M A TE RI A L S C HA RACT ER I ZA TI O N 95 ( 20 1 4 ) 1 2 9–1 3 9

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Property investigation of calcium–silicate–hydrate

(C–S–H) gel in cementitious composites

Chuanlin Hua , Yunge Hanb , Yueyi Gaob , Yamei Zhangb , Zongjin Lia,⁎
a
Department of Civil and Environmental Engineering, The Hong Kong University of Science and Technology, Hong Kong, China
b
Jiangsu Key Laboratory of Construction Materials, Southeast University, Nanjing, China

AR TIC LE D ATA ABSTR ACT

Article history: Calcium–silicate–hydrate (C–S–H) gel, the main product of cement hydration, contributes
Received 27 March 2014 the most to engineering properties of concrete. Hence, the microstructural physical and
Received in revised form 3 June 2014 mechanical properties of C–S–H gel present in cementitious composites were investigated
Accepted 7 June 2014 by the coupled nanoindentation and scanning electron microscope analysis. The physical
Available online 12 June 2014 and mechanical properties were linked through the micro-poromechanical approach.
Through this study, an insight was provided into the microstructural features of C–S–H gel
Keywords: present in cementitious composites. It is found that C–S–H gel is a multi-scale composite
Calcium–silicate–hydrate gel composed of C–S–H solid, pore and intermixtures at the scale of nanoindentation on C–S–H
Microstructure gel, and the physical and mechanical properties of C–S–H gel can be influenced by the
Composition porosity and volume fraction of the intermixtures.
Poroelastic properties © 2014 Elsevier Inc. All rights reserved.

1. Introduction array of nanoindentation tests on the polished surface of

Calcium–silicate–hydrate (C–S–H) gel plays the most impor-
tant role in the engineering performances of concrete and
other cementitious composites. Thus, the study on C–S–H gel
is significantly important in understanding and improving the
macroscopic performances of concrete and other cementi-
tious composites. The mechanical parameters (e.g., indenta-
tion modulus and hardness) of the C–S–H microstructure
present in cementitious composites are generally assessed by
the nanoindentation technique. The mechanical properties of
C–S–H gel reported in the literatures are summarized in
Table 1. From Table 1, it can be seen that most of the results
are obtained from SNT (statistical nanoindentation tech-
nique), except the work of Hughes and Trtik [1], and Chen et
al. [2]. In SNT, statistical analysis was used to deconvolute the
mechanical parameters of individual phases from a large
hardened cement paste, and the researchers do not have to
exactly know the location or material phase where each
nanoindentation test is to be performed [3]. However, the
critical aspects on the application of SNT to study the
microstructure of hardened cement paste were recently
proposed, e.g. [4,5]. The application of SEM (scanning electron
microscope) can help to interpret nanoindentation results
more precisely. In the work of Hughes and Trtik [1], although
SEM was used to locate the position of nanoindentation tests,
while the number of indenter tests was very small: only one
indenter test on inner product C–S–H and four indenter tests
on outer product C–S–H. In the work of Chen et al. [2], a
coupled nanoindentation/SEM technique was performed on a
hardened cement paste at low water to cement ratio of 0.2 to
show the existence of C–S–H/nano-CH composite, while the
mechanical parameters of outer product and inner product

⁎ Corresponding author.
E-mail address: zongjin@ust.hk (Z. Li).

http://dx.doi.org/10.1016/j.matchar.2014.06.012
1044-5803/© 2014 Elsevier Inc. All rights reserved.
130 M A TE RI A L S C HA RACT ER I ZA TI O N 95 ( 20 1 4 ) 1 2 9–1 3 9

Table 1 – Summary of C–S–H mechanical properties mechanical properties of C–S–H gel present in cementitious
characteristics reported in the literatures (Mean ± S.D.). composites were investigated by the nanoindentation tech-
Sample C–S– M H Method Reference nique. After that, SEM equipped with BSE (backscattered
information H (GPa) (GPa) electron) and EDX (energy-dispersive X-ray spectroscopy)
detectors was adopted to visualize and characterize the
w/c = 0.42 Ca/ 20 ± 2 0.8 ± – Acker [35]
Si < 1 0.2 microstructures where the nanoindentation tests had been
Ca/ 31 ± 4 0.9 ± performed. Through the coupled technique on C–S–H gel
Si > 1 0.3 present in cementitious composites with the different mix
w/c = 0.4 LD a 21.7 ± – SNT Constantinides proportions, the physical and mechanical properties of C–S–H
2.2 and Ulm [36] gels were investigated in this work. With the obtained
HD b 29.4 ± –
properties of C–S–H gel, the micro-poromechanical approach
2.4
w/c = 0.45, OP c 25.74 ± 0.88 ± NI/SEM d Hughes and
was used to link the physical and mechanical properties.
1 month in 10.84 0.36 Trtic [1] Through this study, an insight was provided into microstruc-
water IP e 22.97 0.88 tural features of C–S–H gel present in cementitious composites.
w/c = 0.35, LD 23.4 ± 0.73 ± SNT Zhu et al. [37]
28 days in 3.4 0.15
water at 20 ± HD 31.4 ± 1.27 ± 2. Materials and experiments
3 °C 2.1 0.18
w/c = 0.5, LD 18.1 ± – SNT Jennings et al.,
30 days at 4.0 2007 [38]
ASTM Type I Portland cement conforming to ASTM C150
20 °C HD 31.0 ± – (Standard Specification for Portland Cement) was used in this
4.0 work. For the sake of comparison, a total of five mixtures with
w/c = 0.5, LD 18.2 ± 0.45 ± SNT Constantinides the different mix proportions were prepared, as listed in
5 months 4.2 0.14 and Ulm [39] Table 2. In the preparation process, firstly, the raw materials
HD 29.1 ± 0.83 ±
were mechanically mixed with deionized water and then cast
4.0 0.18
into steel molds; after 24 h, the specimens were demoulded
w/c = 0.45, LS f 22.89 ± 0.93 ± SNT Mondal and
1 month in 0.76 0.11 Shah [40] and cured in moist conditions (23 ± 1 °C and 95% relative
water at 25 °C MS g 31.16 ± 1.22 ± humidity) until testing.
2.51 0.07 Fig. 1 shows a typical load–depth curve generated from the
HS h 41.45 ± 1.43 ± nanoindentation test on C–S–H gel. From the initial slope of
1.75 0.29 the elastic unloading in the load–depth curve, two mechanical
w/c = 0.3 LD 23.7 ± 0.68 ± SNT Vandamme et
parameters can be simultaneously obtained [7]. The first one
5.9 0.18 al. [41]
is indentation modulus, M, and the second one is hardness, H,
HD 36.1 ± 1.01 ±
3.4 0.16 as defined below:
w/c = 0.4, LD 26.84 ± 0.88 ± SNT Howind et al. rffiffiffi!
7 days 3.62 0.13 [42] 1 dp π 
M¼  ð1Þ
HD 32.92 ± 1.21 ± 2 dh A 
h¼hmax
3.36 0.20
≈ 44 ≈1.3 p
w/c = 0.2, OP NI/SEM Chen et al. [2] 
1 year of IP/I i ≈ 50 ≈1.7 H¼  ð2Þ
A h¼hmax
sealed
hydration where p is the indentation load, h is the indentation depth and
a
hmax is the maximum indentation depth. A is the projected
LD = low density.
b
contact area and can be extrapolated from the indentation
HD = high density.
c depth h through Oliver and Pharr's method [8]. The indenta-
OP = outer product.
d
NI/SEM: a coupled nanoindentation/SEM technique. tion modulus is related to the elastic modulus, E, and
e
IP = inner product. Poisson's ratio, v, of the local material through [9]:
f
LS = low stiffness.
2
g
MS = medium stiffness. 1 1−v2 1−vtip
h ¼ þ ð3Þ
HS = high stiffness. M E Etip
i
IP/I = inner product and interface.

were not reported; thus, the values given in Table 1 are the Table 2 – Details of mix proportions.
peak values of the probability density distributions of inden- Code Binder composition Water/binder Sand/binder
tation modulus and hardness. (in mass mass ratio mass ratio
Due to the complicated microstructure of C–S–H gel, there percentage) (w/c) (s/b)
is no structural model to relate the physical and mechanical CP0.23 100% cement 0.23 –
properties of C–S–H gel [6]. The aim of this work is to improve CP0.40 100% cement 0.40 –
the current understanding on the microstructures of C–S–H M0.23 100% cement 0.23 1.2
gel in cementitious composites through studying its physical M0.35 100% cement 0.35 1.5
M0.53 100% cement 0.53 2.0
and mechanical properties. To fulfill the aim of this study, the
 M A TE RI A L S C HA RACT ER I ZA TI O N 95 ( 20 1 4 ) 1 2 9–1 3 9
Fig. 1 – A typical load–depth curve of nanoindentation test on
C–S–H gel characterized by M = 26.9 GPa and H = 0.85 GPa.
where Etip is the elastic modulus of the indenter tip, and vtip is
Poisson's ratio of the indenter tip. For the diamond tip used
in this study, Etip and vtip have values 1141 GPa and 0.07,
respectively. The hardness is related to the yield strength of
the local material, while the hardness to yield strength ratio
depends on the material type [10]. After the nanoindentation
tests, the indenter tip left the footprints on the surfaces of the
samples (see Fig. 2). The maximum load used in this work was
2 mN and thus generated a maximum depth hmax between
200 and 400 nm on C–S–H gel. The results from nanoindenta-
tion tests are decided by the mechanical property of the local
material microstructure, generally with the length scale
around 3–5hmax [11]. Thus, the average size of interaction
volume of nanoindentation on C–S–H gel is around 1.23 μm3.
To study the microstructural physical properties of C–S–H
gel, the samples were examined using a JSM-6390 SEM
equipped with BSE and EDX detectors. The SEM–BSE images
Fig. 2 – SPM (scanning probe microscopy) image showing
residual impression of nanoindentation tests on C–S–H gel
present in cement paste at w/c of 0.4 (RMS roughness: 24.6 nm).
131
Fig. 3 – An example of SEM–BSE image showing the major
components in hardened cement paste at w/c of 0.4 (white:
UH; light gray: CH; gray: C–S–H gel composed by inner
product (IP) and outer product (OP); dark: visible pores).
were taken to distinguish the C–S–H gel in cementitious
composites (see Fig. 3). In the SEM–BSE images, the gray value
is mainly a function of the average atomic number of the local
material microstructure, which allows each phase to be
distinguished through the image analysis. The segmentation
of each phase has been done through the application of the
SEM–BSE image analysis, e.g., the segmentations of residual
cement grains (denoted as UH) [12,13], calcium hydroxide
(denoted as CH) [12,14], and pores (denoted as P) [15,14,13,16].
Then, SEM–EDX analyses were performed on each sample
to investigate the microstructural composition of C–S–H gel.
The interaction volume of SEM–EDX analysis on C–S–H gel
was characterized by Monte-Carlo simulation and compared
with that of nanoindentation on C–S–H gel. It was found
that when an operating voltage 15 KV of SEM–EDX analysis
was chosen, the size of the interaction volume of SEM–EDX
analysis on C–S–H gel was comparable to that of nanoinden-
tation on C–S–H gel [17,18]. Thus, the operating voltage of
15 KV was demonstrated in this study.
3. Results and discussion
3.1. Chemical composition
Since C3S and C2S occupy about 75% of cement clinker,
CH occupies the largest amount of hydration products after
C–S–H. Meanwhile, the minor hydration products, such as,
ettringite, monosulfoaluminate and others, are generated
from the hydration of C3A and C4AF. The elemental maps
of cement paste at w/c of 0.4 are shown in Fig. 4. In the area
of C–S–H gel, the non-uniform elemental distributions indi-
cate the variation of microstructural chemical composition of
C–S–H gel.
To characterize the different chemical compositions of the
C–S–H gel, the Si/Ca versus Al/Ca, S/Ca and Fe/Ca atom ratio
plots of SEM–EDX analyses of C–S–H gel present in cement
paste at w/c of 0.4 are drawn in Fig. 5. The high Ca/Si ratios of
C–S–H gels indicate the effect of intermixtures of other
phases, e.g., CH (Si/Ca = 0, Al/Ca = 0, S/Ca = 0 and Fe/Ca = 0),
ettringite (denoted as ETT: Si/Ca = 0, Al/Ca = 0.33, S/Ca = 0.5
and Fe/Ca = 0) and monosulfoaluminate (denoted as MON:
Si/Ca = 0, Al/Ca = 0.5, S/Ca = 0.25 and Fe/Ca = 0). Thus, at the
micro-scale, an intimate intermixture forms inside the C–S–H
132 M A TE RI A L S C HA RACT ER I ZA TI O N 95 ( 20 1 4 ) 1 2 9–1 3 9
Fig. 4 – An example of BSE image and the corresponding elemental maps of cement paste at w/c of 0.4.
gel and can significantly influence the microstructural proper-
ties of C–S–H gel.
The atom ratio plots of C–S–H gel in Fig. 5 show that most of
the C–S–H gels belong to the C–S–H/CH composite. The C–S–H/CH
composite is composed of three phases, C–S–H solid, CH
and pore. C–S–H gels that belong to C–S–H/CH composites
were chosen according to the chemical composition. In the
composite, a significant proportion of CH crystal forms as the
intermixtures of C–S–H gel. The mass fraction (mCH) of CH
included in the composite can be calculated based on the
chemical composition:
 
Ca=Sicomposite −Ca=SiC–S–H ηCH
mCH ¼ : ð4Þ
ηcomposite
Here, the atom mass of CH (ηCH) equals to 74, while the
atomic mass of the composite (ηcomposite) is the total atom mass
of the composite obtained from the SEM–EDX analysis. The
density of C–S–H/CH composite depends on the porosity (ϕ),
the amount of CH and C–S–H solid, and can be expressed as:

1−mCH mCH −1
ρgel ¼ þ ð1−ϕÞ: ð5Þ
ρC−S−H ρCH
Here, the densities of CH (ρCH) and C–S–H solid (ρC–S–H)
equal to 2.24 g/cm3 [19] and 2.6 g/cm3 [20], respectively. The
volume fraction of CH can then be calculated from its mass
fraction:
mCH ρgel
f CH ¼ : ð6Þ
ρCH
For the sample CP0.4, the average Ca/Si ratios of the
composite characterized by inner product (IP) and outer
product (OP) were 2.14 ± 0.17 and 2.30 ± 0.26, respectively.
Through the introduced method, the average volume frac-
tions of CH included in inner product composite and outer
product composite are calculated to be 0.10 ± 0.03 and 0.13 ±
0.06, respectively. At the scale of interaction volume of SEM–
EDX analysis on C–S–H gel, it is found that a higher w/c ratio
leads C–S–H gel a lower Ca/Si ratio, e.g., for C–S–H gel present
in cement paste matrix of M0.23, the average Ca/Si ratio is
3.60 ± 1.18, while for C–S–H gel present in cement paste
matrix of M0.35, the average Ca/Si ratio decreases to 2.55 ±
0.67. The difference of the Ca/Si ratio with varying w/c ratio
indicates that the C–S–H gel at low w/c ratio contains more
intermixtures than that at high w/c ratio.
3.2. Mechanical properties
From the nanoindentation tests on C–S–H gel, the histogram
of indentation modulus of C–S–H gel can be obtained. As an
 M A TE RI A L S C HA RACT ER I ZA TI O N 95 ( 20 1 4 ) 1 2 9–1 3 9
Fig. 5 – Si/Ca versus (a) Al/Ca, (b) S/Ca and (c) Fe/Ca atom ratio
plots of SEM–EDX analyses of C–S–H gel as OP (○) and IP (4)
present in CP0.4.
example, Fig. 6 shows the probability distribution of indenta-
tion modulus of C–S–H gel present in a cement paste matrix of
M0.53, which shows the presence of four distinct phases. To
obtain the mechanical parameters of each phase (or each
peak), a deconvolution method was used with maximum
likelihood estimation of multiple Gaussians model. The
idea of the deconvolution method is briefly introduced here.
A large number of nanoindentation tests (i = 1,….N) were
performed on the microstructures of heterogeneous material
133
Fig. 6 – Probability distribution of indentation modulus of
C–S–H/CH composites present in cement paste matrix of
M0.53.
composed of n material phases. The basic assumption is that
the distribution of the in-situ assessed parameters of individ-
ual phases can be approximated by the normal distribution or
Gaussian distribution, ψj, specified with the average value and
standard deviation. The objective of statistical analysis is
to estimate the unknown parameters (average values, standard
deviations and volume fractions). The theoretical PDF (probabil-
ity density function) of nanoindentation data is formulated as:
X
n
PDF ¼ f jψ j ð7Þ
j¼1
and the volume fractions are constrained by:
X
n
f j ¼ 1: ð8Þ
j¼1
The mechanical parameters were estimated through the
application of expectation maximization algorithm [21]. The
deconvolution results of C–S–H gel present in cement paste
matrix of M0.53 are described in Fig. 6. When a cement paste is
observed in the SEM–BSE image as shown in Fig. 3, the C–S–H
gel exists in two morphologies, the C–S–H gel of less dense
morphology mainly occupies the space originally filled by
water and the C–S–H gel of more dense morphology mainly
occupies the space originally occupied by cement particles.
The two morphologies of C–S–H gel are commonly named as
outer product (OP) and inner product (IP) [22]. However, the
crystalline phase (e.g., CH) with a significantly large size or
proportion that embeds inside the C–S–H matrix can lead to
significantly high elastic modulus and hardness. In cementi-
tious composites at high w/c ratios, pores of significantly large
size or proportion that embed inside the C–S–H matrix can
lead to significantly low elastic modulus and hardness
(denoted as: very porous C–S–H gel). In the order of indenta-
tion modulus from low to high, the four phases present in
M0.53 can be identified as:
1. Very porous C–S–H (VP C–S–H) gel with an average
indentation modulus of 13.6 ± 1.0 GPa, occupying a vol-
ume fraction of 11%.
134 M A TE RI A L S C HA RACT ER I ZA TI O N 95 ( 20 1 4 ) 1 2 9–1 3 9

2. Outer product C–S–H (OP C–S–H) gel with an average

indentation modulus of 20.8 ± 3.2 GPa, occupying a vol-
ume fraction of 51%.
3. Inner product C–S–H (IP C–S–H) gel with an average
indentation modulus of 31.0 ± 3.1 GPa, occupying a vol-
ume fraction of 29%.
4. Crystalline phase with an average indentation modulus of
40.9 ± 1.2 GPa, occupying a volume fraction of 8%.

The deconvolution results of OP C–S–H gel and IP C–S–H gel

present in cementitious composites with different mix propor-
tions are summarized in Table 3. When the water to cement
ratio varies between 0.23 and 0.53, the average indentation
modulus of OP C–S–H gel varies between 20.8 and 28.9 GPa, and
that of IP C–S–H gel varies between 31.0 and 39.8 GPa. The work
of Chen et al. [2] shows that the average indentation modulus
of OP C–S–H gel reaches 44 GPa and that of IP C–S–H gel
reaches 50 GPa for a cement paste at w/c of 0.2. Thus, the
water to cement ratio largely influence the mechanical proper-
ties of C–S–H gel and a lower water to cement ratio leads C–S–H
gel a higher indentation modulus. The influence of the water to Fig. 7 – Geometry of a nanoindentation test on the RVE of
cement ratio on the mechanical properties of C–S–H gel can be C–S–H gel.
explained according to the physical properties of C–S–H gel
through the micro-poromechanical approach.

3.3. Relationship investigation between the physical and

mechanical properties
at the macro-scale through the fourth order localization
tensor Ar:
C–S–H gel is a porous material. For the C–S–H/CH composites
present in a cement paste matrix of mortar, a large variation εr ¼ E : Ar : ð11Þ
of indentation modulus of the C–S–H gels with the similar/
close Ca/Si ratio was observed, which indicates that the If the porous material subjected to a pore pressure p, the
mechanical properties of C–S–H gel with similar chemical local stress and strain relationship at the micro-scale can be
composition can be significantly influenced by the porosity. expressed by:
To study the poroelastic properties of C–S–H gel, micro- σr ¼ C r : εr þ σp : ð12Þ
poromechanics [23] was adopted in this study. Within the
framework of micromechanics [24], RVE (representative vol- Here, Cr is the elasticity tensor of phase r, and σp is the
ume element) of C–S–H gel is defined from a mechanical point eigenstress due to the pore pressure:
of view, as shown in Fig. 7. The stress Σ and strain E at the

macro-scale are described as the averages of the stress σ and −p1 ðporeÞ
σp ¼ : ð13Þ
strain ε at the micro-scale: 0 ðsolidÞ

∑ ¼ hσðzÞiV ; E ¼ hεðzÞiV ð9Þ By decomposing the loading (E, p) into two elementary
where, 〈〉V denotes the average over the whole volume V of loading (E, p = 0) and (E = 0, p), the macroscopic poroelasticity
RVE by: constitutive equations can be derived by:
Z
1
h f iV ¼ fdV: ð10Þ ∑ ¼ C hom : E−pB ð14Þ
V V
p
ϕ−ϕ0 ¼ B : E þ ð15Þ
For the linear elasticity, the strain (εr) in the solid N
phase r is uniformly distributed and related with the strain
where, Chom is homogenized elasticity tensor,

X
C hom ¼ f r C r : hAr iV r : ð16Þ
Table 3 – Summary of indentation modulus of inner r∈all
product and outer product in GPa.
C–S–H CP0.23 CP0.4 M0.35 M0.53 B is homogenized Biot coefficient,
OP Mean 28.9 25.2 26.5 20.8
S.D. 6.1 2.8 2.9 3.2 !
IP Mean 39.8 31.6 34.7 31.0
X
B¼1: 1− f r hAr iV r ð17Þ
S.D. 6.7 2.9 2.4 3.0 r∈solid
 M A TE RI A L S C HA RACT ER I ZA TI O N 95 ( 20 1 4 ) 1 2 9–1 3 9 135

and ϕ − ϕ0 is the change of porosity, which is related to the

pore pressure through homogenized Biot modulus N,

1 X  
hom
¼1: f r C r −1 : 1−1 : hAr iV r : ð18Þ
N r∈solid

For the isotropic material composed by the spherical parti-

cles, the fourth-order localization tensor can be decomposed
into the volumetric (Jijkl = 1/3δijδkl) and deviatoric (Kijkl = Iijkl − Jijkl)
parts:

ð1 þ α ðK r =K 0 −1ÞÞ−1
hAr iV r ¼
X ð1 þ βðGr =G0 −1ÞÞ−1
f r ð1 þ α ðK r =K 0 −1ÞÞ−1 J þ X
r∈all f r ð1 þ βðGr =G0 −1ÞÞ−1 K
r∈all
ð19Þ

with

3K 0 6ðK 0 þ 2G0 Þ
α¼ ; β¼ : ð20Þ
3K 0 þ 4G0 5ð3K 0 þ 4G0 Þ

Here, the subscript 0 represents the reference medium,

and K0 and G0 are the bulk modulus and shear modulus of the
reference medium, respectively; Kr, Gr and fr are the bulk
modulus, shear modulus and volume fraction of phase r
respectively. With the assumption that the three phases (CH,
pore and C–S–H) are disorderly distributed, self-consistent
scheme [25] was adopted to calculate the homogenized
poroelastic constants of C–S–H gel by assigning the reference
medium with K0 = Khom and G0 = Ghom. The Voigt–Reuss–Hill
(VRH) averages of isotropic elastic constants of individual
components are calculated using the stiffness tensor of
the single crystal [26]. The molecular simulation of the
realistic C–S–H model characterized by the chemical formula
C1.65SH1.75 (close to the chemical formula experimentally
determined by Allen et al. [20], C1.7SH1.8) gives the VRH
averages of elastic constants of C–S–H: KCSH = 49.2 GPa, and
GCSH = 22.7 GPa [27]. The molecular simulation of CH crystal
by density functional theory gives the VRH averages of elastic
constants of CH: KCH = 31.4 GPa, and GCH = 18.3 GPa [28]. The
elastic constants of pores are chosen as: if C–S–H gel subjects
to a pore pressure, Kp = 2.3 GPa and Gp = 0 GPa; otherwise,
Kp = 0 GPa and Gp =0 GPa [29].
Based on the micro-poromechanical calculation, when
there is no pore pressure in C–S–H gel, the plots of indentation
modulus versus the volume fraction of CH inclusion at the
different levels of porosity are shown in Fig. 8(a), while the
plots of indentation modulus versus porosity at the different
levels of the volume fraction of CH inclusion are shown in
Fig. 8(b). When C–S–H gel subjects to a pore pressure, the plots
of indentation modulus versus the volume fraction of CH
inclusion and porosity are shown in Fig. 9. From the results
shown in Figs. 8 and 9, it can be seen that the indentation
modulus of C–S–H gel is more sensitive to the porosity than
the volume fraction of the CH inclusion. The variations
of porosity and volume fraction of CH inclusion in C–S–H
gel result in the variations of poroelastic parameters of the
C–S–H/CH composites. The porosity and poroelasitc param-
eters of C–S–H gel present in CP0.4 are summarized in
Table 4. From Table 4, it can be seen that IP C–S–H gel has
Fig. 8 – Comparison between the experimental and predicted
indentation modulus of C–S–H gel as OP (○) and IP (4) present
in CP0.4 (Kp = 0 GPa).
lower porosity, higher elastic modulus, higher Biot coeffi-
cient, and lower Biot modulus than OP C–S–H gel.
From the C–S–H/CH composite present in cement paste
matrix of mortars with varying w/c ratio, the porosity and
poroelastic parameters are summarized in Table 5. The plots
of indentation modulus versus the volume fraction of CH
inclusion and porosity are shown in Fig. 10 for Kp = 0 GPa, and
Fig. 11 for Kp = 2.3 GPa. From the results in Table 5, it can be
seen that the higher w/c ratio leads C–S–H gel a higher
porosity, meanwhile a lower elastic modulus of C–S–H gel and
Biot modulus, a higher Biot coefficient.
The results in Tables 4 and 5 show that the pore pressure do
not significantly influence the porosity of C–S–H gel. Specially,
when there is no pore pressure in C–S–H gel, for C–S–H gel
present in CP0.4, the porosity distribution is drawn in Fig. 12(a).
By the deconvolution method introduced above, the average
porosity of inner product and outer product are obtained as
0.25 ± 0.02 and 0.31 ± 0.03 respectively, which are consistent
with the results listed in Table 5. Thus, the deconvolution
method was used to study the porosity of inner product and
outer product in other cementitious materials. For C–S–H gel
present cement paste matrix of M0.35, the porosity distribution
is shown in Fig. 12(b), where the average porosities of inner
product and outer product are obtained as 0.14 ± 0.05 and
0.26 ± 0.04, respectively; for C–S–H gel present in cement paste
matrix of M0.53, the porosity distribution can be found in
136 M A TE RI A L S C HA RACT ER I ZA TI O N 95 ( 20 1 4 ) 1 2 9–1 3 9

solid, intermixtures and pores. In cementitious composites,

CH occupies a wide range of sizes depending on the available
room for crystal growth of CH. At the micro-scale, a significant
proportion of CH nano- and micro-crystals form as the
inclusion or intermixture in C–S–H gel. On the other hand,
the pores present in cementitious composites, including gel
pores, capillary pores and others, occupy a large range starting
from the sub-nanometer level and have been studied in many
works, e.g., [30–32]. Additionally, the porosity, the volume
fraction of CH crystals, and their size distributions in
cementitious composites may vary with degree of hydration,
water to cement ratio, curing condition, incorporation of
mineral admixtures and other factors [33,34]. Thus, the pores
and CH crystals included in OP and IP C–S–H gels can
influence the physical and mechanical properties of C–S–H
gel, and the influences of the pores and CH crystals on the
microstructural physical and mechanical properties of C–S–H
gels may vary with degree of hydration, water to cement ratio,
curing condition, incorporation of mineral admixtures and
other factors. According to the findings of this work, the
methods to improve the macroscopic mechanical properties
of cementitious materials includes choosing lower water to
cement ratio, enhancing degree of hydration and incorporat-
ing mineral admixtures (e.g., silica fume). Lower water to
cement ratio or higher degree of hydration can lead to C–S–H
gel having lower porosity and higher mechanical proper-
ties [22]. The mineral admixtures can react with CH to
generate the secondary C–S–H and thus improve the pore
structure of C–S–H gel [17,22]. Thus, lower water to cement
ratio, higher degree of hydration and incorporation of mineral
Fig. 9 – Comparison between the experimental and predicted
admixtures (e.g., silica fume) can be used to improve the
indentation modulus of C–S–H gel as OP (○) and IP (4) present
mechanical properties of cementitious materials.
in CP0.4 (Kp = 2.3 GPa).

Fig. 12(c), where the average porosity of inner product and outer
product are obtained as 0.22 ± 0.06 and 0.35 ± 0.06, respectively.
By the statistical nanoindentation technique, conclusions were
drawn that the elastic properties of C–S–H gel do not depend on
the mix proportion, which only affects the volume fractions
[36]. While from this study, it is found that the average porosity
of inner product is significantly lower than that of outer
product, while they both vary with the w/c ratio. The w/c ratio
can significantly influence the porosity of C–S–H gel and further
the poroelastic properties of C–S–H gel.
3.4. Discussion
From the results presented in this work, at the scale of
interaction volume of nanoindentation/SEM–EDX on C–S–H
gel, C–S–H gel is a multi-scale composite composed by C–S–H
4. Conclusions
Through this study, nanoindentation coupled with SEM was
used to characterize the microstructural physical and me-
chanical properties of C–S–H gel present in cementitious
composites. The porosity and poroelastic parameters of C–S–H
gel present in cementitious composites with varying w/c ratio
were reported in this work and the following conclusions can
be drawn:
1. At the scale of interaction volume of SEM–EDX analysis on
the C–S–H gel, it is found that a higher w/c ratio leads to a
C–S–H gel having a lower Ca/Si ratio. The difference of the
Ca/Si ratio with varying w/c ratio indicates that the
intermixtures form more easily in C–S–H gel at low w/c
ratio.

Table 4 – Summary of porosity and poroelasitc parameters of C–S–H gel present in CP0.4.
C–S–H Pore pressure Porosity E (GPa) v B N (GPa)

OP No 0.31 ± 0.04 21.7 ± 4.3 0.25 ± 0.01 0.68 ± 0.08 124.1 ± 18.7
Yes 0.32 ± 0.04 21.3 ± 4.4 0.29 ± 0.00 0.66 ± 0.08 136.4 ± 20.7
Difference 3.2% −1.8% 16% −2.9% 9.9%
IP No 0.25 ± 0.05 27.9 ± 5.0 0.26 ± 0.01 0.58 ± 0.09 147.8 ± 30.3
Yes 0.27 ± 0.05 27.5 ± 5.1 0.28 ± 0.00 0.57 ± 0.09 161.6 ± 33.5
Difference 8.0% −1.4% 7.7% −1.7% 9.3%
 M A TE RI A L S C HA RACT ER I ZA TI O N 95 ( 20 1 4 ) 1 2 9–1 3 9 137

Table 5 – Summary of porosity and poroelasitc parameters of C–S–H gel present in cement paste matrix of mortars.
Sample Pore pressure Porosity E (GPa) v B N (GPa)

M0.23 No 0.14 ± 0.09 35.5 ± 8.8 0.26 ± 0.01 0.33 ± 0.19 272.0 ± 201.4
Yes 0.15 ± 0.09 35.3 ± 8.9 0.27 ± 0.01 0.32 ± 0.19 309.1 ± 238.1
Difference 7.1% −0.1% 3.9% −3.0% 13.6%
M0.35 No 0.23 ± 0.07 28.5 ± 7.7 0.25 ± 0.01 0.51 ± 0.15 171.2 ± 102.9
Yes 0.24 ± 0.08 28.2 ± 7.8 0.28 ± 0.01 0.49 ± 0.15 191.2 ± 119.4
Difference 4.4% −1.1% 12.0% −3.9% 11.7%
M0.53 No 0.28 ± 0.09 23.3 ± 8.6 0.24 ± 0.01 0.62 ± 0.18 135.4 ± 50.2
Yes 0.30 ± 0.09 22.9 ± 8.7 0.29 ± 0.01 0.61 ± 0.17 150.1 ± 55.9
Difference 7.1% −1.7% 20.8% −1.6% 10.9%

2. At the scale of interaction volume of nanoindentation on the
C–S–H gel, the average indentation modulus of OP C–S–H gel
may vary between 20.8 and 28.9 GPa, and that of IP C–S–H gel
may vary between 31.0 and 39.8 GPa, when the water to
cement ratio varies between 0.23 and 0.53. It is found that a
higher w/c ratio leads IP and OP C–S–H gels to have lower
elastic moduli.
3. The results show that C–S–H gel in cementitious compos-
ites is a multi-scale porous composite composed of C–S–H
solid, pore and the intermixtures. The physical and
mechanical properties of C–S–H gel can be influenced by
the porosity and volume fraction of the intermixtures. The
physical and mechanical properties were linked through
the micro-poromechanical approach.
4. From this study, it is found that the average porosity of
inner product is significantly lower than that of outer
product. The average porosity and poroelastic parameters
of C–S–H gel largely depend on the w/c ratio.
Acknowledgments
The financial supports from Hong Kong Research Grant
Council under the Grant of 615412 and China Ministry of

Fig. 10 – Comparison between the experimental and pre- Fig. 11 – Comparison between the experimental and pre-
dicted indentation modulus of C–S–H gel present in M0.23 (○), dicted indentation modulus of C–S–H gel present in M0.23 (○),
M0.35 (4) and M0.53 (□) (Kp = 0 GPa). M0.35(4) and M0.53(□) (Kp = 2.3 GPa).
138 M A TE RI A L S C HA RACT ER I ZA TI O N 95 ( 20 1 4 ) 1 2 9–1 3 9
Fig. 12 – Probability distribution of porosity of C–S–H/CH
composites present in CP0.4 (a), M0.35 (b) and M0.53 (c).
Science and Technology under the Grant of 2009CB623200 are
gratefully acknowledged.
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