Cement and Concrete Composites 96 (2019) 11–20

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Cement and Concrete Composites

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

Statistical modelling of compressive strength controlled by porosity and T

pore size distribution for cementitious materials
Dongwei Houa,∗, Dongyao Lia, Peicheng Huaa, Junda Jianga, Guoping Zhangb
a
State Key Laboratory of Ocean Engineering and Collaborative Innovation Center for Advanced Ship and Deep-Sea Exploration (CISSE), Department of Civil Engineering,
Shanghai Jiao Tong University, Shanghai, China
b
Department of Civil & Environmental Engineering, University of Massachusetts Amherst, USA

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

Keywords: The compressive strength of cementitious materials is significantly affected by its pore system inherent in the
Porosity matrix of cement paste, not only porosity but also pore size distribution. In present work, by deconvolution
Pore size distribution analysis, the total pore size distribution of cement paste is represented by a multiple distribution consisting of
Statistical strength model two single distributions for the capillary pores and the macro pores respectively. In this way, the widely accepted
Fracture probability
Raleigh-Ritz (R-R) function is challenged and the lognormal distribution is found to be best to approximate the
pore size distribution for cementitious materials. With pore size distributions, a statistical model based on
probability principle and fracture criterion is proposed to reveal the physical mechanism of reduction in com-
pressive strength induced by porous structures. Parameters in the model, e.g. fracture toughness of cement paste
matrix, fracture mode, volume of specimen, porosity and pore size distributions, are further discussed and ex-
amined quantitatively.

1. Introduction changed by environmental actions consists of three types of pores [5]:

Concrete is a typical porous material, whose pore structure as an
intrinsic physical property plays a prominent role in both mechanical
property and long-term durability. High strength is a fundamental
performance for modern concrete in many cases such as high-rise
buildings and important constructions with high requirements for
durability. Compressive strength of concrete depends on three main
physical phases, the cement matrix, the aggregates and the interfacial
transition zone [1]. For fiber-reinforcing cementitious materials, the
fibers can improve the whole strength by strengthen the cement matrix
phase [2–4]. Fundamentally, the pore system inherent not only in the
matrix of cement paste but also in the interfacial transition zone, sig-
nificantly affected the concrete strength by weakening both the cement
matrix and the interfaces [5–8]. Although the relationship between
strength and pore structure has been studied for several decades as a
basic issue in both science and technology significance [9–17], it still
attracts great attentions nowadays and needs to be reexamined thor-
oughly to push forward the understanding on the physical mechanism
of reduction in strength induced by porous structure of cementitious
materials.
The pore structure in cement paste formed in hydration process and
(a) gel pores, which are micro pores with characteristic dimension of
0.5–10 nm, rarely harmful to concrete strength but directly related to
creep and shrinkage; (b) capillary pores, which are meso-pores with
average radius ranging from 5 to 5000 nm and usually determined by
water-cement ratio; (c) macro pores due to inadequate compaction of
cement particles and/or entrained air. Capillary pores and macro pores
are responsible for reduction in strength and elasticity, etc. [8]. The
most important characteristics of pore structure are porosity and pore
size distribution, which can be measured through mercury intrusion
porosimetry (MIP) [18–21], Brunauer-Emmett-Teller theory (BET)
[22–24] or low field nuclear magnetic resonance (LFNMR) method
[25,26]. Porosity, which is usually vital to the mechanical performance
and penetrability of cementitious materials, is just an overall descrip-
tion of the pore structure by the ratio of the pore volume over the total
body volume. Pore size distribution, commonly represented either as
cumulative pore volume or derivative pore volume as a function of pore
radius, depicts the pore structure in more details. The pores size dis-
tribution is usually complicated for cementitious materials because it is
formed by multi-mechanism for different ranges of pores. Therefore, the
frequency of pore size distribution is usually characteristic of bimodal
curves or multi-peak curves [27]. An advanced understanding for the

∗
Corresponding author.
E-mail addresses: houdw@sjtu.edu.cn (D. Hou), lidongyao@sjtu.edu.cn (D. Li), huapeicheng@sjtu.edu.cn (P. Hua), jiangjunda@sjtu.edu.cn (J. Jiang),
zhangg@umass.edu (G. Zhang).

https://doi.org/10.1016/j.cemconcomp.2018.10.012
Received 19 March 2018; Received in revised form 22 July 2018; Accepted 15 October 2018
Available online 16 October 2018
0958-9465/ © 2018 Published by Elsevier Ltd.
D. Hou et al. Cement and Concrete Composites 96 (2019) 11–20

multi-peak curve is taking it as a composition of several single dis- uniaxial or biaxial tensile loadings. Up to these days, the Weibull dis-
tributions, each of which is induced by a main forming mechanism and tribution function is a basis of the state of the art in mechanical design
follows an individual distribution law. A simplistic Raleigh-Ritz (R-R) procedure of metallic or ceramic materials [49,50]. Besides, it is also
distribution function is commonly used to describe the pore size dis- introduced and modified to analysis the size effect of concrete fractures
tributions in cementitious materials [27]. However, it should be chal- [51,52]. Although the Weibull distribution is also challenged in some
lenged by normal distribution, lognormal distribution and Weibull aspects [29,51–54], the statistical principles to bridging the gap be-
distribution, which are more generally accepted to approximate pore tween macro performance and disordered microstructures of materials
size distributions in various solid materials [28,29]. is always powerful.
Since recognizing the existence of relationship between strength In present work, a statistical model of strength is build up based on
and pore structure, a number of indirect models to relate concrete the pore structure of cementitious materials, especially the pore size
strength to water-cement ratios were well established in earlier studies distributions. Firstly, the cement paste samples were prepared and
[11,12,15–17], which served their purpose well in design of concrete tested by MIP to obtain their information of pore structures. Analysis of
mixes for traditional concretes, but become less workable for mordent pore structures was conducted by a deconvolution method to disin-
concretes in recent years, which are higher in various performances and tegrate the total pore size distribution into two single distributions re-
thus more complex in components. To link macro properties to mi- presenting the capillary pores and macro pores respectively. By this
crostructures in more details, computational technology was introduced method, the pore size distribution of cementitious materials can be
to simulate hydration mechanisms and microstructure formation in understood clearly in both physical and mathematical sense. Based on
cementitious materials, based on special simulation platforms such as the pore size distribution, a statistical model to estimate the compres-
HYMOSTRUC proposed by Breugel [30,31] and Ye et al. [32], CEM- sive strength of cement pastes was proposed based on the fracture
HYD3D proposed by Benz et al. [33], and μic proposed by Bishnoi and criterion of cementitious materials, with the key parameters in the
Scrivener [34]. Logically, for not only real concrete but also digital model examined quantitatively to offer more understandings into the
concrete, a direct relationship can facilitate the strength estimation effects of various factors, such as the strength of cement paste matrix,
from the knowledge of its pore system characteristics [35,36]. Taking the volume of specimens, the porosity and pore size distributions, etc,
porosity as a key factor for strength, quite a few empirical models have on the strength of cement pastes. This model agrees well with the test
been reported in literature, mainly including the linear relationship by data, and potentially provides a physical framework, based on which
Hasselmann [37], the power exponent relationship by Balshin [38], the both outside and inside physical actions influencing the strength of
exponential relationship by Ryshkevitch [39] and the logarithmic re- cement pastes can be incorporated into this mode in future works, to
lationship by Schiller [40]. However, when plotting abundant of test form a complete description on the mechanical behaviors of modern
data together and fitting them by the strength-porosity relationships, concretes.
Kumar and Bhattacharjee [5] found that poor correlation is observed,
and it appears all the above forms of models are inadequate in ex-
plaining the observed variation of concrete strength with measured 2. Experiments
porosity. This problem can be attributed to the absence of pore size
parameters in these models. To consider the influence of pore sizes, For hardened cementitious materials, the compressive strength, as
Kumara and Bhattacharjeeb [5], Lian, Zhuge and Beecham [41] and well as their pore structures, is determined by various factors such as
Atzeni, Massidda and Sanna [42] took mean pore diameter into account cement grades, water-cement ratio and hydration degree, etc. Cubic
based on fracture theories to modify the model of concrete strength samples of 70.7 mm × 70.7 mm × 70.7 mm in size, 6 samples per
with porosity. Nevertheless, using the mean pore diameter to represent group, were formulated with three grades of cements, P.O.32.5,
all pore sizes is week in physical sense and thus inadequate in accuracy. P.O.42.5, and P.O,52.5, at three typical water-cement ratios w/
To remedy this deficiency, Atzeni et al. [42] and Older and Rößler [43] c = 0.2,0.4,0.6. The chemical components of the cements obtained by
proposed a different form of strength-porosity relationship expressing X-Ray method was listed in Table 1, where a higher content of C3S is
the compressive strength of concrete with a linear function of porosities involved in P.O.52.5 cement, while a higher content of C3A involved in
within multiple ranges of sizes. Meanwhile, supposing the porous ma- P.O.32.5 cement. In addition, the particle size distributions of the three
terial are made up of various sizes of porous bodies connected in par- grades of cements represented in both cumulative volume fraction and
allel, Tang [44] proposed a model to calculate the effect of pores sizes frequency of volume fraction are shown in Fig. 1, indicating that the
on concrete strength and carried it out by computer. Obviously, most of cement powder becomes finer with upgrading of cements. Mix pro-
these existing models are based on observations of phenomenological portions of the cement paste samples, together with their average
relations between strength and pore structures and express them by compressive strength after curing in standard conditions
deterministic mathematical methods. On the contrary, the pore struc-
tures are stochastically generated and randomly distributed. Hence, it is Table 1
difficult to include all the information of pore structure affecting the Oxide composition of cements by XRF (wt%).
strength of cementitious materials in a deterministic mathematical Cements P.O.32.5 P.O.42.5 P.O.52.5
model.
By contrast, a probabilistic model is expected to be more powerful SiO2 37.6629 36.7415 37.0876
CaO 26.8911 36.5607 37.0057
to reveal the mechanism of strength controlled by pore structures. Since
Al2O3 14.8964 8.3166 6.5348
the pore structure in concrete is characterized of anomalous mor- SO3 11.8954 9.783 9.1361
phology and cross-scale sizes, it is hard to describe it in full details. In Fe2O3 3.1039 4.0818 3.5614
this case, a statistical method based on probability principle, with help MgO 2.5606 1.767 3.9262
K2O 1.3764 1.7285 1.3242
of the fracture criterion of the material, is more reasonable to establish
TiO2 0.5932 0.2942 0.34
the relationship between strength and pore structures, including both Cl 0.384 / /
porosity and pore size distributions. More than 70 years ago, Weibull SrO 0.2211 0.2834 0.0648
[45] proposed a statistical theory of brittle fracture to describe the P2O5 0.1972 0.1708 0.3843
variations of observed fracture behaviors. Jayatilaka and Trustrum MnO 0.1127 0.1124 0.4139
Cr2O3 0.0639 0.0691 0.123
[46–48] have successfully related the mathematical form of the Weibull
ZnO 0.0412 0.091 /
statistical theory to the assumed form of the flaw size distribution, and Total 100 100 99.9
analyzed the failure probability for brittle materials subjected to

12
D. Hou et al. Cement and Concrete Composites 96 (2019) 11–20

Fig. 1. Particle size distributions of the three grades of cements.

Fig. 2. Porosity of the cement pastes.

Table 2
Mix proportions and compressive strength of cement pastes. structures for cementitious materials.
The MIP test provides the pore volume versus pore size derived from
Sample Cement Grade w/c Curing Age days Compressive Strength MPa
the intruded volume of mercury into pores at increasing pressure, by
C3-0.4-3 3 27.1 ± 1.6 means of Washburn equation [59]. In present work, two parameters,
C3-0.4-7 P.O.32.5 0.4 7 28.3 ± 2.5 porosity and pore size distribution, were extracted from MIP tested
C3-0.4-28 28 37.1 ± 2.0 results. Porosity is defined as the ratio of the pore volume to the total
C4-0.2-3 P.O.42.5 0.2 3 65.6 ± 3.5
volume of hardened cement paste body, where the volume of cement
C4-0.2-7 7 73.8 ± 1.9
C4-0.2-28 28 84.8 ± 5.4 paste matrix, which is included in the body volume, is transformed from
C4-0.4-3 P.O.42.5 0.4 3 38.3 ± 1.9 the mass of cement pastes by taking their matrix density as 2.604 g/cm3
C4-0.4-7 7 39.7 ± 2.6 [60]. Meanwhile, the volume of pores with specific sizes is normalized
C4-0.4-28 28 45.8 ± 1.7
by the total pore volume both for cumulative distribution function
C4-0.6-7 P.O.42.5 0.6 7 15.3 ± 1.6
C4-0.6-28 28 22.6 ± 1.7 (CDF) and probability distribution functions (PDF) in the following
C5-0.4-3 P.O.52.5 0.4 3 47.8 ± 0.4 texts.
C5-0.4-7 7 57.2 ± 2.4
C5-0.4-28 28 59.3 ± 2.7 3.1. Porosity

The porosity of every cement sample is shown in Fig. 2. Agreeing

(T = 23 ± 0.5 °C, RH ≥ 95%) for desired ages (3 days, 7 days, 28
days), are all summarized in Table 2, where the sample names are
denoted as “cement grade-water to cement ratio-curing ages”. Con-
sistent with conventional conclusions, the compressive strength of the
cement pastes increases with upgrading of cement class, decreasing of
water to cement ratio and extension of curing ages.
The cement paste samples curing for desire ages were crashed into
grains of about 3 mm in diameter, and then immersed in large volume
of isopropanol for 24 h to exchange the water out of pores, followed by
drying in a vacuum desiccator at temperature of 55 °C for 48 h. Then
the dried cementitious grains are kept in desiccative materials before
tested to measure their pore structures by standard MIP with a contact
angle of 130° and the pressure from 0 to 414 MPa (6000 psia).
3. Analysis of pore structures
Despite its extensive use, the MIP technique and moreover the in-
terpretation of MIP data are controversial [55–57] because of the so-
called “ink-bottle” effect of pores within cementitious materials, which
may lead to an overestimation of small pores and an underestimation of
large pores. However, Muller and Scrivener [58] reassessed the stan-
dard MIP technique by comparison with 1H Nuclear Magnetic Re-
sonance (NMR), confirming that the “ink-bottle” effect is not apparent
for MIP to measure the capillary pores, even the interhydrate pores
(which are the smallest capillary pores), because capillary pores form a
continuous network across the sample that is well connected to the
exterior. Since the strength of cementitious materials is predominantly
dependent on capillary pores and macro pores but rarely rest with gel
pores, the MIP method is reliable to be employed to measure the pore
with conventional results, the porosity increases with water-cement
ratio (showing as dashed line in Fig. 2), because thicker coating water
expands the interspaces among cement particles and leaves coarser
capillary pores after filled by hydration products of cement. Meanwhile,
higher grade cement with finer particles generates denser pore struc-
ture according to geometric principles, and leaves smaller unoccupied
capillary pores after hydration than lower grade cement, thus resulting
in lower porosity in hardened cement paste (showing as solid line in
Fig. 2). Besides, with increasing of hydration degree, more and more
hydration products fill the spaces occupied originally by water, causing
finer pores and lower porosity. Obvious changes of porosity with
synthesis parameters of cement pastes answer the question why it is
commonly considered as a predominant factor relating to mechanical
and penetration performance of cementitious materials.
3.2. Pore size distribution
3.2.1. Distribution functions
According to pore size scales, the pore system within cement paste
can be categorized into gel pores, capillary pores and micro-pores. Gel
pores was recognized to be contained in calcium silicate hydrate (C-S-
H) gels, including both the high density C-S-H gels with a higher con-
stant porosity and larger size of gel pores, and the low density C-S-H
gels with a lower constant porosity and smaller size of gel pores
[60,61]. As the gel pores rarely influence the strength of cementitious
materials, they are not concerned too much in present work. When the
cement particles coated with water films are packed together, the space
not taken up by the cement or the hydration products consists of ca-
pillary voids, whose volumes and sizes are determined by the original

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D. Hou et al. Cement and Concrete Composites 96 (2019) 11–20

f (x ) =
⎧
⎨
1
2π x ln(δ ) (
exp −
(ln(x ) − ln)(μ)2
2 ln2 (δ ) ) x>0

⎩0 x≤ 0 (4)

1 1 ln(x ) − ln(μ) ⎤
F (x) = + erf ⎡
2 2 ⎢
⎣ 2 ln(δ ) ⎥ ⎦ (5)
2
where ln(μ) is the mean of ln(x) and ln (δ) is the standard variation for
values of ln(x).
In addition, in probability fracture theory, the most extensively used
is Weibull distribution to represent the occurrence of flaws or variations
of strength. The PDF f(x) and CDF F(x) of Weibull distribution is

α / β (x / β )α − 1 exp(−(x / β )α ) x≥ 0
f (x ) = ⎧
⎨
⎩0 x<0 (6)

F (x) = 1 − exp(−(x/ β )α ) (7)

Fig. 3. Pore size distribution of a typical cement paste sample (C4-0.2-3).
distance between the anhydrous cement particles in the freshly mixed
cement paste and the degree of subsequently cement hydration. For
inadequately compacted cement, large caves or voids due to packing of
coarse powders, together with air bubbles entrained in mixing process,
forms the macro pores after filled partly by hydration products.
As the cement particle sizes are distributed randomly in a vast range
of scales, as well as hydration products growing disorderly, together
with air bubbles incorporated randomly in mixing process, the voids
among cement particles are also formed stochastically in cement pastes.
Obviously, the capillary pores and macro-pores are generated sub-
jecting to different physical mechanism, therefore the size distributions
of them follow different distribution laws. As shown in Fig. 3, the PDF
curve of pore size distribution behaves with three peaks at the scales of
gel pore sizes, capillary pore sizes and macro pore sizes, respectively.
Correspondingly, the S-shape of CDF curve dose not increase smoothly
and continually from 0 to the normalized value (100%), but appears
three rapid-ascent stages with decreasing of pore sizes at the matched
pore size scales with PDF curve peaks.
To describe the pore system of cementitious materials, the mostly
adopted mathematical method is Raleigh-Ritz (R-R) function [27]. As-
suming the porosity of interlayer pores Φl keeps constant and both the
gel pores and the capillary pores follow the R-R rule, the commutative
volume fraction of pores in terms of radius is expressed as follows:
Φ (r ) = Φl + Φg (1 − exp(−Bg r )) + Φc (1 − exp(−Bc r ))
where, Φ, Φg, Φc are the porosity of total pores, gel pores and capillary
pores, respectively; r is the pore radius; Bg and Bc are empirical para-
meters. In present work, the R-R function is challenged by three other
distributions, normal distribution function, lognormal distribution
function and Weibull distribution function, which are examined and
compared with R-R function to optimize the mathematical tool simu-
lating the pore size distributions of cementitious materials.
The normal distribution or Gaussian distribution is a general
mathematical method to describe a random process, and thus is po-
tentially available to simulate the pore size distribution of cement
paste. Its PDF f(x) and CDF F(x) are given as follows:
1 (x − μ)2 ⎞
f (x ) = exp ⎛−⎜ ⎟ can be determined by minimizing the standard error:
2π δ ⎝ 2δ 2 ⎠
x 1 (t − μ)2
F (x ) = ∫−∞ exp ⎛−
⎜
⎞ dt
⎟ ⎝
2π δ ⎝ 2δ 2 ⎠ (3)
Where μ is the mean and δ2 is the standard variation.
Besides, a more frequently used probability method to describe
flaws size distributions in rock materials is the lognormal distribution
function, with the PDF f(x) and CDF F(x) expressed by
where, α is the shape parameter and β is the location parameter.
To break the monopoly of R-R function and improve the re-
presentation of real pore size distributions in cementitious materials,
the above four distribution functions will be examined in the next
section to find an optimal method among them, based on which the
statistical strength model will be build up in section 4.
3.2.2. Deconvolution analysis of pore size distribution
Since the gel pores are very low in volume content (Fig. 3) and have
little influence on the compressive strength of cement pastes, they are
combined with capillary pores in the following analysis, which will lead
to negligible deviations to the cement paste strength. By assuming that
the sizes of either capillary pores or macro pores follow a same dis-
tribution law, the total pore size distribution can be separated into
single distributions with particular parameters and independent with
each other. In mathematical view, the decomposition analysis can be
conducted by the deconvolution method [62,63].
By taking the normal or Gaussian distribution as an example, the
deconvolution of realistic pore size distribution is performed as follows.
Let us assume that the total pore size distribution consists of n groups of
pores ranging within different scales, which are distinguished from
each other and can be best approximated by the normal or Gaussian
distribution. Then the total cumulative pore size distribution function is
given by:
2
n n x 1 1 t−μi ⎞ ⎞
F (x) = ∑i=1 λ i Fi (x; μi , δi) = ∑i=1 λ i ∫−∞ exp ⎜⎛− ⎛
⎜ ⎟
⎟ dt
(1) 2π δi ⎝ 2 ⎝ δi ⎠ ⎠
(8)
where the weight coefficient for each group of pores, λi, subjecting to
n
∑i= 1 λ i = 1, is proportional to the volume content of this group of pores;
μi is the arithmetic mean of all pore sizes of ith group containing Ni
pores, while the standard deviation, δi2, is a measure of the dispersion
of these values.
1 N 1 N
μi =
Ni
∑k=i 1 x k, δi2 (x ) = ∑ i (xk − μi )2
Ni − 1 k = 1 (9)
Hence, there is a total 3n unknowns {λ i , μi , δi} for i = 1∼ n. If em-
pirical cumulative pore volume fraction or response distributions are
obtained by MIP in form of discrete diameter values X, the unknowns
(2)
2
N ⎛⎜ n
min∑
k= 1
∑i=1 λ i F (Xk ; μi , δi) − D (Xk ) ⎞⎟
⎠ (10)
where D(Xk) for k∈[1,N] is the observed value of the experimental
cumulative pore volume fraction at pore size Xk, while F(Xk; μi,δi) is the
value of the theoretical cumulative distribution function shown in Eq.
(8).
After all the parameters are obtained, the theoretical PDF can also

14
D. Hou et al. Cement and Concrete Composites 96 (2019) 11–20

Fig. 4. Deconvolution of CDF and PDF of pore size distribution for sample C4-
0.4-28 and comparison of theoretical results with test data.
distribution laws.
From the lognormal distribution parameters, several similar varia-
tion trends, but in less strictness, can be observed. For most of cement
paste samples, the mean size of either capillary pores or macro pores
increases with water-cement ratio, but decreases with curing age.
Meanwhile the volume content of capillary pores increases with curing
age, indicating that with development of hydration process, some
macro pores are filled and transformed into capillary pores. In the re-
sults, some deviations from anticipations are also observed, because the
amount of samples in present work is limited and more tests are re-
quired to find the statistical laws of these parameters. The deviations
indicate that the parameters of pore size distributions are still variable
from one sample to another, although they are statistically obtained
from all the pores in one sample. Despite of deviations of pore structure
parameters, the strength of cement pastes agrees well with conventional
anticipations, which can be deduced from the data in Table 2. Actually,
the strength of cement paste is determined by multiple physical char-
acteristics of its micro structures collaboratively, the mechanism of
which will be explained by the statistical strength model.

be calculated by the derivative of F(x). Practically, the distribution
parameters can also be determined by fitting the PDF with experimental
frequency density just by replacing the core function in equation (10)
with PDF. However, the experimental frequency density is affected
dramatically by the step size of mercury intrusion volume in MIP tests,
which will lead to instable fitted parameters of distributions. Therefore,
fitting of CDF was found to be better than that of its derivative PDF
[63,64].
To conduct deconvolution analysis on the three other distribution
laws, one can only substitute the core distribution function in equation
(10) with the CDF of R-R function, lognormal distribution or Weibull
distribution. By this deconvolution method, the total pore size dis-
tribution is separated into single distributions, each of which follows
the same distribution law but with particular distribution parameters. A
typical example for the pore size distribution decomposed with two
single distributions both in CDF and PDF is shown in Fig. 4. The fitting
parameters of the lognormal distributions, with the correlation coeffi-
cient R2 of normal distribution, R-R distribution and Weibull distribu-
tion are summarized in Table 3.
By comparing the fitting level denoted by the correlation coefficient
R2, the lognormal distribution is confirmed to be best to represent the
realistic pore size distributions for cement pastes, with the next is
Weibull distribution. Moreover, not like the Weibull distribution, the
parameters of lognormal distribution is clearly defined in physical
nature, hence it is avoid to furtherly find the correlations between
statistical parameters (e.g. mathematical expectation and variance) and
the real pore structures. By contrast, the widely accepted R-R function is
the worst to simulate the realistic pore size distributions among the four
4. Statistical strength model
4.1. Theoretical derivation
Assuming the probability dense of pore sizes f (a) consists of n single
distributions, we can express it as
n
f(a) = ∑ λ i fi (a)
i= 1 (11)
where a is pore diameter. Then, for a flaw with size a in an elemental
volume of cement paste, the Griffith fracture theory [65] gives the re-
lationship between the flaw size, a, and the critical stress driving the
flaw just begin to crack, σ, yielding [66,67].
2 KIC 2
a= ⎛ ⎞
π ⎝ Yσ ⎠ (12)
where, KIC is the mode I critical stress intensity factor of cement paste
matrix with zero flaws. Especially, for cementitious materials, KIC re-
presents the fracture toughness of C-S-H gel clusters containing gel
pores within them. In present work, the gel pores are excluded in the
measurable pores by MIP but included in the basic structure of cement
paste matrix. Y is a dimensionless geometrical factor, related to the flaw
shape and the specimen shape for homogeneous materials. However,
for cement pastes, which is heterogeneous and multiple phases, Y de-
pends on the fracture modes and related factors influencing the initia-
tion and propagation of cracks, such as interaction of flaws, inner
moisture state and property of interfacial bonding between interphases,
etc.

Table 3
Pore structure parameters of cement pastes by deconvolution method based on lognormal distribution function.
Samples Porosity μ1 nm δ1 nm λ1 μ2 nm δ2 nm λ2 2
Rlognorm 2
Rnorm RR2 − R 2
RWB

C3-0.4-3 0.353 34.26 3.61 0.869 106850 2.76 0.131 0.996 0.979 0.996 0.996
C3-0.4-7 0.341 24.40 2.78 0.946 116760 5.34 0.054 0.997 0.992 0.995 0.997
C3-0.4-28 0.341 18.43 2.31 0.913 64760 13.28 0.087 0.995 0.993 0.986 0.994
C4-0.2-3 0.191 62.50 2.30 0.754 179402 3.37 0.246 0.995 0.985 0.987 0.992
C4-0.2-7 0.164 20.36 1.61 0.801 136941 4.41 0.199 0.993 0.994 0.965 0.993
C4-0.2-28 0.174 44.05 1.44 0.814 3885 61.39 0.186 0.998 0.994 0.939 0.990
C4-0.4-3 0.316 38.14 3.39 0.959 110986 2.30 0.041 0.996 0.988 0.992 0.991
C4-0.4-7 0.304 39.69 2.08 0.880 112840 4.47 0.120 0.995 0.994 0.984 0.996
C4-0.4-28 0.281 26.11 2.15 0.875 89701 8.22 0.125 0.996 0.997 0.986 0.998
C4-0.6-7 0.448 40.38 4.23 0.948 169484 2.43 0.052 0.997 0.982 0.996 0.996
C4-0.6-28 0.423 60.19 2.68 0.902 63865 7.40 0.098 0.999 0.987 0.995 0.996
C5-0.4-3 0.323 34.79 3.00 0.944 117327 2.272 0.056 0.992 0.998 0.994 0.991
C5-0.4-7 0.286 29.74 2.91 0.961 114248 2.264 0.039 0.991 0.997 0.996 0.993
C5-0.4-28 0.203 39.00 2.30 0.902 194916 2.28 0.098 0.997 0.996 0.989 0.998

15
D. Hou et al.
Fig. 5. Comparison of theoretical strength with test data of cement pastes.
In an elemental volume V0 containing one pore, the fracture prob-
ability at stress σ equal to the probability of occurrence of a pore with
size above the critical crack length a, yielding
∞ by best fitting the strength data of the cement paste samples, which are
F(σ ) = ∫a f(x) d x
where a is determined by equation (12). When a specimen with volume
V contains N elemental volumes, that is N]V/V0, the fracture prob-
ability Pf at stress σ is
1−Pf (σ ) = [1 − F (σ )]N
N is also the amount of pores. For cementitious materials, N is
usually difficult to count clearly. Firstly, it is hard to detect all the pores
with sizes ranging from nanometer scale to millimeter scale even by
state of the art test technologies, such as computed tomography (CT),
nuclear magnetic resonance (NMR) or small angle neutron scattering
(SANS). Secondly, the pores in cementitious materials are amorphous in
shape and usually partly connected with adjacent ones, therefore it is
hard to identify one unique pore clearly. Thirdly, how to identify an
isolated pore in mechanical meanings for connected pores has not been
understood comprehensively and needs further investigations in future.
In this case, N is estimated simply in terms of porosity p and volume V
as
N = kpm V
where, k and m are empirical parameters. If all the pores are the same in
both shape and volume, m equals to 1. However, the realistic pore
volume and pore shape are variable dramatically, thus the linear re-
lationship between N and p switches to a supposed power law. For a
specific cementitious sample, N will change with cement types, water-
cement ratio and hydration degree in some extent. However, in present
work N is believed to be dominantly controlled by the porosity p and
specimen volume V, but slightly affected by other factors.
Substituting equation (15) into equation (14), one can rearrange the
fracture probability at stress σ to:
m
Pf (σ ) = 1 − [1 − F (σ )]kp V
If N is large enough, which is achievable for most practical cases,
equation (16) can also be simplified to [47]:
Pf (σ ) = 1 − exp(−kpmVF (σ ))
which is a similar form to Weibull distribution function. When a far
field stress σ∞ acts on a cement paste sample, nonuniform stresses are
inspired around the micro flaws because of stress concentrations near to
flaw tip zones, where a local crack will occur when the critical stress is
Cement and Concrete Composites 96 (2019) 11–20
achieved. Moreover, cracking propagation is a stochastic process with
the flaws growing and coalescing until throughout the whole sample to
lead to a final failure. For these reasons, the macro strength of ce-
mentitious materials is controlled by the whole stress distribution and
can be represented by the mathematical expectation of strength, which
is an average of local stresses by weighting them with the probability of
critical stresses achieved [52,68]. Thus, the macro compressive strength
is obtained by Refs. [47,48,68].
1 σmax
f c = σ¯ = ∫0 σdPf = ∫σ
min
(1 − Pf ) dσ
(18)
where, σmin and σmax are taken to be the minimum and maximum loads,
which must be chosen when considering a defective material. Theore-
tically, σmin = 0 and σmax tends to infinity, but in practice those values
are usually finite and greater than zero [69]. In present work, σmin and
σmax are taken as 0 and 200 MPa respectively. At σmax = 200 MPa, the
fracture probability expressed by equation (13) extremely approaches
to 1, ensuring that all the stresses above 200 MPa have no contributions
to the integration of survival probability in equation (18) and thus to
the average strength.
Based on the above model, the compressive strength of cement
pastes are calculated using the lognormal distribution function, which
is the optimal method to describe the realistic pore size distributions of
cement pastes. Parameters in the model, KIC, Y, k and n, are determined
(13) KIC = 0.7714 MPa m , Y = 157.49, k = 29397/m3, n = 2.922. A good
agreement of model results with test data is observed in Fig. 5, with the
correlation coefficient R2 = 0.988. It should be noted that KIC acquired
by fitting experimental data is 0.7714 MPa m , which is close to the
experimental fracture toughness of cement based material reported by
(14) Shah [70], who suggested an approximate value of fracture toughness is
about 0.5 MPa m for hardened cement paste with compressive
strength of 40 MPa.
4.2. Further discussions
The proposed model is established to relate the compressive
strength to the main factors including porosity, pore size distribution,
fracture toughness of cement paste matrix and body volume of speci-
mens. As a basic framework modelling the strength of cementitious
materials, this model can be further refined, for example, by taking
account of hydration degree into the development of C-S-H fracture
strength and the evolution of microstructures of cement pastes. Besides,
environmental actions on the hydration process and hence the micro-
(15) structures and fundamental mechanical behaviors [71–73], as well as
the effect of reinforcing fibers on the fracture mode of cement paste
matrix [74–77], can also to be incorporated to expand the model in
future works. Assuming the empirical parameters k and n are always
available for most of cementitious materials, the roles of the main
factors correlated to the compressive strength can be quantitatively
examined in more details.
4.2.1. Fracture toughness of cement paste matrix
From the proposed model, it can be easily deduced that the macro
strength of hardened cement paste strongly depends on its fracture
toughness of cement paste matrix KIC, which is further determined by
(16) the contents of cement chemical minerals such as C3S, C2S, C3A, C4AF
and their hydration products. If blended materials are incorporated, e.g.
fly ash, silica fume and slag, the additional reaction products will also
contribute to the matrix fracture strength of cementitious materials. To
examine the relationship between KIC and the macro strength of cement
(17)
pastes more clearly, various KIC values ranging from 0.1 to 2.0, which
cover most of possible values of KIC for cementitious materials, are
taken to calculate the strength of cement pastes, with the pore structure
parameters taken from the samples of C3-0.4-28, C4-0.4/0.6–28 and
C5-0.4-28. Nearly linear relationships are observed from the curves of
16
D. Hou et al.
Fig. 6. Relationship between macro strength and fracture toughness of cement
paste matrix.
macro strength versus KIC shown in Fig. 6, suggesting that the apparent
strength is founded on the fracture strength of cement paste matrix, but
affected by the pore structures remarkably at the same time. Consistent
with conventional concepts, the strength-KIC curves imply that an ef-
fective way to improve the strength of cementitious materials is to
enhance the fracture strength of matrix.
4.2.2. Fracture mode parameter Y
The geometric parameter Y in equation (12) essentially denotes the
fracture mode of cementitious materials in the proposed model. It re-
lates to the pore geometric configuration, pore density, specimen shape,
moisture status in pores, elastic and plastic modulus and Poisson ratio
of the material, etc. [78]. Actually, the fracture modes of cement pastes
in micro and meso scales are controlled by different fracture mechan-
isms. For initiation of cracks in cement paste matrix, the dislocation
theory [68] is reasonable to explain the micro-fracture. It shows that
the dislocations will be active when the stress exceeds the critical stress
of the material, and then propagate and produce dislocation pile-up if
encumbered by obstacles. Growing and coalescence of the dislocation
pile-ups will produce micro-cracks or plastic flow, leading to the failure
of C-S-H clusters. Meanwhile, as for the propagation of cracks in cement
paste with flaws or pores, a wing crack model [78–81] is powerful to
explain the fracture mode in meso scale. This damage mechanics model
tells that for a inclined pre-existing flaw, when a shear traction induced
by applied stresses is sufficiently high to overcome the frictional re-
sistance, frictional slip results in tensile stress concentrations at the two
tips of the sliding crack, which in turn may induce “wing cracks'’ to
nucleate there and extend along the principle stress direction after the
driving force attained the critical stress intensity factor value. As the
applied stress is increased, shorter and less favorably oriented sliding
cracks will be activated, thus nucleating an increasing number of wing
cracks distributed throughout the sample and lead to the failure of
cement pastes. This theory can well explain the vertical cracking per-
formance of cement paste samples under uniaxial compression but
without constraints on the top and bottom of the sample. Wong et al.
[78,82] proposed an expression of Y taking into account of the “wing-
cracks” effect in rock materials.
Besides of fracture mode, moisture state in cement materials will
affect the strength in a certain extent, which is usually described as
“drying-strengthening” and “wetting-weakening” [83]. The same ob-
servations were also obtained in the experimental researches of
Wittman [84], Haynes et al. [85] and Cadoni [86] and Wang and Li
[87].
As the fracture mode is vital for the physical mechanism of failure
17
Cement and Concrete Composites 96 (2019) 11–20
and therefore the strength performance of cementitious materials, it
deserves comprehensive investigations in more details in future works.
In present model, the fracture mode parameter Y is only estimated by
best fitting the experimental results.
4.2.3. Volume size effect of strength
As a matter of fact, the strength of cementitious materials decreases
with increasing size of the specimen. The mechanism of size effect of
compressive strength is complex and can be partly explained by Weibull
statistics theory based on the assumption of “weakest link concept”
[52]. Bazant et al. have systematically studied the size effect of fracture
of quasi brittle materials based on energy release analysis and nonlocal
Weibull theory. They also proposed a model of size effect of compres-
sion following fc ∝ z−2/5 [88]. Both the classical Weibull theory of
statistical size effect and Bazant's size effect model for compression is
essentially a power scale law in terms of specimen size. In present work,
the size effect of compressive strength is caused by randomness of pore
sizes and probability of failure for a certain volume of cement bulk with
numerous flaws inside it. It should be noted that the prediction strength
based on specimen sizes by present model are only satisfied within an
estimated limit range of 100–1000 cm3, which is in the same magnitude
of our sample volume of 350 cm3, but not always available for the
whole ranges of scales. Checking the theoretical results shown in Fig. 7,
we should point out that this model overestimates the macro strength of
the cement pastes with small volumes, but underestimate them with
large volumes. This may be due to the difference of cracking propa-
gation process in small specimens from that in large ones. For a large
volume of specimen, stress redistribution at fracture process zone will
slow down the propagation of local cracks, which will improve the
whole compressive strength in some extent compared with the model
predictions based on an estimation of average critical stresses. In con-
trast, if the volume of cement paste sample is very small, a local destroy
will quickly lead to a complete failure of the sample, reducing the
practical strength.
4.2.4. Porosity p
As aforementioned, the experimental relationships between
strength and porosity were widely investigated, with several forms of
models proposed in the literature. In present work, the proposed model
offers some deeply understandings on the correlations of strength with
porosity in more details. Taking the values of porosity p from 0 to 1, we
calculate the theoretical strength of cement pastes, with the pore
structure parameters taken from the samples of C3-0.4-28, C4-0.4/
0.6–28 and C5-0.4-28. As shown in Fig. 8, for most of cement pastes, the
compressive strength is notably dependent on the porosity when the
Fig. 7. Variation of compressive strength with volume of cement pastes.
D. Hou et al. Cement and Concrete Composites 96 (2019) 11–20

4.2.5. Pore size distribution

The proposed model offers the quantitative relationship between
the strength and full distribution of pore sizes in cementitious materials.
With lognormal distribution function to represent the pore size dis-
tribution, the mean diameters, as well as the volume content ratio, of
both capillary pores and macro pores are taken as main parameters to
calculate the strength of cement pastes. Other parameters of pore
structure are taken from the sample of C4-0.4-28.
For the capillary pores with diameters ranging from 10 nm to
1000 nm, the strength of the cement pastes decreases with increasing
pore sizes significantly at fixed volume content (Fig. 9 (a)). Meanwhile,
the strength is enhanced by increasing the volume content of capillary
pores and correspondingly reducing the content of macro pores.
In contrast, for the macro pores with diameters ranging from
1000 nm to 1 mm, the strength of the cement pastes is less sensitive to
the pore size, especially in low volume contents of macro pores (Fig. 9
(b)). Therefore, the key parameter for macro pores to control the
strength of cement pastes is the volume content rather than the pore
size.
Fig. 8. Relationship between strength and porosity of cement paste samples.

5. Conclusions

In this paper, to establish the relationship between the compressive

strength of cement paste and its pore structure, including not only the
porosity but also the pore size distribution, a statistical model based on
probability principle and fracture criterion is build up. Firstly, the re-
presentation of pore size distribution in cement paste is reexamined,
with the deconvolution analysis method introduced to separate the
total pore size distribution into single distributions representing the
capillary pores and micro pores respectively. Based on deconvolution
analysis, the commonly accepted R-R function is challenged and log-
normal distribution is confirmed to be best to approximate the pore size
distribution for cementitious materials. Then, from pore size distribu-
tions, a fracture probability function is established based on Griffith
fracture relationship between flaw size and critical stress level. The
compressive strength is in turn obtained by averaging the survival
probability of all sizes of pores, which agrees well with the tested data
of cement paste samples. Finally, the main parameters in this model are
examined quantitatively and further discussed, with some meaningful
findings obtained. A similar linear relationship between macro strength
and fracture toughness of cement paste matrix is confirmed quantita-
tively. Besides, a critical porosity of about 0.3 to control the macro
strength significantly is observed, implying that the compressive
strength of cement pastes can be improved dramatically by controlling
the porosity under 0.3 and decreasing it within this range. For the ca-
pillary pores with sizes ranging from 10 nm to 1000 nm, both pore size
and volume content are significant to control the compressive strength
of cement pastes. However, for macro pores with sizes above 1000 nm,
the macro strength of cement pastes is less sensitive to the pore size but
more dependent on the volume content. The proposed model put for-
ward the understanding on the mechanism of compressive strength
controlled by the pore structure, and can be potentially expanded in
future as a basic framework of modelling the strength of cementitious
materials by taking both outer and inner actions into account in the
model parameters.

Acknowledgements

Fig. 9. Variations of theoretical compressive strength with mean diameters of

This work was supported by the National Natural Science
capillary pores (a) and micro pores (b) respectively. Foundations of China (No. 51308334; No. 51479113), which are
gratefully acknowledged.

porosity is lower than about 0.3, but becomes less sensitive to the
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