitious materials on the predicted per-
dominating transport. This can be clearly seen from the greater dif- meability, five blocks at the locations of the center, the left, the
ference between the permeability computed from the GEM and the right, the up, and the down of the microstructure reconstructed
 Y. Wei et al. / Construction and Building Materials 244 (2020) 118298
from the X-ray CT scanned images were selected for permeability
prediction based on the Navier-Stokes method. As shown in
Fig. 11a, each block contains 300 voxels. The average computed
permeability at the five locations and their standard variance are
plotted in Fig. 11b for pastes of 5P-7d, 3P-1d, and 3P-7d. It is seen
that the average permeability of the five blocks can represent the
permeability of each sample, the COV ranges between 10~20%.
The permeability calculated at the center of the sample based on
the Navier-Stokes method is used to compare with permeability
calculated based on other methods.
The calculated permeability based on X-ray CT results by using
the Katz-Thompson equation and the Navier-Stokes method is
shown in Fig. 12 for the control 3P and 5P pastes and the pastes
subject to freeze-thaw cycles at the age of 1 and 7 days. The input
pore parameters for both Katz-Thompson and Navier-Stokes meth-
ods were obtained from the X-ray CT scanned images.
It is seen that the magnitude of the calculated intrinsic perme-
ability by Katz-Thompson equation is about 1~2 orders of magni-
tude greater than that computed from the Navier-Stokes method,
though the same set of pore parameters from X-ray CT measure-
ment was used. The magnitude of the calculated permeability by
the Katz-Thompson equation is 1014~1013 m2, whereas, it is
1016~1013 m2 by Navier-Stokes method. Similar trend was
found by [19] that the Navier-Stokes method computed smaller
permeability compared to the Katz-Thompson method, they calcu-
lated the intrinsic permeability of 5  1014 m2 and 5. 2  1016 m2
by using Katz-Thompson equation and the Navier-Stokes method,
respectively, for the fly ash-based geopolymer with porosity of
32%. In addition, the calculated intrinsic permeability by Navier-
Stokes method in this study is consistent with the reported in
the literature [19,40]. Ref. [40] calculated the intrinsic permeability
based on the 3D microstructure model reconstructed from the CT
scanned images was 1015~1013 m2 for pastes with porosity of
20~30%.
The computed permeability by Navier-Stokes method well
reflects the effects of the freeze-thaw cycles and the w/c ratio on
the specimen permeability. Based on the Navier-Stokes method,
a clear increase in permeability was observed for the high w/c ratio
paste of 5P, the increase of w/c ratio from 0.3 to 0.5 will increase
the permeability by 2~3 orders of magnitude. The early-age
freeze-thaw cycles increase the permeability by 2 orders of magni-
tude compared to the control sample. However, the computed per-
meability by Katz-Thompson method does not reflect the effect of
freeze-thaw cycles, and the permeability of control paste and the
paste subject to early-age freeze-thaw cycles is almost the same.
Therefore, it is reasonable to conclude that the Navier-Stokes
method is more applicable to predict permeability of cement paste
compared to the Katz-Thompson equation when pore parameters
obtained from X-ray CT measurement are used.
The calculated intrinsic permeability from MIP results based on
the Katz-Thompson method was two orders of less than that from
(a)
Micro-CT Specimen Calculation element
up
left right
down
center
Fig. 11. Sensitivity analysis of calculated permeability by Navier-Stokes method to the locations of selected voxels for calculation.
11
1.E-12
Intrinsic permeability (m2)
Katz-Thompson
1.E-13 Navier-Stokes
1.E-14
1.E-15
1.E-16
3P-1d 3P-7d 3P 5P-1d 5P-7d 5P
Fig. 12. Calculated intrinsic permeability by Katz-Thompson and Navier-Stokes
methods based on X-ray CT data for control 3P and 5P pastes and pastes subject to
freeze-thaw cycling at the age of 1 and 7 days.
the the X-ray CT results based on the Navier-Stokes method,
because the pores with smaller size were measured in the MIP
measurement. This agrees with the findings by [18], they mea-
sured the pore size distribution by using the X-ray CT and the
MIP methods for the same materials, and calculated the intrinsic
permeability by using Navier-Stokes and Katz-Thompson method,
respectively. They found that the magnitude of the calculated per-
meability by the X-ray CT results was 1014 m2, and it was
1016 m2 calculated from the MIP results [18]. Ref. [19] calculated
the permeability by using Navier-Stokes and Katz-Thompson
method from the X-ray CT and the MIP result, respectively. The
permeability is 5  1014 m2 based on the X-ray CT measured pore
data, and it was 5.2  1016 m2 based on the MIP measured pore
data. Ref. [19] thought that the permeability calculation based on
the X-ray CT measured pores is more accurate.
6. Discussion
6.1. Effect of early-age freeze-thaw cycles on pore characteristics and
permeability
Early-age freeze-thaw cycles affect pore characteristics of hard-
ened paste, including porosity, pore size distribution, and the crit-
ical pore diameter. The influence magnitude depends on the w/c
ratio of samples as well as the age when paste was subject to
freeze-thaw cycles. The significant effect occurs in high w/c
ratio = 0.5 paste compared to the w/c ratio = 0.3 paste, and the ear-
lier the application of the freeze-thaw cycles, the greater the dam-
age will be caused in terms of the porosity and the content of the
large-size pores.
Within all the three pore size ranges measured by using MIP,
BSE, and X-ray CT techniques, the porosity of 5P paste is signifi-
(b) (
3HUPHDELOLW\ P 
(
(
(
(
3G 3G 3G
12 Y. Wei et al. / Construction and Building Materials 244 (2020) 118298
cantly increased if freeze-thaw cycles were applied at the age of 1
and 7 days compared to the control sample. The critical pore diam-
eter is also increased when subject to early-age freeze-thaw cycles,
indicating that the pore size become greater in addition to the
increased porosity, and the early-age freeze-thaw cycles coarsen
the pore size. The pore with size greater than 1 lm is significantly
increased when subject to early-age freeze-thaw cycles. The earlier
the freeze-thaw cycles, the greater the porosity in paste with high
w/c ratio.
Since the pore parameters are slightly affected by the freeze-
thaw action on 3P paste, the calculated permeability by using
Katz-Thompson method (Eq. (3)) or the GEM method (Eq. (4))
tends to change very little under different freeze-thaw conditions.
Thus, low-diffusivity is reasonable for 3P paste and the expected
results from the NEL test are also obtained. Unlike the 3P sample,
the permeability of 5P paste increases obviously when subjected
to freeze-thaw cycles at early ages due to the greater volume,
radius, and size distribution of pores.
Therefore, freeze-thaw cycles at early ages damages the
microstructure of high w/c ratio paste such that the further hydra-
tion after freeze-thaw cycles cannot recover completely the pore
structure by continuous hydration and the filling of the pores by
hydration products. It is recommended that a protection process
must be applied for concrete with high w/c ratio to minimize the
effect from freeze-thaw cycles at early ages. Low w/c ratio concrete
is highly recommended to minimize the freeze-thaw effect on
porosity and the related strength and permeability issues.
6.2. Comparison of permeability between this study and from
literatures
The diffusivity of chloride in concrete with the same w/c ratio as
the pastes was measured in this study according to the NEL
method. The measured diffusivity coefficient of chloride in con-
crete is shown in Fig. 13 for 3C and 5C concretes subject to
freeze-thaw cycles at the age of 1d and 7d as well as under the
sealed cured conditions. It is seen that the diffusivity coefficient
of chloride in concrete is in the magnitude of 108 cm2/s. High
w/c ratio = 0.5 concrete (5C) shows much greater diffusivity than
that of the low w/c ratio = 0.3 concrete (3C). The diffusivity of all
5C concrete is in the range of medium or high category according
to CCES 01 [41]. Earlier exposure to the freeze-thaw cycles renders
concrete to a significantly higher diffusivity. The low w/c ratio con-
crete (3C) shows low diffusivity, suggesting the good permeability
resistance even under the condition of subject to early-age freeze-
thaw cycles.
7
3O 5O
10-8cm2/s)
6 high
5 The purpose of this study is to provide the insight into the fea-
Diffusivity coefficient (
4 the predicting methods for permeability, particularly for cementi-
medium
3 intrinsic permeability of cement paste is calculated by using
2 and Navier-Stokes method based on the pore parameters measured
1
low
0
1d 7d control
Fig. 13. Measured diffusion coefficient of chloride in concrete by NEL method.
For the convenience of comparison, the intrinsic permeability (k
in m2) of pastes computed from either Katz-Thompson equation or
the Navier-Stokes method is converted to permeability in units of
linear flow (k’ in m/s) by:
  qg
0
k ðm=sÞ ¼ k m2 ð23Þ
g
where, q is density of the fluid, g is acceleration of gravity, g is vis-
cosity of fluid. For chloride solution, the conversion term qg=g = 9.
79  106/(ms), the viscosity of sodium chloride solution is assumed
to equal to that of water. If the fluid is water, the intrinsic perme-
ability can be converted into saturated water permeability by the
above conversion coefficient.
The computed permeability (k’ in m/s) is then compared to the
measured diffusivity coefficient of chloride (in m2/s) for specimens
of 3C-1d, 3C-7d, 3C, 5C-1d, 5C-7d, and 5C, as shown in Fig. 14. It is
seen that there is no systematic relationship between the com-
puted permeability of paste and the measured diffusivity of con-
crete. For the same diffusivity of chloride, the computed
permeability depends much on the techniques used for measuring
the pore characteristics and the method for computing permeabil-
ity. The computed permeability (k’ in m/s) of paste with w/c ratio of
0.3 and 0.5 is in the magnitude of 109~106 (m/s).
By reviewing the calculated and the measured permeability in
the literature, discrepancies exist due to the different testing and
computing methods used. Banthia and Mindess [42] measured
the permeability of w/c = 0.35 pastes of 1  1010 and
8  1013 m/s after 7 and 28 days of hydration, respectively. As
measured by [43], the permeability of paste with degree of hydra-
tion greater than 0.5 is less than 1014 m/s. Ref. [7] compared the
permeability of neat pastes with w/c ratio between 0.23 and 1.0 to
the calculated by using Katz-Thompson equation based on the MIP
data, they found that the calculated results tracked well with the
experimental data as a function of time, with the experimental
value slightly higher at most time, and the difference between
the experimental and the calculated permeabilities is within 1.5
order of magnitude, the largest differences occurred at late time
for the samples with low w/c ratio. Ref. [44] found that the perme-
ability predicted from Katz-Thompson equation was two orders of
magnitude lower than the experimentally measured for concrete
with w/c ratio of 0.65 and 0.55. Ref. [4] measured permeability of
concrete subject to freeze-thaw of about 600 cycles, and found that
OPC concrete without air-entrainment showed almost constant
permeability for w/c ratio up to 0.55, an increase of w/c ratio from
0.55 to 0.65 will drastically increase the chloride permeability.
Therefore, the computed permeability is suitable for comparing
and selecting mixture under the conditions of using the same tech-
nique on pore measurement and the same calculating method on
permeability.
7. Conclusions
sibility of different measuring techniques for pore parameters and
tious materials subject to freeze-thaw cycles. To this end, the
Katz-Thompson method, general effective media (GEM) method,
from MIP, BSE, and X-ray CT scanning techniques. The major find-
ings are:
The freeze-thaw cycles at early ages damages the microstruc-
ture of high w/c ratio paste such that the further hydration after
freeze-thaw cycles cannot recover completely the pore structure
through filling of the pores by the hydration products. It is recom-
 Y. Wei et al. / Construction and Building Materials 244 (2020) 118298 13

Calculated permeability of paste by Eq.23 (m/s)

Calculated permeability of paste by Eq.23 (m/s)

1.E-08 MIP pore measurement 6.E-08 BSE pore measurement
K-T equation prediction K-T equation prediction
5.E-08
8.E-09

4.E-08
6.E-09
3.E-08
4.E-09
2.E-08

2.E-09
1.E-08

0.E+00 0.E+00
0.E+00 2.E-14 4.E-14 6.E-14 8.E-14 0.E+00 2.E-14 4.E-14 6.E-14 8.E-14
Measured chloride diffusivity of concrete (m2/s) Measured chloride diffusivity of concrete (m2/s)
Calculated permeability of paste by Eq.23 (m/s)

Calculated permeability of paste by Eq.23 (m/s)

6.E-06 X-ray CT pore measurement 1.5E-06 X-ray CT pore measurement
K-T equation prediction N-S equation prediction
5.E-06
1.2E-06

4.E-06
9.0E-07
3.E-06

6.0E-07
2.E-06

3.0E-07
1.E-06

0.E+00 0.0E+00
0.E+00 2.E-14 4.E-14 6.E-14 8.E-14 0.E+00 2.E-14 4.E-14 6.E-14 8.E-14
Measured chloride diffusivity of concrete (m2/s) Measured chloride diffusivity of concrete (m2/s)

Fig. 14. Qualitative comparison of the measured chloride diffusivity of concrete and the calculated permeability of pastes by different pore measuring techniques and
computing methods.

mended that a protection measure must be taken for concrete with disturbance, particularly for concrete subject to freeze-thaw dam-
high w/c ratio upon the potential of subject to freeze-thaw cycles at age. The Navier-Stokes method is more applicable to predict per-
early ages. Low w/c ratio concrete is highly recommended to min- meability of cement paste compared to the Katz-Thompson
imize the freeze-thaw effect on porosity and the related durability equation, when pore parameters obtained from X-ray CT measure-
issues, because low w/c ratio paste is not sensitive to the early-age ment are used. The computed permeability by Navier-Stokes
freeze-thaw cycling, and the porosity at later age is not affected method well reflects the effects of the freeze-thaw cycles and the
very much by the early-age frozen compared to the control sample. w/c ratio on the specimen permeability.
The pore parameters obtained from the MIP measurement is However, it should be aware that the computed permeability of
more applicable than that obtained from the BSE and the X-ray cementitious materials is suitable for comparing and selecting
CT measurement, when Katz-Thompson equation is used for the mixture under the conditions of using the same technique for pore
permeability prediction. The effect of w/c ratio and the early-age measurement and the same calculating method for permeability
freeze-thaw cycles on the permeability is revealed very well by prediction.
the predicted permeability based on the MIP measurement. The
Katz-Thompson equation performs well for pore size below 1 lm.
The GEM method is a more suitable tool for cementitious mate- CRediT authorship contribution statement
rials with low porosity. Generally, the computed intrinsic perme-
ability by the GEM method shows a similar trend to that by the Ya Wei: Funding acquisition Supervision Writing - original draft
Katz-Thompson equation for the same pore measuring technique, Methodology Conceptualization. Weiqiang Guo: Writing - review
such as the MIP and BSE measurements. Nevertheless, for the & editing. Zehong Wu: Methodology. Xiang Gao: Methodology.
low w/c ratio pastes of 3O, which is less porous than other paste,
the predicted intrinsic permeability by GEM method is expected Declaration of Competing Interest
to be closer to the real permeability.
X-ray CT scanning is a promising technique to detect the pore The authors declare that they have no known competing finan-
characteristics of cementitious materials nondestructively, the cial interests or personal relationships that could have appeared
original microstructure of the sample can be preserved without to influence the work reported in this paper.
14 Y. Wei et al. / Construction and Building Materials 244 (2020) 118298
Acknowledgements
The authors wish to thank the supports from National Natural
Science Foundation of China under Grant No. 51778331.
References
[1] P.K. Mehta, P.J.M. Monteriro, Concrete structures, properties and materials,
McGraw-Hill, New York, 2006.
[2] Y. Wei, W.Q. Guo, Q.Q. Zhang, A model for predicting evaporation from fresh
concrete surface during the plastic stage, Dry. Technol. (2019), doi: 10.1080/
07373937.2019.1691012.
[3] Z.H. Wu, Y. Wei, M. Yang, X.F. Yao, Application of X-ray micro-CT for
quantifying degree of hydration of slag-blended cement paste, J. Mater. Civ.
Eng. 32 (3) (2020) 04020008.
[4] M. Saito, M. Ohta, H. Ishimori, Chloride permeability of concrete subjected to
freeze-thaw damage, Cem. Concr. Compos. 16 (4) (1994) 233–239.
[5] P. Soroushian, M. Elzafraney, Damage effects on concrete performance and
microstructure, Cem. Concr. Compos. 26 (7) (2004) 853–859.
[6] A.J. Katz, A.H. Thompson, Prediction of rock electrical conductivity from
mercury injection measurements, J. Geophys. Res.-Solid Earth. 92 (B1) (1987)
599–607.
[7] B.J. Christensen, T.O. Mason, H.M. Jennings, Comparison of measured and
calculated permeabilities for hardened cement pastes, Cem. Concr. Res. 26 (9)
(1996) 1325–1334.
[8] P. Halamickova, R.J. Detwiler, D.P. Bentz, E.J. Garboczi, Water permeability and
chloride ion diffusion in Portland cement mortars: relationship to sand content
and critical pore diameter, Cem. Concr. Res. 25 (4) (1995) 790–802.
[9] L. Cui, J.H. Cahyadi, Permeability and pore structure of OPC paste, Cem. Concr.
Res. 31 (2) (2001) 277–282.
[10] Y. Ma, J. Hu, G. Ye, The pore structure and permeability of alkali activated fly
ash, Fuel. 104 (2013) 771–780.
[11] B.H. Oh, S.Y. Jang, Prediction of diffusivity of concrete based on simple analytic
equations, Cem. Concr. Res. 34 (3) (2004) 463–480.
[12] D.S. McLachlan, M. Blaszkiewicz, R.E. Newnham, Electrical resistivity of
composites, J. Am. Ceram. Soc. 73 (8) (1990) 2187–2203.
[13] J. Zhang, Z. Li, Application of GEM equation in microstructure characterization
of cement-based materials, J. Mater. Civ. Eng. 21 (11) (2009) 648–656.
[14] Z. Liu, Y. Zhang, L. Liu, Q. Jiang, An analytical model for determining the
relative electrical resistivity of cement paste and C-S–H gel, Constr. Build.
Mater. 48 (2013) 647–655.
[15] M.D. Wimalasiri, D.J. Robert, C.Q. Li, New method to investigate the
permeability of stressed concrete, in: Mechanics of Structures and Materials
XXIV: Proceedings of the 24th Australian Conference on the Mechanics of
Structures and Materials (ACMSM24), Perth, Australia, 6–9 December 2016,
CRC Press, (2016) 317.
[16] D.P. Bentz, S. Mizell, S. Satterfield, J. Devaney, W. George, P. Ketcham, H. Sallee,
The visible cement data set, J. Res. Natl. Inst. Stand. Technol. 107 (2) (2002)
137–148.
[17] D.P. Bentz, N.S. Martys, A stokes permeability solver for three-dimensional
porous media, US Department of Commerce, Technology Administration,
National Institute of Standards and Technology, 2007.
[18] X. Sun, Q. Dai, K. Ng, Computational investigation of pore permeability and
connectivity from transmission X-ray microscope images of a cement paste
specimen, Constr. Build. Mater. 68 (2014) 240–251.
[19] S. Das, P. Yang, S. Singh, J.C. Mertens, X. Xiao, N. Chawla, N. Neithalath,
Effective properties of a fly ash geopolymer: Synergistic application of X-ray
synchrotron tomography, nanoindentation, and homogenization models, Cem.
Concr. Res. 78 (2015) 252–262.
[20] S. Chung, T. Han, S. Kim, Reconstruction and evaluation of the air permeability
of a cement paste specimen with a void distribution gradient using CT images
and numerical methods, Constr. Build. Mater. 87 (2015) 45–53.
[21] M. Promentilla, S. Cortez, R. Papel, B. Tablada, T. Sugiyama, Evaluation of
microstructure and transport properties of deteriorated cementitious
materials from their X-ray computed tomography (CT) images, Materials 9
(5) (2016) 388.
[22] M. Zhang, Pore-scale modelling of relative permeability of cementitious
materials using X-ray computed microtomography images, Cem. Concr. Res.
95 (2017) 18–29.
[23] R. Pieralisi, S.H.P. Cavalaro, A. Aguado, Advanced numerical assessment of the
permeability of pervious concrete, Cem. Concr. Res. 102 (2017) 149–160.
[24] Y. Wei, Z. Wu, X. Yao, X. Gao, Quantifying effect of later curing on pores of
paste subject to early-age freeze-thaw cycles by different techniques, J. Mater.
Civ. Eng. 31 (8) (2019) 04019153.
[25] E. Garboczi, Permeability, diffusivity and microstructural parameters: a critical
review, Cem. Concr. Res. 20 (4) (1990) 59–601.
[26] A. Ei-Dieb, R. Hooton, Evaluation of the Kata-Thompson model for estimating
the water permeability of cement-based materials from mercury intrusion
porosimetry data, Cem. Concr. Res. 24 (3) (1994) 443–455.
[27] D.S. McLachlan, An equation for the conductivity of binary mixtures with
anisotropic grain structures, J. Phys. C: Solid State Phys 20 (7) (1987) 865–877.
[28] D.S. McLachlan, Measurement and analysis of a model dual-conductivity
medium using a generalized effective-medium theory, J. Physica A. 157 (1)
(1989) 188–191.
[29] B.J. Christensen, T. Coverdale, R.A. Olson, S.J. Ford, E.J. Garboczi, H.M. Jennings,
T.O. Mason, Impedance spectroscopy of hydrating cement-based materials:
measurement, interpretation, and application, J. Am. Ceram. Soc. 77 (11)
(1994) 2789–2804.
[30] E.J. Garboczi, D.P. Bentz, Computer simulation of the diffusivity of cement-
based materials, J. Mater. Sci. 27 (8) (1992) 2083–2092.
[31] T.C. Power, Structure and physical properties of hardened Portland cement
paste, J. Am. Ceram. Soc. 41 (1) (1958) 1–6.
[32] D.P. Bentz, E.J. Garbozi, N.S. Martys, Application of digital-image-based models
to microstructure, transport properties, and degradation of cement-based
materials, in: The modelling of microstructure and its potential for studying
transport properties and durability, Springer, Dordrecht, 1996, pp. 167–185.
[33] E.W. Washburn, Note on a method of determining the distribution of pore
sizes in a porous material, Proc. Natl. Acad. Sci. U S A 7 (4) (1921) 115–116.
[34] J. Hu, Z. Qian, Y. Liu, M. Zhang, High-temperature failure in asphalt mixtures
using micro-structural investigation and image analysis, Constr. Build. Mater.
84 (6) (2015) 136–145.
[35] B. Olivier, F.J. Ulm, E. Lemarchand, A multiscale micromechanics-hydration
model for the early-age elastic properties of cement-based materials, Cem.
Concr. Res. 33 (9) (2003) 1293–1309.
[36] X. Lu, Application of the nernst-einstein equation to concrete, Cem. Concr. Res.
27 (2) (1997) 293–302.
[37] F. Leng, N. Feng, X. Lu, An experimental study on the properties of resistance to
diffusion of chloride ions of fly ash and blast furnace slag concrete, Cem. Concr.
Res. 30 (6) (2000) 989–992.
[38] J.Y. Jehng, D.T. Sprague, W.P. Halperin, Pore structure of hydrating cement
paste by magnetic resonance relaxation analysis and freezing, Magn. Reson.
Imaging. 14 (7–8) (1996) 785–791.
[39] D.A. Lange, H.M. Jennings, S.P. Shah, Image analysis techniques for
characterization of pore structure of cement-based materials, Cem. Concr.
Res. 24 (5) (1994) 841–853.
[40] E.J. Garboczi, D.P. Bentz, The effect of statistical fluctuation, finite size error,
and digital resolution on the phase percolation and transport properties of the
NIST cement hydration model, Cem. Concr. Res. 31 (10) (2001) 1501–1514.
[41] CCES 01 (2004), Department of civil, hydraulic and architectural engineering,
Chinese Academy of Engineering, China Construction Industry Press, 2005.
[42] N. Banthia, S. Mindess, Permeability measurement on cement paste, in: L.R.
Roberts, J.P. Skalny (Eds.), Proc. of Material Research Society Symposium 137,
Boston, 1989, pp. 173–179.
[43] B.K. Nyame, J.M. Illston, Relationships between permeability and pore
structure of hardened cement paste, Mag. Concr. Res. 33 (116) (1981) 139–
146.
[44] P. Tumidajski, B. Lin, On the validity of the Katz-Thompson equation for
permeabilities in concrete, Cem. Concr. Res. 28 (5) (1998) 643–647.