Construction and Building Materials 202 (2019) 589–602

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Construction and Building Materials

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

Quantitative characterization of pore morphology in hardened cement

paste via SEM-BSE image analysis
Kai Lyu a,b,c, Wei She a,⇑, Changwen Miao a,b,c, Honglei Chang d, Yue Gu e
a
School of Materials Science and Engineering, Southeast University, Nanjing 211189, China
b
State Key Laboratory of High Performance Civil Engineering Materials, Nanjing 211103, China
c
Jiangsu Research Institute of Building Science CO., Ltd, Nanjing 211100, China
d
School of Qilu Transportation, Shandong University, Jinan 250002, China
e
College of Mechanics and Materials, Hohai University, 210098, China

h i g h l i g h t s

DIP was applied to analysis the microstructure.

The relationship between pore size and pore shape was established.

The forming mechanisms of capillary pores was studied.

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

Article history: Pore structure is a significant microstructural characteristic in cement-based materials and dominates
Received 5 September 2018 the mechanical and transport properties of the materials. In this study, sectional plane analysis based
Received in revised form 8 January 2019 on backscattered electron scanning electron microscope (SEM-BSE) images was used to provide insights
Accepted 9 January 2019
into the nature of the pore structure. The effects of the w/c ratio on the total porosity and heterogeneity of
Available online 17 January 2019
the local porosity were analyzed. By coupling using Digital Image Processing (DIP) method, each single
pore displayed on SEM-BSE images was captured, and the equivalent circular diameter, hydraulic radius,
Keywords:
and roundness of each single pore were calculated to describe its size and shape characteristics. The rela-
Pore structure
W/c ratio
tionship between the pore size and pore shape was also established by comparing the pore size distribu-
Equivalent circular diameter tion and the shape parameter distributions. Results indicates that pores become less spherical with
Hydraulic radius increasing pore sizes. Status oriented model was further introduced to simulate the hydration process
Roundness and investigate the forming mechanisms of capillary pores.
Forming mechanisms Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction
Hardened cement-based materials, such as cement pastes,
cement mortars, and concrete are typically porous materials
[1,2]. Pore structure is a primary microstructural characteristic in
a porous material because many important properties including
mechanical properties and transport properties are strongly
affected by the characteristic of the pore system [3,4]. Mechanical
properties such as compressive strength and elasticity are primar-
ily determined by the total porosity. However, they are also
affected by the size and spatial distribution of the pores, as well
as the pore shape and connectivity [5]. Transport properties
including diffusion and permeability primarily depend on the
⇑ Corresponding author.
E-mail address: weishe@seu.edu.cn (W. She).
porosity, size, shape, and connectivity. The ingress of water into
the internal part from surrounding environment is determined
by the pore structure of the materials. Also, through pore trans-
portation, aggressive species like carbonate, chloride, and sulfate
ions can intrude into the concrete matrix, which is highly possible
to generate a chemical stress concentration in the concrete and
leads to the service life loss of the composite. The formation of
the pore structure is affected by various factors, such as cement
composition, water-to-cement (w/c) ratio, use of admixtures, sand
content, and degree of hydration [6,7].
Pores in cement pastes, mortars, and concrete have various
sizes, shapes, and origins, and were originally subdivided into
micropores, mesopores, and macropores by concrete researchers,
with different borderlines, e.g., 2.5 nm and 50 nm by M. Dubinin
[8]; 2.5 nm and 100 nm by Young et al. [9]. Dubinin also proposed
the term ‘‘ultramicropores,” with pore size less than 0.6 nm and

https://doi.org/10.1016/j.conbuildmat.2019.01.055
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
590 K. Lyu et al. / Construction and Building Materials 202 (2019) 589–602
‘‘supermicropores,” with pore size ranging from 0.6 nm to 1.6 nm
[10]. Currently, a more general classification is adopted in concrete
science and technology; the pores are distinguished by terms such
as gel pores, capillary pores, hollow-shell pores, and air voids [11–
14]. Gel pores are inside of the calcium silicate hydrates. Capillary
pores are primarily created by chemical shrinkage resulting from
the reduced volume occupied by the hydration products compared
to the volume of anhydrous clinkers plus water [15,16]. Air voids
are caused by incomplete compaction [17–19].
To reliably describe and predict the properties and performance
of hardened cement-based materials, it is paramount to accurately
characterize the pore structure parameters, i.e., not only total pore
volume, but also the surface area of the pores, pore size distribu-
tion, shape, and connectivity [20]. It is widely recognized that
materials with the same total pore volume with varying pore size
distribution can have completely different mechanical and trans-
portation behaviors [21]. An important challenge in the current
concrete research is to precisely determine the pore structure
parameters, and describe the evolution of the pore structure in
terms of the hydration process, and finally establish a reliable rela-
tionship between the microstructure and macro properties of the
cement-based materials.
Various advanced techniques have been introduced to charac-
terize the pore structure of hardened cement-based materials. Each
method has its own advantages and drawbacks, and is most suit-
able for a specific range of size. Adsorption methods are effective
to measure micropores with sizes down to several nanometers
[22–26]. The mercury intrusion porosimetry (MIP) method is a
widely used method to characterize the pore structure albeit with
some limitations [6,27]; it can detect pores ranging from 3 nm to
100 mm [4,26,28–32]. Zhou [33] proposed the pressurization–dep
ressurization cycling mercury intrusion porosimetry (PDC-MIP)
method to overcome the limitations of the MIP method, in which
the total volume of the throat pores and ink-bottle pores can be
detected at every pore size.
The samples for both the adsorption and MIP test must be dried,
and the drying procedure leads to the slight change in the pore
structure. Compared to the methods mentioned above, the small
angle scattering and nuclear magnetic resonance (NMR) method
can be used to determine the micropores without the drying pro-
cess of the specimens [12,34]. The methods listed above are all
indirect methods of measuring the pore structure. Some direct
methods are available that can produce a direct physical image
of the microstructure examined, and exhibit the size and shape
of the phases. By coupling using digital image processing method
(MIP) and digital images, the pore structure is both qualitatively
and quantitatively analyzed [35]. For large pores, like entrapped
and entrained air voids, they are more frequently measured by
optical microscopy and electron microscopy [17,18,36–38]. In the
last decade, X-ray computed tomography (X-CT) technology was
introduced into concrete research. Based on the X-CT method,
not only the basic porosity and pore size distribution, but also
the shape, connectivity, and spatial heterogeneity of the porosity
can be obtained [39–41]. Images from scanning electron micro-
scopy of backscatter detector (SEM-BSE) can also be used to char-
acterize the pores down to a size limit [14,27,42–44]. Compared
with the X-CT method, the SEM-BSE images are in two dimensions
but with a higher resolution [45]. Even though research has been
conducted by S. Diamond [14,46] et al. and Shu Jian Chen [47] per-
taining to using SEM-BSE images to investigate the total porosity
and pore size distribution, the analysis of the size and shape of
pore structures down to the single pore level is insufficient.
Thus, in this research, SEM-BSE images were applied to study
the pore structure of the cement pastes, and the effects of the w/
c ratio on the evolution of the pore structure were also investi-
gated. By coupling using digital image processing software, each
single pore detected was captured and the equivalent circular
diameter, hydraulic radius, and roundness of each pore were calcu-
lated to obtain a distribution of these indices. The relationships
between these parameters were also established. Status oriented
model was further introduced to simulate the hydration process
and investigated the forming mechanisms of capillary pores.
2. Experimental methodology
2.1. Materials
Portland cement of 42.5 MPa strength grade produced by Xiao
Yetian Cement Co., Ltd. (Jiangsu China) was used in this study.
The apparent density of the cement was 3110 kg/m3. The chemical
and mineral composition of the cement obtained from X-ray fluo-
rescence and X-ray diffraction, respectively, are listed in Table 1.
The particle size distribution of the cement is shown in Fig. 1.
The average size of the cement particle is 11.44 lm. Tap water
was used during the casting process. To study the effects of the
w/c ratio on the pore structure and pore shape, no superplasticizer
and other kinds of chemical admixtures were added to the cement
pastes to eliminate the effects of other factors.
2.2. Mix preparation
Three w/c mass ratios of 0.30, 0.35, and 0.40 were determined
to prepare six groups of cement pastes. The fresh cement paste
was cast into 25-mm cubic molds after the mixing process. The
specimens were sealed and stored in a curing room (95% ± 5% rel-
ative humidity and 20 °C ± 1 °C) for 24 h. Subsequently, the speci-
mens were demolded and cured until the designed age of
28 days under the same environmental conditions.
2.3. BSE image analysis
2.3.1. Sample preparation
After being cured for 28 days, each specimen was cut into small
cubic pieces of approximately 1 cm. Subsequently, the cut pieces
were immersed into isopropyl alcohol solution for 3 days and the
isopropyl alcohol was replaced every 24 h to remove the unbound
water and stop the hydration process [48,49]. After this procedure,
the samples were dried and vacuum impregnated with low viscos-
ity epoxy resin to solidify the internal microstructure, and provide
an atomic contrast to the capillary pores. The accuracy of the quan-
titative analysis is related to the quality of the captured BSE
images; thus, a proper grinding and polishing strategy was care-
fully chosen to obtain an extremely smooth testing surface [50–
52]. The samples were first ground using SiC paper of 180 grit,
300 grit, 600 grit, and 1200 grit for 2 min each. Subsequently,
3 lm, 1 lm, and 0.25 lm diamond pastes were used for polishing
for 30 min each. After each step, the samples were cleaned in iso-
propyl alcohol solution using an ultrasonic cleaner to remove the
polishing residues.
2.3.2. BSE image acquisition and processing
The polished samples were scanned under the BSE detector of
the electron microscopy and the magnification was set at 1000
at a compromise of image quality [53,54]. To obtain the optimum
brightness and contrast, some trials were performed. For each sam-
ple, the values of brightness and contrast were set as a constant to
guarantee the reliability of the results. Thirty images were col-
lected randomly throughout the testing surface. The size of the
images is 1280 pixels  960 pixels and the pixel size is 0.148 lm.
Thus, a field of size 0.19 mm  0.14 mm was imaged. Three typical
BSE images with different w/c ratios are shown in Fig. 2(a). The
 K. Lyu et al. / Construction and Building Materials 202 (2019) 589–602 591

Table 1
Chemical and mineral composition of the cement.

Chemical composition (% by mass) (X-ray fluorescence)

SiO2 Al2O3 CaO MgO Fe2O3 K2O Na2O TiO2 Ignition Loss
20.57 4.57 62.78 2.00 2.84 0.56 0.12 0.27 1.32
Mineral composition (% by mass) (X-ray diffraction)
C3S C2S C3A C4AF Amorphs
51.20 8.20 3.80 8.80 25.7

(2) Then, the brightness histogram of pre-processed image was

selected and for determination of exact upper threshold
value via overflow point method. By comparing the image
with segmented image, the value was roughly estimated to
range between 0 and 100. Then, two linear segments were
chosen from the curve and fitted with linear line as indicated
by dashed in Fig. 3. The intersection point between the two
linear segments was set to be the upper threshold value for
pores [55,56].

Once the upper threshold value of the pores was determined,

Fig. 1. Particle size distribution of the cement clinker.
three images on the left half are the typical original images of the
cement pastes with w/c = 0.30, 0.35, and 0.40, respectively.
In each original BSE image, three primary phases exist: hydra-
tion products, anhydrous clinkers, and pores. The unreacted
cement clinkers are the brightest phases with the highest gray val-
ues, while the pores are the darkest phases. The hydration products
constituted the most fraction in each image among the three
phases.
Each image was processed in the following steps:
(1) Pre-treatment was performed on each original image (as
shown in Fig. 2(a)) to increase image quality for quantitative
analysis. The 3  3 median filter function was applied to the
image for three times to reduce the noise and enhance the
boundary between different phases (as shown in Fig. 2(b)).
The histograms of the original image and pre-processed
image are as compared in Fig. 2(c).
the original grayscale images were converted into binary images
to better exhibit the distribution of the pore phases, which are
shown in Fig. 2(b). A binary image is a specific two-dimensional
(2D) image, in which the pixels have only two gray scales, i.e.,
white (2 5 5) and black (0) [57]. In Fig. 2(b), the white pixels repre-
sent the segmented pores, and the black pixels represent the solid
phases including the hydration products and anhydrous clinkers.
The segmented pores are composed of the capillary pore, hollow
shells, and some micro-cracks. The binary image clearly shows that
with the w/c ratio increasing from 0.30 to 0.40, the number of
white pixels increased, indicating an increase in total porosity.
3. Experimental results
3.1. Porosity
3.1.1. Total porosity
As been mentioned above, at the magnification of 1000, the
pixel size is approximately 0.148 lm, and the boundary size
between the gel pores and capillary pores is 10 nm. Thus, the pores
shown in the BSE images are all capillary pores, and the obtained
porosity are the capillary porosity. For each w/c ratio, 30 BSE
images of randomly chosen areas from the polished section were
analyzed according to the BSE image processing method men-
tioned in the former section, and the grayscale BSE image was con-
verted into a binary image with pore pixels in white and solid-
phase pixels in black. Subsequently, the number of white pixels

Fig. 2. Illustration of pre-processed results of each image (w/c = 0.35): (a) original image; (b) pre-processed image; (c) comparison of histograms between original image and
pre-processed image.
592 K. Lyu et al. / Construction and Building Materials 202 (2019) 589–602
Fig. 3. Illustration of determination of upper threshold value for pores via overflow
point method.
was counted and divided by the total pixels included in each image
to obtain the porosity of the cement paste within the image. An
average value based on 30 images was adopted as the total poros-
ity of the cement paste.
The variation in the total porosity as a function of w/c ratio is
shown in Fig. 3. The graph clearly shows that with the w/c ratio
increasing from 0.30 to 0.40, the measured total porosity of the
cement paste increases from 5.56% to 20.55%. At a certain curing
age, the w/c ratio has a determinant influence on the total porosity.
However, the porosities obtained by BSE images in this study is
slightly different from the porosities measured by the MIP test,
which often lies between 10% and 25% [58]. For the SEM’s finite
resolution limit, gel pores and capillary pores that are smaller than
the resolution of the technique cannot be detected where the res-
olution of the image is 0.148 lm in this study.
3.1.2. Number of pores detected
For each image, not only the number of total pore pixel, but also
the number of pores was counted by coupling using image process-
ing method. Fig. 4 shows the variation of the number of pores
detected in each image as a function of w/c ratio. When the w/c
ratio of the cement pastes increases from 0.30 to 0.40, the number
of pores also increases. However, it did not change as sharply as the
change in the total porosity. The porosity of the cement paste with
w/c = 0.40 is nearly four times the porosity of the cement paste
with w/c = 0.30, while the number of pores only doubled. This indi-
cates that, with the increasing w/c ratio, not only the total porosity,
but also the average pore size increased. Here, the size of a BSE
image is viewed as a unit area.
3.1.3. Heterogeneity of local porosity
Cement-based materials are highly heterogeneous materials.
Their random distribution of pores contributes significantly to the
heterogeneity of the system. However, the pore size distribution is
often ill defined. Instead of considering different pore sizes as the
primary source of the heterogeneity, the local porosity theory is
introduced to consider porosity itself as the random variable
[13,59,60]. The BSE technique enables local porosity fluctuations
to be considered directly. For each cement paste, 30 images of the
area chosen from the polished section, and each porosity obtained
from each image can represent the local porosity of the correspond-
ing area. A porosity range (which is equal to the gap between max-
imum and minimum porosity) was calculated for each mix and
listed in Table 2 and the results indicates that the porosity range
increases with the increasing w/c ratio. The standard deviation of
the three series of porosities was calculated to further describe the
local porosity fluctuations. The result shows that the standard devi-
ation of each porosity series increases stably with the w/c ratio
changing from 0.30 to 0.40, which indicates a more heterogeneous
internal microstructure. The standard deviation was further normal-
ized by the average porosity and listed in the fourth row in Table 2.
3.2. Pore size
The size and shape of an individual pore are important for
understanding the heterogeneity of cement-based materials. By
coupling using image processing software, each individual pore
was captured and saved. The minimum pore detected in each
cement paste is similar in size and shape, based on the limited res-
olution of the BSE technique. Thus, only the maximum pore size,
average pore size, and pore distribution were analyzed and
illustrated.
To compare the size of different single pores, the equivalent cir-
cular diameter (ECD) of each pore was calculated by equating the
area of a perfect circle to the pixel area of a pore (Ap), as shown
in Eq. (1), where Ap is the number of pixels included within each
single pore. Further, the value obtained was further multiplied by
the pixel size to convert the pixel size into the real size.
 1
Ap 2
ECD ¼ 4  ð1Þ
p
3.2.1. Maximum and average pore size
The equivalent circular diameters of the largest pores in each
cement paste detected are calculated based on Eq. (1). The average
pore size was calculated based on the average pore area obtained
by dividing the total pore area with the number of pores. The
results are summarized in Table 3. It is clear that for both the max-
imum and average pore sizes, with the increasing w/c ratio, they
both increase stably. However, the maximum pore size increases
much sharply than the average pore size.
3.2.2. Pore size distribution
For each cement paste, each individual pore was captured and
the equivalent pore diameter was calculated. Based on the calcula-
tion, both the pore size distribution and cumulative pore size dis-
tribution of each cement paste were determined. In this study, two
kinds of pore size distribution curves were constructed from the
quantitative analysis of the BSE images: equivalent circular pore
diameter vs. number of pores, and equivalent circular pore diame-
ter vs. pore area and area fraction.
3.2.2.1. Equivalent circular pore diameter vs. number of pores. As
mentioned previously, the cement paste with size equal to the size
of a BSE image is viewed as the unit are. The number of pores per
unit area and the equivalent circular diameters were counted and
calculated. The differential and cumulative pore size distribution
curves in terms of the equivalent circular pore diameter are shown
in Figs. 5–8. Two graphs are included in each figure labeled (a) and
(b). Graph (a) describes the characteristics of the pores of all sizes
detected, while graph (b) is a detailed description of the pores
smaller than 4 lm. The value of 4 is determined based on the
experimental finding that for all cement pastes, more than 95%
percent of pores are within this range (<4 lm) and this is shown
in Figs. 6 and 8, the cumulative curve.
Fig. 5 shows the exact number of pores in each size range. As
shown from Fig. 5(a) and (b), the pores in each cement paste are
in the similar distribution in that with the increasing pore size,
the absolute number of pores decreases. The cumulative pore size
 K. Lyu et al. / Construction and Building Materials 202 (2019) 589–602 593

Fig. 4. Comparison of the BSE image examples of cement pastes with different w/c ratios (each image is 0.19 mm  0.14 mm): (a) original BSE images, (b) binary images.

distribution in Fig. 6 indicates that pores (<1 lm) constitute the accounts for less than 5% of the entire pore distribution, they con-
most among all size ranges. When the w/c ratio changes from tribute significantly to the entire porosity.
0.30 to 0.40, in each size range up to 4 lm, the number of pores The number of pores in each size range was further divided by
also increases. Even though the number of these large pores only the total number of pores in each cement paste. Additionally, the
594 K. Lyu et al. / Construction and Building Materials 202 (2019) 589–602

Table 2 3.2.2.2. Equivalent circular pore diameter vs. pore area. The relation-
Maximum and minimum measured porosity and porosity heterogeneity of each ship between pore size and pore area is illustrated in Figs. 9 and 10.
cement paste as a function of w/c ratio.
For all three cement pastes, nearly in each pore size range, the
Measured porosity(%) Water: Cement mass ratio absolute pore area increases with the elevated pore size. A clear
0.30 0.35 0.40 peak exists in each curve in Fig. 9(a) and (b), implying that the
Porosity range (%) 2.98 5.66 8.85
pores in the corresponding size range constitute the most among
Average porosity (%) 5.56 11.81 20.55 the size ranges. If we define this pore range as the dominant pore
Standard deviation 1.01 2.16 3.31 range, with the increasing w/c ratio, the dominant pore size range
Normalized standard deviation 0.18 0.18 0.16 increases gradually from 1 lm to 2 lm. Fig. 10(a) and (b) show the
cumulative pore size distributions. Further, the pore structure in
cement pastes with w/c = 0.30, 0.35, and 0.40 is similar in distribu-
Table 3 tion; the difference in the total pore area increases with the
Equivalent circular diameters of largest pores in cement paste with different w/c
increasing w/c ratio, which corresponds well with the results of
ratios.
the porosity analysis.
Pore size Water: Cement mass ratio Subsequently, the absolute pore area was further normalized by
0.30 0.35 0.40 the total value of pore area in each cement paste; the results are
Maximum (lm) 9.47 19.28 35.87 shown in Figs. 11 and 12. These normalized curves describe the rel-
Average (lm) 1.36 1.44 1.78 ative proportion constituted by each pore size range. Further, three
clear peaks are shown in Fig. 11(b); they represent the dominant
size range and correspond well with the results in the former sec-
tion. With the increasing w/c ratio, the value of the peak in each
curve also increases stably.

3.3. Shape analysis of the pore structure

The shape of pores in each cement paste is also analyzed and

two parameters, hydraulic radius and roundness, are introduced
to describe the shape of each single pore and the total pore system.

3.3.1. Hydraulic radius

Apart from the equivalent circular diameter, the hydraulic
radius is another useful geometrical parameter for defining the size
of the pores. The hydraulic radius can be defined as the cross-
sectional area of the pore divided by the perimeter of the space.
Compared with the typical pore size, the hydraulic radius contains
more information about the pore structure. In addition to the size,
the shape information including the area and perimeter of the
Fig. 5. Variation in the total porosity as a function of w/c ratio.
pores are considered in the calculation. Two series of cements hav-
ing the similar pore size distribution may have differing hydraulic
radius. For definite pore shapes, the hydraulic radius is a fixed mul-
tiple of the pore size. When a pore is a perfect circle, the hydraulic
radius is equal to half the radius of the circle. Therefore, the
hydraulic can exhibit pore irregularities. In two dimensions, the
single pore and the entire system can be calculated from two
levels, according to Equation (2).

Ap
rh ¼ ð2Þ
Pp

where rh is the hydraulic radius (lm), Ap the cross-sectional area of

Fig. 6. Variation in number of pores detected in each BSE image as a function of w/c
ratio.
normalized differential and cumulative pore size distribution curve
are shown in Figs. 7 and 8, respectively. As well, a similar distribu-
tion of pore size can be found in these figures for all sample series.
The smaller the pore size, the higher is the fraction it occupies
among all pore sizes in absolute pore numbers.
a pore (lm2), Pp is the perimeter of the pore space (lm).
Thus, the hydraulic radius of all three cement pastes and each
single pore in the cement pastes are calculated according to Eq.
(2). The hydraulic radius for the total pore structure is regarded
as the average hydraulic radius of the system which is calculated
based on the total area and perimeter of the pore system. The
results are shown in Table 4.
The value of the average hydraulic radius listed in Table 4 sug-
gests an approximate relationship between the hydraulic radius
and the w/c ratio: with the increasing w/c ratio, the hydraulic
radius also increases. It indicates that, at a higher w/c ratio, both
the pore size and irregularity increase.
The differential hydraulic radius distribution is shown in Fig. 13.
For the pore structure in all three series of the cement pastes, the
hydraulic radii are in a similar distribution, that the fraction
decreases with increasing hydraulic radius. Also, it can be drawn
 K. Lyu et al. / Construction and Building Materials 202 (2019) 589–602 595

Fig. 7. Differential pore size distribution: Equivalent Circular Diameter vs. Number of pore per unit area: (a) Pores of all sizes, (b) pores (<4 lm).

Fig. 8. Cumulative pore size distribution: Equivalent Circular Diameter vs. number of pore per unit area: (a) Pores of all sizes, (b) pores (<4 lm).

Fig. 9. Differential pore size distribution: Equivalent Circular Diameter vs. number fraction of pores per unit area: (a) Pores of all sizes, (b) pores (<4 lm).
596 K. Lyu et al. / Construction and Building Materials 202 (2019) 589–602

Fig. 10. Cumulative pore size distribution: Equivalent circular diameter vs. number fraction of pores per unit area: (a) Pores of all sizes, (b) pores (<4 lm).

Fig. 11. Differential pore size distribution: Equivalent circular diameter vs. pore area of pores per unit area: (a) Pores of all sizes, (b) pores (<4 lm).

Fig. 12. Cumulative pore size distribution: Equivalent circular diameter vs. pore area of pores per unit area: (a) Pores of all sizes, (b) pores (<4 lm).
 K. Lyu et al. / Construction and Building Materials 202 (2019) 589–602
Table 4
Hydraulic radius of pores in three cement pastes.
Hydraulic radius (lm) Water: Cement mass ratio
0.30 0.35
Maximum 1.89 2.44
Average 0.39 0.40
Standard deviation 0.12 0.12
from the graph that, more than 90% of the hydraulic radii are in the
size range smaller than 0.4 lm.
When we analyze the hydraulic radius distribution curve in
detail and compare it with the differential pore size distribution
curve in Fig. 7(a), we found that these two curves are similar in
shape. This implies a potential relationship between the equivalent
circular diameter and hydraulic radius. The pore structure in the
cement paste with w/c = 0.30 is chosen as an example to perform
further investigation, and the result is shown in Fig. 14. The scatter
points in the figure are the data points, and a linear line was
applied to fit these points and represented by the dashed pink line
in Fig. 14. As mentioned above, if a pore is in a perfect circle, the
value of the hydraulic radius of this pore is equal to half the radius
and a quarter of the diameter. The solid blue line in Fig. 14 illus-
trates the relationship between these two indices if all the pores
are spherical. The graph clearly shows that with increasing pore
size, the difference between the two lines increases, indicating that
the pores are becoming less spherical and more irregularly shaped
with elevated pore size. The fitting results of all cement pastes are
listed in Table 5. For the pore structure in all series of cement
pastes, an approximate relationship exists between the hydraulic
radius and pore size.
Subsequently, all the pores in the three cement pastes were
viewed as a whole without considering the effect of the w/c ratio.
The result is illustrated in Fig. 15 and a similar conclusion can be
obtained from the figure, in that with increasing pore size, the
gap between the blue and pink line also increases, indicating the
increasing shape irregularity of the pores.
3.3.2. Roundness of pores
To better describe the shape of the single pores, two other
related shape parameter, roundness (R) and circularity (C), were
introduced. For each single pore, the roundness and circularity
are related. Thus, only the roundness of each individual pore was
calculated for the quantitative analysis. In two dimensions, R can
Fig. 13. Differential pore size distribution: Equivalent circular diameter vs. pore area fraction: (a) Pores of all sizes, (b) pores (<4 lm).
597
be calculated according to Eq. (3), where Ap is the voxel-based area
of a pore (lm2), and Pp is the perimeter of the pore space (lm).
0.40
P2p
R¼ ð3Þ
2.79
4pAp
0.43
The roundness has a value of 1 for a pore of a perfect circle. The
0.11
roundness of all the pores was calculated and a differential round-
ness distribution was obtained. As shown in Fig. 15, the roundness
in all three cement pastes are of nearly the same distribution. Fur-
ther, the curve trend appears similar to the pore size distribution in
Fig. 7(a), implying that the shapes and pore sizes may be
correlated.
Fig. 16 shows that the shape parameter increased approxi-
mately quadratically with the equivalent circular pore diameter,
suggesting that as the pores increase in size, they become less
spherical. Fig. 16(a)–(c) present three typical images of the pores
with increasing pore size. As shown, with increasing pore size,
the pore become irregularly shaped and tortuous.
Inspired by the definition of the hydraulic radius for the entire
pore structure, the roundness for the entire pore structure was cal-
culated by the total pore area and the perimeter, in which the val-
ues are 2.07, 2.11, and 2.37 for all three pore structure. If we define
this value to be the average roundness, the average roundness
increases with the increasing w/c ratio, implying that the shapes
of the pores are becoming less regular with increasing w/c ratio
(Fig. 17.).
4. Discussion
Commonly, the capillary pores can be divided into large capil-
lary pores and small capillary pores and they are in different form-
ing mechanisms. For large connected capillary pores are primarily
generated by the insufficient packing of the cement grains. Small
capillary pores are more generated by chemical shrinkage and
mainly exist in the hydration products. In this research, the mini-
mum size of the cement is small than 0.5 lm and the smallest
pores detected is about 0.16 lm in diameter. Thus, the value of
0.25 which is equal to the half size of the smallest cement particles
is determined as the boundary between the small and large capil-
lary pores. For all series of cement pastes, considering converting
the mass ratio between water and cement into volume fraction
based on the assumption that all the space is fully occupied the
cement and cement clinkers at fresh stage. The volume fractions
598 K. Lyu et al. / Construction and Building Materials 202 (2019) 589–602

Fig. 14. Cumulative pore size distribution: Equivalent circular diameter vs. pore area fraction: (a) Pores of all sizes, (b) pores (<4 lm).

Table 5
Fitting results of relationship between hydraulic radius and equivalent circular
diameter.

W/C ratio Fitting equation: Y = mx + n

m n R-square
0.30 0.115 0.151 0.7449
0.35 0.110 0.154 0.7241
0.40 0.079 0.186 0.6558
All 0.071 0.193 0.6192

Fig. 16. Relationship between hydraulic radius (lm) and equivalent circular
diameter (lm) of pore structure in cement paste (w/c = 0.30).

Fig. 15. Differential hydraulic radius distribution.

constituted by the cement are 51.7%, 47.9%, 44.6% respectively, for

three mass ratios. Referring to H. W. Hong’s study [15], the hydra-
tion degree of cement pastes ranges from 0.66 to 0.72 with w/c
mass ratio increasing from 0.30 to 0.40. Hence, for all cement
pastes, the absolute amount of hydrated cement is similar for all
three series of cement pastes, resulting in a similar amount of
small pores located in the outer hydration products which is oppo-
Fig. 17. Relationship between hydraulic radius (lm) and equivalent circular
site to the experimental findings in Fig. 5 that the number of small
diameter (lm) of pore structure in all three cement pastes.
capillary pores in cement pastes with w/c = 0.30 is much smaller in
another two series of cement pastes. Given that, the small capillary
pore could originate from another mechanism. the hydration process and study the formation of the capillary pore
To further probe into the forming mechanisms of the capillary structure. There are two steps included in the model, original
pores. Status oriented model [2,21,61] was introduced to simulate microstructure generation and hydration reaction.
 K. Lyu et al. / Construction and Building Materials 202 (2019) 589–602
Fig. 18. Differential roundness distribution.
4.1 Original microstructure generation
The generation of the unhydrated cement paste is simulated by
randomly distributing cement particles in a cubic RVE (representa-
tive elementary volume) [62]. To simplify the calculation, the
cement grains were represented by the spheres and 2D microstruc-
ture was adopted. The particles are placed into the created RVE by
a subrountie, which chooses random points from the RVE to serve
Fig. 19. (a), (b) and (c) Example of 2D visualization of pore shapes, (d) relationship between the roundness and equivalent circular diameter.
599
as the centers for particles, starting from the largest ones to the
smallest. Each time a particle is placed, a check is performed to
see whether it overlaps with other placed particles. Once overlap
happens, a new random points is generated.
4.2 Hydration reaction
The hydration process is simulated by the particles corroding
inward representing the growth of the inner hydration products
and expanding outward representing the growth of the outer
hydration products. In each hydration step, the anhydrous particles
are assumed to corrode a layer with a thickness of 1 pixel. Once
overlapping between outer product layer happens, the remained
free space which are closest to the hydrated pixels are allowed
for continuous growth of outer products. After each hydration step,
the hydration degree was calculated via pixels counting.
In this study, four sizes, 0.5 lm, 1.5 lm, 3.5 lm, and 7.5 lm of
cement grains were applied. The cement paste with w/c = 0.35
was chosen to act as an example to illustrate the model and the
original unhydrated microstructure is shown in Fig. 18(a). Consid-
ering converting mass ratio to volumetric ratio, the anhydrous
clinkers occupy approximately half of the RVE and the four sizes
of particles were set to occupy 15%, 15%, 15%, and 5%, respectively.
The pixel size is 0.05 lm. Based on the growing spheres method,
the microstructure of partly hydrated cement pastes in different
hydration degrees were obtained and shown in Fig. 18(b)–(d).
These four images are all gray- scale images. There are two kinds
of pixels in Fig. 18(a), white (2 5 5) and black (0) representing
two phases, anhydrous cement clinkers and pores structure
600 K. Lyu et al. / Construction and Building Materials 202 (2019) 589–602
Fig. 20. Simulated microstructure of the cement paste (w/c = 0.35) with varying hydration degree.
Fig. 21. Simulated microstructure of the zone labelled by the yellow square in Fig. 18(a).
respectively. While in the next three images, there exist four gray-
scales, 0, 100, 200, and 255 representing pore structure, outer
hydration products, inner hydration products, and remained uhhy-
drated cement grains respectively. The hydration degree is calcu-
lated according to the Eq. (4), where a is the hydration degree,
Aunhydrated is the amount of the unhydrated cement, and Acem repre-
sents the amount of the original cement. The Aunhydrated and Acem
can be obtained by counting the number of pixels belong to each
group in each image.
Aunhydrated
a¼1
Acem
It can be seen from the 2D images, with the hydration going on,
the remaining space between different cement particles are gradu-
ally occupied by the growth of the outer hydration products. Sub-
sequently, the total porosity decreases with the hydration going
on. A small area with 100 pixels  100 pixels in size labelled by
the yellow square in Fig. 18(a) was chosen from the whole 2D
microstructure and enlarged, shown in the Fig. 19(a). The Fig. 19
(b)–(d) shows the same area with Fig. 19(a) with varying hydration
degrees (Fig. 20).
From the Fig. 19, it can be seen that with the hydration process-
ing, the space between the small cement clinkers is partly occupied
by the hydration products, however there is some space remained
with unoccupied forming the pore structure. It is apparent that the
size of some pores located in the red circle in Fig. 19(d) is smaller
than the value of defined boundary between the large capillary
pores and small capillary pores. Thus, it can be concluded that,
not all the small capillary pores are inside of the outer hydration
products, some of them can also be generated by the insufficient
packing of the small cement particles which are in the similar sizes
with the small capillary pores. The amount of small capillary pores
in this forming mechanism is related to the amount of original
remaining space. Based on this conclusion, the effect of the w/c
ratio on the number of small capillary pores which is shown in
Fig. 5 can be explained. For three series of cement pastes, the
amount of small capillary pores in the outer hydration products
is similar. However, for cement paste (w/c = 0.30), the cement
grains accounts for a higher volume fraction in fresh cement state.
Subsequently, less space between small cement grains is left and
only adequate for the growth of outer hydration products. Less
small capillary pores formed compared to another two cement
pastes (w/c = 0.35, and 0.40) (Fig. 21).
ð4Þ 5. Conclusions
In this study, the pore structure in cement paste with varying
w/c ratios were investigated by coupling using the SEM-BSE tech-
nique and image processing software. The size and shape of each
single, and the entire pore structure were both described by the
porosity, pore size distribution, hydraulic radius, and roundness.
Based on the results obtained, the following conclusions can be
drawn:
(a) With increasing w/c ratio from 0.30 to 0.40, the total poros-
ity of each cement paste increased from 5.56% to 22.55%. The
pore structures in three cement pastes were of similar distri-
bution, in that pores smaller than 4 lm constituted more
than 95% of the total number of pores.
(b) The shape of each single pore was characterized by two
parameters: hydraulic radius and roundness. The distribu-
tion of these two indices were drawn based on the calcula-
tion for each single pore and were similar to the
differential pore size distribution of the curve shape. The
increasing values of the hydraulic radius and roundness
along with the increasing equivalent circular pore diameter
implied that with the increasing pore size, the pores became
less spherical and more irregularly shaped.
 K. Lyu et al. / Construction and Building Materials 202 (2019) 589–602
(c) The capillary pores were subdivided into small capillary
pores and large capillary pores and the borderline is deter-
mined as the half size of the minimum cement grains. Large
capillary pores are mainly generated by the insufficient
packing of the cement particles. Small capillary pores are
partly generated by the chemical shrinkage located in the
outer hydration products and partly caused by the insuffi-
cient packing of the small cement grains.
Conflict of interest
None.
Acknowledgements
The authors gratefully acknowledge the financial support from
the National Key R&D Program of China (2017YFB0309904),
National Natural Science Foundation of China (Grant Nos.
51508090 and 51890904), 973 Program (2015CB655100), State
Key Laboratory of High performance Civil Engineering Materials
(2016CEM005), China Scholarship Council for financial support
(201706090128). Also, greatly appreciate Jiangsu Research Insti-
tute of Building Science Co., Ltd and the State Key Laboratory of
High Performance Civil Engineering Materials for funding the
research project
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