Relation between Chemical Composition and Physical

Properties of C-S-H Generated from Cementitious Materials

Yuya Suda , TatsXhikR Saeki , Tsuyoshi Saito
Journal of Advanced Concrete Technology, volume 13 ( 2015 ), pp. 275

Nano-structural changes of C-S-H in Hardened Cement Paste during drying at 50°C

Yoshimichi Aono, Fumiaki Matsushita, Sumio Shibata, Yukio Hama
Journal of Advanced Concrete Technology, volume 5 ( 2007 ), pp. 313-323

Cement reaction and resultant physical properties of cement paste

Ippei Maruyama, Go Igarashi
Journal of Advanced Concrete Technology, volume 12 ( 2014 ), pp. 200-213
Journal of Advanced Concrete Technology Vol. 13, 275-290, May 2015 / Copyright © 2015 Japan Concrete Institute 275

Scientific paper

Relation between Chemical Composition and Physical Properties of

C-S-H Generated from Cementitious Materials
Yuya Suda1*, Tatsuhiko Saeki2 and Tsuyoshi Saito3

Received 5 September 2014, accepted 4 May 2015 doi:10.3151/jact.13.275

Abstract
Calcium silicate hydrate (C-S-H) is a dominant hydration product of cementitious materials. Therefore, its chemical
composition and physical properties affect the performance of concrete. The purpose of this study is to investigate the
chemical composition (CaO/SiO2 molar ratio (Ca/Si ratio), and H2O/SiO2 molar ratio (H2O/Si ratio)) and physical prop-
erties, such as density and specific surface area, of C-S-H. These factors are measured using synthesized C-S-H samples
and C-S-H generated from various cementitious materials. Experimental results show that the H2O/Si ratio of C-S-H is
proportional to the Ca/Si ratio independent of the mix proportion, curing temperature and type of binder. The density and
specific surface area of C-S-H are affected by its Ca/Si ratio. A linear relationship is observed between the Ca/Si ratio and
density of C-S-H independent of the mix proportion, curing temperature and type of binder. An inversely proportional
relationship is found between the Ca/Si ratio and specific surface area of C-S-H.

1. Introduction thesized C-S-H and that generated from various cemen-

Calcium silicate hydrate (C-S-H) is a dominant hydration
product of cementitious materials, hence its chemical
composition and physical properties also affect the
properties of concrete. However, the composition and
physical properties of C-S-H, and the relationship be-
tween these, have not been entirely clarified. To accu-
rately evaluate the performance of concrete, its physical
properties should be determined with high accuracy. In
particular, the strength, drying shrinkage and diffusion of
gases and ions such as CO2, O2 and Cl- of concrete are
controlled by its pore structure characteristics including
pore volume, size distribution and tortuosity. Pores are
formed in concrete by hydration products generated from
cementitious materials. The structural characteristics of
these pores are determined by the physical properties of
hydration products, such as density and specific surface
area. Therefore, it is important to clarify the chemical
composition and physical properties of C-S-H, which is a
dominant hydration product of cementitious materials.
The purpose of this study is to estimate the chemical
composition of C-S-H from its molar ratios of CaO/SiO2
(Ca/Si ratio) and H2O/SiO2 (H2O/Si ratio), and determine
its physical properties, such as density and specific sur-
face area. The relationship between the composition and
properties of C-S-H will also be investigated using syn-
1 cement (NC), moderate heat portland cement (MC), low
Assistant Professor, Department of Civil Engineering,
National Institute of Technology, Toyota College, Toyota
Japan. *Corresponding author,
E-mail: ysuda@toyota-ct.ac.jp
2 ratio of mineral admixture and curing temperature of
Professor, Department of Civil Engineering, Niigata
University, Niigata, Japan.
3
Associate Professor, Department of Civil Engineering,
Niigata University, Niigata, Japan.
titious materials.
2. Chemical composition of C-S-H
This section discusses the relationship between the Ca/Si
and H2O/Si ratios of C-S-H. It is known that the Ca/Si
and H2O/Si ratios of C-S-H are influenced by environ-
mental conditions such as temperature and humidity,
curing age, mix proportion and type of materials. In
general, the composition of C-S-H is expressed as
C1.70SH4.0 (Taylor 1997). The relationship between the
Ca/Si and H2O/Si ratios of C-S-H has also been ex-
pressed as CxSHx+0.63 (Fujii et al. 1983), CxSHx+1.70
(Taylor 1985), CxSHx+1.50 (Brouwers 2004) and
CxSH(19x-7)/17 (Richardson 2014). In addition, this rela-
tionship has been evaluated by experiments and nu-
merical calculation, such as molecular dynamics simu-
lation and thermodynamic modeling (Kulik 2011; Ab-
dolhosseini et al. 2014). However, the relationship be-
tween the Ca/Si and H2O/Si ratios varies among these
studies. In addition, the effects of various conditions such
as type of binder, mix proportion and curing conditions
on the composition of C-S-H were not clarified.
Therefore, the purpose of this section is to clarify the
effect of various conditions on the Ca/Si and H2O/Si
ratios of C-S-H. In this study, C-S-H and alite (C3S) were
synthesized to evaluate the composition of C-S-H.
Various cement pastes, consisting of ordinary portland
heat portland cement (LC), blast furnace slag (BFS), fly
ash (FA) and silica fume (SF), were also used. The ef-
fects of changing the water-to-binder ratio, replacement
cement paste were investigated.
Y. Suda, T. Saeki and T. Saito / Journal of Advanced Concrete Technology Vol. 13, 275-290, 2015 276

Table 1 Chemical composition of binders.

Density Blaine LOI Chemical composition (%)
(g/cm3) (cm2/g) (%) SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O K2O
C3S 3.17 3040 -0.28 24.8 1.2 0.5 72.2 1.0 - 0.1 0.1
NC 3.16 3480 0.16 21.4 5.3 2.7 65.0 1.5 2.1 0.3 0.5
MC 3.21 3210 0.11 23.5 3.7 4.2 64.0 0.9 2.4 0.3 0.4
LC 3.22 3400 0.37 26.5 2.6 2.9 63.0 0.7 2.6 0.2 0.3
BFS 2.88 3960 -0.53 35.8 14.2 - 42.8 5.4 2.2 0.3 0.3
FA-A 2.14 3500 1.80 56.7 27.6 4.4 3.6 1.2 - 0.5 0.5
FA-B 2.20 3840 3.25 73.8 17.9 3.3 1.0 1.2 0.4 0.4 0.4
SF-A 2.20 - 2.89 96.5 0.5 0.1 0.4 0.4 - 0.2 0.9
SF-B 2.20 - 1.21 89.3 0.3 1.0 0.7 - 0.4 0.9 3.0

Table 2 Mineral composition of each (a) cement and (b) FA.

(a) C3S C2S C3A C4AF Gypsum Bassanite Calcite Periclase
NC 58.2 19.2 9.5 9.3 0.1 1.8 0.4 0.8
MC 40.2 39.6 5.2 10.6 0.2 2.5 1.1 0.2
LC 22.2 63.2 4.4 6.3 1.4 1.9 0.4 0.3

(b) Mulite Quartz Magnetite Gypsum Calcite Glass

FA-A 22.9 9.8 0.5 2.3 0.1 64.4
FA-B 9.8 13.8 0.7 2.1 0.1 73.6

Table 3 Chemical composition (%) of glass in FA.

SiO2 Al2O3 Fe2O3 CaO MgO Na2O K2O
FA-A 66.0 18.3 4.7 4.2 2.0 0.8 0.8
FA-B 77.9 14.8 2.7 0.1 1.6 0.5 0.5

2.1 Experimental procedure
2.1.1 Materials
Four C-S-H samples with a wide range of Ca/Si ratios
were synthesized. The target Ca/Si ratios were 0.80,
1.00, 1.25 and 1.50. C-S-H samples were synthesized by
reacting calcium hydroxide, ethyl silicate and water for
2 days at 40 °C. Solid and aqueous phases were then
separated by filtration. The concentrations of Ca and Si
in the aqueous phase were measured by EDTA titration
and spectrophotometer. Therefore, Ca/Si ratios were
determined from the concentrations of Ca and Si in the
aqueous phase before and after synthesis of C-S-H.
Alite (C3S) was synthesized by reference to the
chemical composition reported by Yamaguchi and Ta-
kagi (Yamaguchi and Takagi 1969). The chemical for-
mula of alite (Ca106Mg2(Na1/4K1/4Fe1/2)O36(Al2Si34O144))
reported by Yamaguchi and Takagi is shown in Table 1.
Alite was synthesized by conducting calcination 3 times
in an electric furnace at the temperature of 1600 °C for 3
h. The amount of CaO in the synthesized alite was
measured by the ethylene glycol method. The quantita-
tive value of CaO was 0.47%. In addition, it was con-
firmed through measurement by powder X-ray diffrac-
tion (XRD) that the synthesized alite was pure tricalcium
silicate, and it was evaluated to have been properly
synthesized in this study. The physical properties (den-
sity and Blaine fineness) are shown in Table 1.
NC, MC and LC were used as cement paste samples.
In addition, NC was also replaced by BFS, two types of
FA (FA-A and FA-B) and two types of SF (SF-A and
SF-B). The physical properties and chemical composi-
tions of each binder are listed in Table 1. The mineral
compositions of NC, MC, LC and FA were measured by
the XRD/Rietveld method (Table 2). The chemical
composition of glass in FA was calculated from the
chemical and mineral compositions of FA (Table 3).
2.1.2 Mix proportion and curing conditions
The experimental conditions used for the cement paste
samples are shown in Table 4. Each sample was mixed
for 3 min. Samples were remixed regularly to prevent
bleeding. After mixing, each sample was placed in a
plastic bottle (φ32×65 mm), and then cured at a specified
temperature (5, 20 or 40°C) for 1, 3, 7, 28 or 91 days for
C3S, and 1, 3, 7, 28, 91, 182 or 365 days for cement.
2.1.3 Pretreatment and drying condition
After each curing period, C3S paste and cement paste
samples were broken into small pieces, and immersed in
acetone for 2 days to prevent further hydration. Synthe-
sized C-S-H was also immersed in acetone for 2 days.
Samples were dried under decompression by aspirator at
0.1 kPa for 6 h to vaporize acetone. Moreover, these
samples placed in a vacuum desiccator in the presence of
silica gel at 0.1 kPa for 3 days to completely dry acetone.
The dried C3S paste and cement paste samples were
crushed into particles smaller than 90 μm. Samples were
then dried at 20°C-11% RH (using saturated LiCl solu-
Y. Suda, T. Saeki and T. Saito / Journal of Advanced Concrete Technology Vol. 13, 275-290, 2015 277

Table 4 Experimental conditions and measured properties.

Experimental conditions Measured properties
Binder W/B (%) Replacement ratio (%) Temp. (°C) Composition Density Specific surface area
C3S 30 - 20 ○ ○ ○
- 5 ○ ○ ○
40 - 20 ○ ○ ○
- 40 ○ ○ ○
50 - 20 ○ ○ ○
NC 35 - 20 ○ ○ ○
40 - 20 ○
45 - 20 ○ ○ ○
- 5 ○ ○
55 - 20 ○ ○ ○
- 40 ○ ○
65 - 20 ○ ○
MC 40 - 20 ○
55 - 20 ○ ○ ○
LC 40 - 20 ○
55 - 20 ○ ○ ○
NC-BFS 45 50, 70 20 ○ ○
55 35, 50, 70 20 ○ ○ ○
65 50, 70 20 ○ ○
NC-FA-A 45 15, 30 20 ○ ○
55 15, 30 20 ○ ○ ○
65 15, 30 20 ○ ○
NC-FA-B 55 15, 30 20 ○ ○
NC-SF-A 45 4, 8 20 ○ ○
NC-SF-B 45 4 20 ○ ○

tion) in a vacuum desiccator for 1-2 weeks at 0.1 kPa or
oven-drying at 110°C for 1-3 days until the mass no
longer changed. In order to prevent carbonation, soda
lime was placed in each vacuum desiccator. In this study,
drying at 110°C is defined as 0% RH.
2.1.4 Analysis
(1) Thermogravimetric analysis
The amount of combined water in the dried samples was
measured by thermogravimetric analysis (TGA). The
amount of combined water in the samples dried at 11%
RH was calculated from their weight reduction upon
heating from 50 to 1000°C, while that in the sample dried
at 0% RH was calculated from the weight reduction from
110 to 1000°C. To prevent the oxidation of sulfide in
BFS, the highest temperature investigated for the hy-
drated samples containing BFS was 900°C. The amount
of calcium hydroxide in each sample was determined
from the mass loss between 415 and 500°C.
(2) XRD/Rietveld method
The amounts of unhydrated clinker and hydration prod-
ucts were measured by the XRD/Rietveld method.
Samples dried at 11% RH were used in XRD experi-
ments. α-Al2O3 (10 mass%) was mixed with each sample
as an internal standard. XRD patterns were measured
using a tube voltage of 40 kV, tube current of 40 mA,
scan range of 2θ=5 to 70°, step width of 0.02°, and scan
rate of 2°/min. The software used for Rietveld analysis
was Topas4.2 (Bruker AXS). The target substances for
quantification were alite (C3S), belite (β-C2S), aluminate
phase (cubic-C3A and orthorhombic-C3A), ferrite phase
(C4AF), portlandite (Ca(OH)2), ettringite
(C6Ax3SO3xH32), monosulfate (C4AxSO3xH12), hydro-
garnet (C3AH6), calcite (CaCO3), periclase (MgO), lime
(CaO), gypsum (CaSO4x2H2O), bassanite
(CaSO4x0.5H2O), and corundum (α-Al2O3). In NC-BFS
samples, hydrotalcite (M6AxCO3xH12) was added as a
target substance for quantification. Moreover, for NC-FA
samples, quartz (SiO2), mullite (Al6O13Si2) and magnet-
ite (Fe3O4) were added as target substances for quanti-
fication. The amount of amorphous phase was calculated
using Eq. (1) from the quantitative value of the internal
standard (α-Al2O3).
100 ⋅ (A − R) 100
G= ⋅ (1)
A 100 − R
where G is the amount of amorphous phase (%), R is the
amount of α-Al2O3 (%), and A is the value measured for
α-Al2O3 (%). Previous results noted that the amount of
calcium hydroxide measured by TGA was higher than
that measured by XRD using an internal standard. This is
because calcium hydroxide contains the amorphous
phase (Bentur et al. 1979; Ramachandran 1979; Esca-
lante-Garcia et al. 1999). From these studies, the amount
of calcium hydroxide in each sample was measured by
TGA in this study.
Y. Suda, T. Saeki and T. Saito / Journal of Advanced Concrete Technology Vol. 13, 275-290, 2015
(3) Heat-treated XRD/Rietveld method
The amount of unhydrated BFS was measured by the
heat-treated XRD/Rietveld method (Sagawa et al. 2006).
The hydrated sample dried at 11% RH was fired at 900°C
for 30 min to crystallize the amorphous phase of unhy-
drated BFS. The amount of unhydrated BFS was then
measured by the XRD/Rietveld method. The target sub-
stances for quantification were gehlenite (Ca2Al2SiO2),
akermanite (Ca2MgSi2O7), merwinite (Ca3MgSi2O8) and
α’-C2S. The reaction ratio of BFS was calculated using
Eq. (2):
⎡ a+b+c ⎤
Fa = ⎢1 − ⎥ ⋅100
⎢⎣ M ⋅ (1 − I g ) ⎥⎦
where Fa is the reaction ratio of BFS (%), a, b and c are
the quantitative values of gehlenite, akermanite and
merwinite, respectively, M is the replacement ratio of
BFS, and Ig is the loss on ignition of unhydrated BFS.
(4) Selective dissolution method
The amount of unhydrated FA and SF was measured by
the selective dissolution method (Ohsawa et al. 1999). A
hydrated sample (1 g) dried at 11% RH was added to a
centrifuge tube containing aqueous HCl (2N, 30 mL).
The hydrated sample was shaken for 15 min in a water
bath at 60°C. The sample was separated by centrifuga-
tion, and then the sample was washed with hot water. The
tube containing the sample was filled with aqueous
Na2CO3 (5wt%, 30 mL), and then shaken for 20 min in a
water bath at 80 °C. The sample was separated by cen-
trifugation and then washed with hot water. The residue
was dried at 110°C. The reaction ratio of FA or SF was
calculated from Eq. (3):
⎡ X '(1 − I g ') / k2 ⎤
Fb = ⎢1 − ⎥ ⋅100
⎣⎢ (1 − I g )k1 ⎦⎥
where Fb is the reaction ratio of FA or SF, k1 is the re-
placement ratio of FA or SF, k2 is the residue extracted of
unhydrated FA or SF, X’ is the residue extracted of hy-
drated FA or SF, Ig is the loss on ignition of the hydrated
sample, and Ig’ is the loss on ignition of the extracted
residue.
Ca(OH) 2 Ca(OH)
Ca(OH) 2 2 1.50
1.25
1.00
0.80
Silica gel
5 15 25 35 45 55
2θ /degree
Fig. 1 XRD patterns of synthesized C-S-H.
278
Table 5 Composition of synthesized C-S-H.
Target Obtained Obtained Obtained
Ca/Si ratio Ca/Si ratio H2O/Si ratio*1 H2O/Si ratio*2
0.80 0.80 0.63 1.31
1.00 0.99 0.67 1.41
1.25 1.24 0.92 1.79
1.50 1.40*3 1.25 1.98
*1 Drying conditions: 0% RH (110 °C dry)
*2 Drying conditions: 11% RH (saturated LiCl solution)
*3 Quantitative value of calcium hydroxide is 4.81wt. %.
2.2 Experimental results
(2) 2.2.1 Composition of synthesized C-S-H
Figure 1 shows the XRD patterns of four synthesized
C-S-H samples and silica gel synthesized from ethyl
silicate. A peak from silica gel at 21° (2θ) was not ob-
served in the patterns of C-S-H. When the Ca/Si ratio
was 1.50, a peak was observed at 18° (2θ) from calcium
hydroxide. Therefore, the amount of calcium hydroxide
in C-S-H with a Ca/Si ratio of 1.50 was measured by
TGA, as shown in Table 5.
2.2.2 Relation between the Ca/Si and H2O/Si
ratios of C-S-H
Figure 2 show the relationship between the reaction ratio
and amount of combined water in C3S paste dried at RH
of 0% and 11%. The amount of combined water in ce-
ment paste is generally used to indicate the development
of hydration (Nagamatsu et al. 1986). Linear relation-
ships are observed between the reaction ratio and com-
bined water of C3S pastes independent of the wa-
ter-to-binder ratio and curing temperature. Therefore, the
chemical equation of hydration of C3S can be written as:
a ⋅ C3 S + b ⋅ H → a ⋅ ( C3 SH n ) → a ⋅ ( C p SH q ) + c ⋅ CH (4)
(3) where n is calculated from the slope of the graph in Fig. 2
(n=b/a). In this study, n was 2.65 for 0% RH and 3.47 for
11% RH. The Ca/Si ratio (p) and H2O/Si ratio (q) of
C-S-H were calculated from the reaction ratio and
amount of calcium hydroxide in C3S paste. In addition,
the H2O/Si ratio (q) can be formulated as a function of
the Ca/Si ratio from p=3-c/a and q=n-c/a, hence the
relationship between the Ca/Si and H2O/Si ratios can be
written as:
q = p + ( n − 3) (5)
The composition of C-S-H obtained from these
chemical equations is the temporal and spatial mean for
C-S-H generated from the beginning of hydration until a
specified age.
Figure 3 shows the relationships between the Ca/Si
and H2O/Si ratios of synthesized C-S-H generated from
C3S under RH of 0% and 11%, and the previous results
(Cong et al. 1996; Thomas et al. 2003; Richardson 2014).
65 The relationships between the Ca/Si and H2O/Si ratios
calculated from Eq. (5) are consistent with the results
obtained for C-S-H synthesized at RH of 0% and 11%.
Y. Suda, T. Saeki and T. Saito / Journal of Advanced Concrete Technology Vol. 13, 275-290, 2015 279

3.0 Table 6 Composition of hydration products under different

Sy nthesized C-S-H (0% RH)
Sy nthesized C-S-H (11% RH)
drying conditions.
2.5
H2 O/Si ratio (mol/mol)

X. Cong et al. Drying Molar mass

Thom as et al. (D-dry ) Composition
2.0 conditions (g/mol)
Eq. (5) 11% RH 56.1x+60.1
1.5 1000 °C CxSH0
56.1x+60.1+18(x-0.35)
C-S-H 0% RH CxSHx-0.35
56.1x+60.1+18(x+0.47
1.0 Richardson 2014 11% RH C xSH x+0.47
)
0.5 1000 °C CaO 56.1
Eq. (5) 0% RH
CH 0% RH Ca(OH)2 74.1
0.0 11% RH Ca(OH)2 74.1
0.6
1.0 1.2 1.4 1.6 1.8 2.0 0.8 1000 °C C6Ax3SO3xH0 678.6
Ca/Si ratio (mol/mol) AFt 0% RH C6Ax3SO3xH7 803.9
Fig. 3 Relationship between Ca/Si and H2O/Si ratios of 11% RH C6Ax3SO3xH32 1254.8
C-S-H. 1000 °C C4AxSO3xH0 406.3
AFm 0% RH C4AxSO3xH9 568.4
Thus, there is a linear relationship between the Ca/Si and 11% RH C4AxSO3xH12 621.7
H2O/Si ratios of C-S-H. In addition, the slopes obtained 1000 °C C3AH0 270.2
HG 0% RH C3AH6 378.2
from Eq. (5) show the same tendency as the results of
11% RH C3AH6 378.2
previous studies, especially research on C-S-H dried at
1000 °C C4AH0 325.9
0% RH (Thomas et al. 2003; Richardson 2014). In par- CAH 0% RH C4AH10 506.5
ticular, the relation between the Ca/Si ratio and H2O/Si 11% RH C4AH13 559.1
ratio reported by Thomas et al. is the result of D-dried 1000 °C C3FH0 327.9
C-S-H, and that reported by Richardson is the results of CFH 0% RH C3FH6 436.0
C-S-H based on structure model. The structure model is 11% RH C3FH6 436.0
based on C-S-H dried to the greatest possible extent 1000 °C M6AxCO3xH0 343.9
without collapsing the tobermorite-like structure. It can HT (BFS) 0% RH M6AxCO3xH12 604.2
probably be agreed that the relation between Ca/Si ratio 11% RH M6AxCO3xH12 604.2
and H2O/Si ratio of C-S-H with tobermorite-like struc- * CH: Calcium hydroxide, AFt: Ettringite, AFm: Monosul-
ture was properly assessed in this study. fate, HG: Hydrogarnet, CAH: C4AH13, CFH: C3FH6, HT:
Hydrotalcite
2.2.3 Relationship between Ca/Si and H2O/Si
ratios in C-S-H (Maruyama and Igarashi 2014).
The accuracy of the linear relationship between the Ca/Si A flowchart of the method used to calculate the
and H2O/Si ratios of C-S-H obtained using synthesized amount of hydration products from the mass balance is
C-S-H and C3S paste was evaluated by the composition presented in Fig. 4. Table 6 shows the composition of
of C-S-H generated from various cement pastes (Table each hydration product considered as a target substance
4). To evaluate the amount of hydration products in ce- for quantification of the mass balance. The hydration
ment paste and quantify unmeasured hydration products products measured by Rietveld analysis and TGA were
such as C2AH8, C4AH13 and C3FH6, the amount of hy- converted to anhydrites, and then the mass balance be-
dration products in various cement pastes was calculated tween starting materials and hydration products was
by mass balance in accordance with previous research calculated. The amounts of CAH and CFH were then

30 30
W/B: 30% 20 ºC
Amount of combined water

Amount of combined water

(% of binder at 11% RH)
(% of binder at 0% RH)

25 W/B: 40% 20 ºC 25
W/B: 50% 20 ºC
20 W/B: 40% 40 ºC 20
W/B: 40% 40 ºC
15 15

10 10 y=0.273x
y=0.201x 2
5
2
R : 0.971 5 R : 0.984
n: 2.65 n: 3.47
0 0
0 20 40 60 80 100 0 20 40 60 80 100
Reaction ratio of C3 S (% of binder) Reaction ratio of C3S (% of binder)
(a) 0% RH (b) 11% RH
Fig. 2 Relationship between reaction ratio of C3S and amount of combined water. (a) 0% RH, dry sample, (b) 11% RH, dry
sample.
Y. Suda, T. Saeki and T. Saito / Journal of Advanced Concrete Technology Vol. 13, 275-290, 2015
[No. 1] Amount of hydration products, unhydrated
clinker and admixture measured by XRD/Rietveld,
TGA and selective dissolution methods
[No. 2] Convert hydration product into anhydrite
[E.g. Ca(OH)2 ⇒CaO]
[No. 3] Calculate amount of hydration clinker and
admixture [C3S, C2S, C3A, C4AF, BFS, FA, SF]
[No. 4] Calculate amount of reacted oxides in
hydration clinker and admixture (CaO, SiO2, Al2O3,
Fe2O3) and amount of consumed oxides in hydra-
tion products (CaO, Al2O3)
Fig. 4 Flow chart showing method used to calculate mass balance.
determined from the amount of residual oxides (Al2O3
and Fe2O3) that were not consumed as hydration products
(CH, AFt, AFm, C3AH6 and HT (BFS)). The amount of
C-S-H and the Ca/Si ratio was determined from the re-
sidual CaO and SiO2 that were not consumed as hydra-
tion products (CH, AFt, AFm, C3AH6, HT (BFS), CAH
and CFH). The amount of combined water in each hy-
dration product was determined from the composition of
each hydration product (Table 6). In this study, the
chemical compositions of CAH and CFH were assumed
to be C4AH13 and C3FH6, respectively. Therefore, the
amount of combined water in each cement paste sample
calculated from the composition of hydration products
was compared with the amount of combined water de-
termined by TGA. The amount of combined water in
C-S-H was calculated from Eq. (5) by considering the
effect of the Ca/Si ratio.
It is reported that the Ca/Si ratio of C-S-H generated
from BFS and FA is lower than that generated from
Portland cement. The Ca/Si ratio generated from Port-
land cement is approximately 1.70 (Taylor, 1997). The
Ca/Si ratio generated from BFS is approximately 1.00
(Richardson and Groves, 1992; Thomas et al. 2012).
Measurements using a scanning electron microscope
(SEM) and transmission electron microscope (TEM)
revealed that C-S-H with various Ca/Si ratios are dis-
tributed in blended cement paste (Taylor et al. 2010).
However, the chemical composition of C-S-H generated
from NC-BFS, NC-FA and NC-SF is expressed as a
mean value in this study. For this reason, the C-S-H
generated from each material, such as NC, BFS and FA,
cannot be distinguished with this calculation method of
phase composition. On the other hand, Richardson and
Groves found that the mean value of Si/Ca ratio and
Al/Ca ratio of C-S-H in NC-BFS paste measured by
280
[No. 5] Calculate mass balance of Al2O3 and Fe2O3 between hydra-
tion clinker and admixture and hydration products
[C-A-H and C-F-H were assumed to be C4AH13 and C3FH6]
[No. 6] Calculate mass balance of CaO and SiO2 between hydration
clinker, admixture and hydration products
[No. 7] Calculate amount of C-S-H and Ca/Si ratio
[No. 8] Calculate mass balance between hydration clinker, admixture
and hydration products
[No. 9] Determine amount of combined water at 0% and 11% RH
from composition of hydration products in Table 6
[No. 10] Determine amount of hydration products at 0% and 11%
TEM is a linear relation (Richardson and Groves 1993).
Sasaki and Saeki reported that the relation between Ca/Si
and adsorbed chloride ion of synthesized C-S-H shows
the same tendency as that of NC paste, NC-BFS paste,
and NC-FA paste (Sasaki and Saeki 2006). Moreover, a
linear relation between the Ca/Si ratio and H2O/Si ratio
was obtained from this study. This allows the water
content of C-S-H with various Ca/Si ratios in cement
paste to be evaluated from the mean Ca/Si ratio. Even
though the chemical composition of C-S-H is evaluated
by mean value, this calculation method of phase com-
position can reflect the difference of chemical composi-
tion of C-S-H. The evaluation of mean value is simple
and easily handled in engineering. Therefore, in subse-
quent studies, the chemical composition of C-S-H is
expressed by the mean value.
Figure 5 shows the changes in phase composition of
the various cement pastes at each age. In these figures,
C-S-H can be seen to be the most abundant of the hy-
dration products. In addition, when mineral admixtures
were used, the amount of calcium aluminate hydrates
increased in the hydration products. The Ca/Si ratio of
C-S-H in various cement pastes is illustrated in Fig. 6.
The Ca/Si ratio of C-S-H in NC-BFS and NC-FA pastes
is also affected by the water-to-binder ratio and curing
age. In addition, when the same admixture was used, the
Ca/Si ratio in each sample decreased as the replacement
ratio increased. The tendencies of the NC-BFS and
NC-FA pastes are the same as those reported previously
(Richardson and Groves 1992; Sakai et al. 2004; Girão et
al. 2010).
Figure 7 compares the calculated and experimental
values for the amount of combined water in cement
pastes containing NC, MC, LC, BFS, FA and SF. The
calculated values agree well with the experimental values.
Y. Suda, T. Saeki and T. Saito / Journal of Advanced Concrete Technology Vol. 13, 275-290, 2015 281

1.0
CSH
CFH
Phase composition (g/g)

0.8
CAH
HT
0.6 HG
AFm
0.4 AFt
CH
0.2 FA, BFS
Cement
0.0
1
3 7 28 91 365 1 3 7 28 91 365 1 3 7 28 91 365 1 3 7 28 91 365
Age (days) Age (days) Age (days) Age (days)
(a) (b) (c) (d)
Fig. 5 Change in the phase compositions at each age (a) NC, W/B=55%, Curing temperature 20 ºC (b) LC W/B=55%,
Curing temperature 20 ºC (c) NC+FA, W/B=55%, Replacement ratio of FA=15%, Curing temperature 20 ºC (d) NC+BFS,
W/B=55%, Replacement ratio of BFS=50%, Curing temperature 20 ºC.

This confirms that the H2O/Si ratio of C-S-H is propor- 1.8

28d 91d 365d NC
tional to the Ca/Si ratio independent of mix proportion, BFS 50%
curing temperature and type of binder. Ca/Si ratio (mol/mol) 1.6 BFS 70%
FAA15%
Although, in the case of the use of mineral admixture
such as BFS, FA or metakaolin, it is known that Si in 1.4 FAA30%

C-S-H was substituted for Al (Richardson and Groves Replacement

1.2
1992). In this study, the effect of Al substituted C-S-H ratio
(named as C-A-S-H) was not taken into consideration. 1.0
Accordingly, in order to evaluation the effect of Si-Al
substitution in C-A-S-H for phase composition, a part of 0.8
Si in C-S-H was made to substitute Al. For the calcula- 45 55 65 45 55 65 45 55 65
tion method, after SiO2 (molar) was calculated by mass W/B (%) W/B (%) W/B (%)
balance in the flow chart [No. 6] in Fig. 4, Al was added Fig. 6 Ca/Si ratio of C-S-H in different cement pastes.
to Si. Once more, the phase compositions were deter-
mined by mass balance. The additive rate of Al (molar) comparison between the calculated values as Al substi-
was 10 % (BFS) or 7 % (NC, MC and LC) of Si (molar), tuted C-S-H and calculated values as C-S-H for the
based on previous research results (Richardson and amount of combined water in cement pastes. As shown in
Groves. 1992; Girão et al. 2007). Figure 8 shows the Fig. 9, the correlation factor is 0.968. The calculated
relation between the Al/Ca molar ratio and Si/Ca molar value as C-A-S-H is in good agreement with the calcu-
ratio. The Al/Ca molar ratio increases with increasing lated value as C-S-H. Hence, it is thought that the phase
Si/Ca molar ratio. The relation in this study shows the compositions are seldom affected by Al substituted
same tendency as the results of previous research C-S-H.
(Richardson and Groves, 1993). Figure 9 shows the

40 N40 20 ºC 40 BFS35%
Combined water (%) -test-

BFS50%
Combined water (%) -test-

N55 20 ºC
M40 20 ºC BFS70%
30 30
M55 20 ºC FAA15%
L40 20 ºC FAA30%
L55 20 ºC 20 FAB15%
20
N55 5 ºC FAB30%
N55 40 ºC SFA4%
10 10 SFA8%
W/B Temp. SFB4%
R: 0.977 R: 0.940
0 0 Replacement
0 10 20 30 40 0 10 20 30 40 ratio
Combined water (%) -calculated- Combined water (%) -calculated-
(a) (b) BFS, FA, SF
Fig. 7 Comparison of calculated and experimental values of combined water in each cement paste. (a) NC, MC and LC
paste dried at 11% RH, (b) NC-BFS, NC-FA and NC-SF paste dried at 11% RH.
Y. Suda, T. Saeki and T. Saito / Journal of Advanced Concrete Technology Vol. 13, 275-290, 2015
0.35
Richardson
0.30
NC-BFS (Al/Si: 10%)
Al/Ca ratio (mol/mol)
0.25
NC, MC, LC (Al/Si: 7%)
0.20
0.15
0.10
0.05
0.00
0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2
Si/Ca ratio (mol/mol)
Fig. 8 Relationship between Si/Ca and Al/Ca ratios of
C-S-H.
3. Physical properties of C-S-H
In this section, the density and specific surface area of
C-S-H are evaluated. Previous research reported that the
density of C-S-H is influenced by its composition
(Beaudoin et al. 1978). However, the density of C-S-H
reported in the literature varies widely because of dif-
ferent drying conditions (Skalny et al. 1980; Taylor
1997; Bentz et al. 1997). Moreover, the relationship
between the composition and density of C-S-H is not
fully understood. With regard to the specific surface area
of C-S-H, it is known that a lower Ca/Si ratio tends to
lead to a higher specific surface area (Beaudoin et al.
1978; Sasaki et al. 2006). However, these tendencies
were observed in results obtained for synthesized C-S-H
studied by nitrogen adsorption. The properties of C-S-H
in cement paste have not been studied sufficiently. In
addition, it has been reported that specific surface areas
obtained with the nitrogen absorption method differ from
those obtained with the water adsorption method (Dai-
mon et al. 1976; Jennings 2000; Odler 2003).
Therefore, the purpose of this study is to obtain fun-
damental data about the density and specific surface area
of C-S-H. The samples for measurement were synthe-
sized hydration products, C3S paste and various cement
pastes.
3.1 Experimental procedure
3.1.1 Materials, mixture and curing conditions
C-S-H, ettringite, monosulfate, C3AH6 and C4AH13 were
synthesized for subsequent measurement. The method
used to synthesize C-S-H is described in Section 2.1.1.
Ettringite and monosulfate were synthesized by reac-
tion of C3A and CaSO4x2H2O. C3A was first prepared by
mixing CaCO3 and Al2O3 in the molar ratio of 3:1, and
then firing at 1400°C for 3 h in an electric furnace. Et-
tringite and monosulfate were then synthesized by mix-
ing C3A and CaSO4 ⋅ 2H2O in the molar ratios of 1:3 and
1:1, respectively, with a water-to-solid ratio of 10. Sam-
ples were cured for 14 days at 20°C.
C3AH6 was synthesized by reaction of C3A and water
with a water-to-solid ratio of 1.0. Samples were cured for
28 days at 40°C.
282
40
NC , MC , LC , BFS
-calculated for C-A-S-H-
Combined water (%)
30
20
10
R: 0.968
0
0 10 20 30 40
Combined water (%) -calculated for C-S-H-
Fig. 9 Comparison of calculated (as C-S-H or C-A-S-H)
values of combined water in each cement paste.
C4AH13 was synthesized according to a reported
method (Werner 1967) by mixing NaAlO2 and CaO with
the molar ratio of 1:2 in water with the water-to-solid
ratio of 10.0. Samples were cured for 28 days at 20 °C.
The density and specific surface area of commercial
calcium hydroxide (Kanto Chemical Co., Inc.) and hy-
drotalcite (Wako Pure Chemical Industries, Ltd.) were
also measured.
Table 4 shows the combination of measurement items
of density and specific surface area of the C3S paste and
cement paste samples. Hydrated samples for density
measurement were cured for 28 and 91 days, whereas
samples for specific surface area measurement were
cured for 1, 3, 7, 28, 91, 182 and 365 days.
3.1.2 Analysis
(1) Density of synthesized hydration products and
cement pastes
The synthesized hydration products and cement pastes
samples were dried at 11% RH and then crushed into
particles smaller than 90 μm. The crushed cement paste
samples were also finely milled, and dried again at 11%
RH before their density was measured using a gas
pycnometer with helium gas.
(2) Porosity of cement pastes
Hardened cement paste samples cured for 1, 3, 7, 28, 91,
182 and 365 days were broken into pieces of about 5 mm
to measure porosity. Porosity was calculated from the
weight difference between saturated surface-dried sam-
ples and those dried at 50°C for 3 days. These hydrated
samples were saturated by pouring water over them un-
der reduced pressure. After saturation, the surface water
was removed from saturated samples by wiping.
(3) Specific surface area of synthesized hydration
products and cement pastes
The specific surface areas of the synthesized hydration
products and cement paste specimens were calculated
from the amount of water adsorbed at RH of 11%, 22%
and 33%, as determined by gravimetric analysis. Sam-
ples were prepared by crushing them into particles
smaller than 90 μm. Samples were dried at 0% RH until
Y. Suda, T. Saeki and T. Saito / Journal of Advanced Concrete Technology Vol. 13, 275-290, 2015 283

Table 7 Physical properties of synthesized hydration products.

Density (g/cm3) Specific surface area (m2/g)
This study Taylor (1997) Balonis (2009) This study
0.80 1.60 - - 332.5
0.99 1.73 - - 284.6
C-S-H
1.24 1.96 - - 214.3
1.40 2.04 - - 192.9
Calcium hydroxide 2.24 2.24 2.25 19.0
Ettringite 1.78 1.78 1.78 194.5
Monosulfate 2.05 2.01 2.02 207.3
Hydrogarnet 2.50 2.53 2.53 12.0
C4AH13 2.08 2.05 2.04 199.3
Hydrotalcite 2.00 - 1.95 102.9

their water vapor sorption was measured. LiCl (11% RH),
CH3COOK (22% RH) and MgCl2 ⋅ 6H2O (33% RH)
were used as saturated salts. The specific surface area of
each sample was calculated by the BET method (Brun-
auer et al. 1938).
To evaluate the specific surface area of C-S-H, the
total amount of combined and adsorbed water in C3S
paste at each RH was calculated by adding the amount of
water adsorbed at RH of 11%, 22% and 33% to the
amount of combined water in each sample at 0% RH. A
model of the combined water + adsorbed water in a
sample under each RH is shown in Fig. 10.
3.2 Experimental results
3.2.1 Density of synthesized hydration products
The density of synthesized hydration products are pre-
sented in Table 7. When the Ca/Si ratio of synthesized
C-S-H decreased, the density of C-S-H also decreased.
The densities of ettringite, monosulfate, hydrogarnet and
C4AH13 are consistent with those reported previously
(Taylor 1997; Balonis et al. 2009).
admixtures and hydration products in cement paste were
calculated from the mass balance described in Section
2.2.3. The density of C3FH6 was assumed to be 2.81
g/cm3 (Balonis et al. 2009).
The relationships between the density and Ca/Si ratio
of C-S-H generated from various cementitious materials
are presented in Fig. 11. Linear relationships are ob-
served independent of mix proportion, curing tempera-
ture and type of binder. A linear equation for this data
was obtained using regression analysis, which can be
written as:
ρC − S − H = 0.459 ⋅ ( Ca Si ) + 1.392 (7)
This allows the density of C-S-H with various Ca/Si
ratios in hardened cement paste to be evaluated from the
mean Ca/Si ratio, because the relationship is expressed
linearly. The correlation factor is 0.844. Figures 12 (a),
Dry at 110 °C → TGA Water adsorption

3.2.2 Relationship between Ca/Si ratio and den- Combined water i% RH Adsorbed water
sity of C-S-H generated from cementitious ma-
terials Combined water + i% RH Adsorbed water
As decreases in the Ca/Si ratio of synthesized C-S-H lead i% RH: 11%, 22%, 33%
to decreases in density, the density of C-S-H in cement
paste was evaluated. The density of C-S-H generated by Fig. 10 Model of combined water at different relative
various cementitious materials was calculated from Eq. humidity.
(6):
2.6
mC − S − H (6) y=0.459x+1.392
ρC − S − H = 2.4
Density of C-S-H (g/cm3)

1 m R2 =0.844
−∑ i
P ρi 2.2
2.0
where ρC-S-H is the density of C-S-H (g/cm3), mC-S-H is the Cement paste
1.8 NC, MC, LC
amount of C-S-H (g/g of sample dried at 11% RH), P is
NC-BFS
the density of cement paste dried at 11% RH (g/cm3), mi 1.6
NC-FA
is the amount of each hydration product (except C-S-H), 1.4 NC-SF
unhydrated clinker mineral and unhydrated admixture 1.2 C3 S paste
(g/g of sample dried 11% RH), and ρi is the density of C-S-H
each hydration product (except C-S-H), unhydrated 1.0
0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4
clinker mineral and unhydrated admixture (g/cm3).
Ca/Si ratio (mol/mol)
The densities of hydration products except C-S-H are Fig. 11 Relationship between density and Ca/Si ratio of
listed in Table 7. The amounts of unhydrated clinkers, C-S-H generated from various cementitious materials.
Y. Suda, T. Saeki and T. Saito / Journal of Advanced Concrete Technology Vol. 13, 275-290, 2015 284

2.8 2.8 1.1nm Toberm orite

1.4nm Toberm orite
Density of C-S-H (g/cm )

2.6

Density of C-S-H (g/cm )

3

2.6

3
Metajenite
y=0.242x+1.978 Jennite
2.4 2.4 Allen et al. 2007
Thom as et al. 2010
Beaudoin et al. 1998
2.2 2.2 Muller et al. 2013
Pellenq et al. 2009
2.0 2.0 Manzano et al. 2012
Tay lor 1997
1.8 1.8 Eq.(7): T his study
Young and Hansen 1987
Eq.(7): T his st udy Benz 1997
Richardson 2014
1.6 1.6
0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
Ca/Si ratio (mol/mol) Ca/Si ratio (mol/mol)
(a) Various H2O/Si ratio (b) Normalized H 2O/Si ratio
Fig. 12 Relationship between density and Ca/Si ratio of C-S-H reported by previous research. (a) Various H2O/Si ratio, (b)
Normalized H2O/Si ratio.

(b) show the relation between the density and Ca/Si ratio 40

(% of binder dried at 50 ºC)

of C-S-H reported in previous studies (Allen et al. 2007;
Thomas et al. 2010; Beaudoin et al. 1998, Muller et al.
2013; Pellenq et al. 2009; Manzano et al. 2012; Taylor
1997; Young and Hansen 1987; Benz 1997; Richardson
2014). As shown in Fig. 12 (a), at the same Ca/Si ratio,
the density of C-S-H reported by researchers differs. This
is because the hydrated samples were dried under various
condition, such as 110ºC, d-drying, 11% RH and satu-
rated condition. A major factor was also the fact that the
H2O/Si ratio of each C-S-H sample was not standardized.
In this study, in order to standardize the H2O/Si ratio of
each C-S-H sample, the H2O/Si ratio of each C-S-H was
normalized by Eq. (5). Figure 12 (b) shows the relation
between the density and Ca/Si ratio of C-S-H normalized
by Eq. (5). Similar to this study, the densities reported in
former studies decreased with decreasing Ca/Si ratios
(Fig. 11). However, the relation between the density and
Ca/Si ratio in this study differs from past research results.
When the Ca/Si ratio is the same value, densities in this
study are smaller than past research results, possibly
because small pores and closing pores were not evaluated
in this study.
Therefore, to estimate the engineering adequacy of Eq.
(7), the porosity measured after drying at 50°C was
compared with the theoretical porosity calculated from
the amount and density of hydration products, unhy-
drated binder and unhydrated admixture. Densities were
measured at 11% RH. In this case, the porosity after
drying at 11% RH differed from that of samples dried at
50°C. However, as shown in Fig. 13, the amount of
combined water in the sample dried at 11% RH was very
nearly equal to that in the sample dried at 50°C. There-
fore, it was assumed that the samples dried at 11% RH
and 50°C were of equal porosity.
The theoretical porosity of each cement paste dried at
11% RH was calculated from the amount and density of
hydration products, unhydrated clinkers and unhydrated
mineral admixtures. The densities of the hydration
products shown in Table 7 were used, while the density
of C-S-H was calculated using Eq. (7). This means that
NC
BFS
30
Combined water
FA
20
10
R: 0.987
0
0 10 20 30 40
Combined water
(% of binder dried at 11% RH)
Fig. 13 Comparison of amount of combined water at 11%
RH and after drying at 50 °C.
the density of C-S-H was calculated considering the
change in Ca/Si ratio shown in Fig. 6.
Figure 14 compares the theoretical porosity calculated
from the amount and density of hydration products dried
at 11% RH and that measured following drying at 50°C.
Figures 14 (a) and (b) show the porosity evaluated by Eq.
(7) (y=0.459x+1.392). Figures 14 (c) and (d) show the
porosity evaluated based on previous research results
(y=0.242x+1.978). As shown in Figs. 14 (a) and (b), the
change in theoretical porosity with Ca/Si ratio agrees
with experimental values. The correlation factors are
0.947 (a) and 0.927 (b). The slopes of the regression
equation are 1.01 (a) and 1.00 (b). Therefore, the linear
relationship between the Ca/Si ratio and density of
C-S-H is adequately described by Eq. (7). As shown in
Figs. 14 (c) and (d), the correlation factors are 0.950 (c)
and 0.907 (d). The slopes of the regression equation are
0.940 (c) and 0.956 (d). The values calculated based on
previous research results (y=0.242x+1.978) were larger
than the experimental value due to these results. This is
because the density values in the earlier research results
are larger than the densities measured in this study. The
differences between this study and previous research on
Y. Suda, T. Saeki and T. Saito / Journal of Advanced Concrete Technology Vol. 13, 275-290, 2015 285

60 N40 20 ºC 60 BFS35%
De n si ty: Eq. (7) De nsi ty: Eq. (7)
N55 20 ºC BFS50%
50 M40 20 ºC 50 BFS70%

Porosity (%) -test-

Porosity (%) -test-
M55 20 ºC FAA15%
L40 20 ºC FAA30%
40 40
L40 20 ºC FAB15%
N55 5 ºC FAB30%
30 N55 40 ºC 30 SFA4%
SFA8%
20 y=1.01x 20 y=1.00x
SFB4%

R: 0.947 R: 0.927
10 10
10 20 30 40 50 60 10 20 30 40 50 60
Porosity (%) -calculation- Porosity (%) -calculation-
(a) NC, MC, LC paste (b) BFS, FA, SF
60 N40 20 ºC 60 BFS35%
De n si ty: Re fe re nce value De nsi ty: Re fe re nce val ue
N55 20 ºC BFS50%
50 M40 20 ºC 50 BFS70%

Porosity (%) -test-

Porosity (%) -test-

M55 20 ºC FAA15%
L40 20 ºC FAA30%
40 40
L40 20 ºC FAB15%
N55 5 ºC FAB30%
30 N55 40 ºC 30 SFA4%
SFA8%
20 y=0.940x 20 y=0.956x
SFB4%

R: 0.950 R: 0.907
10 10
10 20 30 40 50 60 10 20 30 40 50 60
Porosity (%) -calculation- Porosity (%) -calculation-
(c) NC, MC, LC paste (d) BFS, FA, SF
Fig. 14 Comparison of calculated and experimental porosity. (a) NC, MC and LC pastes with Eq. (7), (b) NC-BFS, NC-FA
and NC-SF pastes with Eq. (7), (c) NC, MC and LC pastes with earlier research, (d) NC-BFS, NC-FA and NC-SF paste
with earlier research.

200
Specific suraface area (m2/g)

150

100

50 W/B: 35% Replacement ratio: 15% Replacement ratio: 35%

W/B: 45% Replacement ratio: 30% Replacement ratio: 50%
W/B: 55% Replacement ratio: 70%
0
28 1
91 182 500 1 3 73 28 91 182 500
7 1 3 7 28 91 182 500
Age (days) Age (days) Age (days)
(a) NC (b) NC-FA (c) NC-BFS
Fig. 15 Change of specific surface area at each age (a) NC paste, Curing temperature: 20 ºC (b) NC-FA paste W/B: 55%,
Curing temperature: 20 ºC (c) NC-BFS paste, W/B: 55%, Curing temperature: 20 ºC.

the density of C-S-H is considered to be the result of curing age. As shown in Fig. 15 (a), even though the
differences among the various experimental methods W/B ratios differed, the specific surface area of the
employed, including the Archimedes method, helium samples were the same value until 7 days. After 7 days of
pycnometer method, molecular dynamics method and curing, increases in W/B tend to lead to higher specific
small-angle neutron scattering method. However, the surface area. The specific surface area at each age was
porosity of hardened cement paste can be evaluated from affected by the replacement ratio of mineral admixture in
Eq. (7) in engineering. Figs. 15 (b), (c).
For pretreatment of specific surface area measure-
3.2.3 Specific surface area of cement paste ments, samples were oven dried at 110ºC for 1-3days
Figures 15 (a), (b) and (c) show the change of specific after immersion in acetone (Section 2.1.3). Previous
surface area of cement paste samples at each age. The studies have pointed out that the capillary pressure due to
specific surface of each cement paste increases with surface tension of the removed water caused by
Y. Suda, T. Saeki and T. Saito / Journal of Advanced Concrete Technology Vol. 13, 275-290, 2015
oven-drying at high temperature causes the collapse of
small pores such as gel pores in C-S-H (Juenger et al.
2001; Korpa et al. 2006; Snoeck et al. 2014). Compared
with other drying methods, the oven drying method
causes the specific surface area decrease owing to the
collapse of small pores as the result of capillary pressure.
On the other hand, the solvent exchange method, using
solvents such as methanol and isopropanol, preserves the
microstructure due to the reduction of capillary pressure
on drying by the decrease of surface tension (Juenger et
al. 2001; Collier et al. 2008; Snoeck et al. 2014). How-
ever, in this study, the values of specific surface area (NC,
W/B=45% and 55%, Age: 6 months) were 133 m2/g
(W/B=45%) and 139 m2/g (W/B=55%). These values are
in agreement with the value (131 m2/g) of the saturated
sample (NC, W/C=50%, Age: 6 months) reported in a
prior study (Snoeck et al. 2014). Additionally, other
features of specific surface area, such as differences by
W/B and age, are the same as reported previously (Ma-
ruyama et al. 2014). These results might be due to the
preservation of the microstructure by acetone exchange.
Therefore, in this study, it seems possible to investigate
evaluation methods and the relative effect of various
features with the specific surface area.
3.2.4 Specific surface area of hydration prod-
ucts
The BET specific surface areas of synthesized hydration
products are presented in Table 7, and increase as the
Ca/Si ratio decreases. The specific surface area of cal-
cium hydroxide and hydrogarnet are lower than those of
other hydration products. The specific surface area of
ettringite, monosulfate and C4AH13 are similar.
3.2.4 Specific surface area of C-S-H
Figure 16 depicts the relationship between the reaction
ratio and amount of combined water + adsorbed water in
C3S paste at different RH. At the same RH, there is a
linear relationship between the reaction ratio and amount
40
30% 20 ºC y=0.201x
Combined water + Adsorbed water (%)
2
30 40% 20 ºC R : 0.971
50% 20 ºC
40% 5 ºC
20
40% 40 ºC
10
0% RH
0 0.08
y=0.244x
30 2
R : 0.977
20
10
22% RH
0
0 20 40 60 80
Reaction ratio (%)
Fig. 16 Relationship between the reaction ratio of C3S
and combined water at different relative humidities.
286
of combined water + adsorbed water in C3S. Therefore,
the H2O/Si ratio of C-S-H at each RH can be expressed as
a function of the Ca/Si ratio from Eq. (5). The values of n
are shown in Fig. 16. The amount of water adsorbed by
C-S-H can be calculated from the composition of C-S-H
at each RH using the equation:
18.0 ⋅ ( qi % RH − q0%RH )
AC − S − H = (8)
56.1 ⋅ p + 60.1 + 18.0 ⋅ q0%RH
where AC-S-H is the amount of water adsorbed by C-S-H
(g/g of C-S-H dried at 0% RH), qi%RH is the H2O/Si ratio
at each RH (11%, 22% and 33%), q0%RH is the H2O/Si
ratio at 0% RH, and p is the Ca/Si ratio. Equation (8)
indicates that the amount of water adsorbed by C-S-H
can by expressed as a function of the Ca/Si ratio.
Figure 17 shows the relationship between the Ca/Si
ratio and amount of adsorbed water in C-S-H. The
amount of water adsorbed by C-S-H at each RH in-
creases with decreasing Ca/Si ratio. This relationship
indicates that a lower Ca/Si ratio increases the specific
surface area of C-S-H.
The specific surface area of samples with different
Ca/Si ratios was calculated using BET plots. The rela-
tionship between the Ca/Si ratio and specific surface area
of each sample can be formulated using regression
analysis. In this study, the logarithm function
(y=a-bxlog(x)) was used as the regression expression
because it gave the highest correlation factor of the ex-
pressions investigated. The relationship between Ca/Si
ratio and specific surface area can be written as:
SC − S − H = 269.3 − 325.1 ⋅ log( Ca Si ) (9)
where SC-S-H is the specific surface area of C-S-H (m2/g).
The correlation factor is 0.998. The relationship between
the Ca/Si ratio and specific surface area calculated from
Eq. (9) is shown in Fig. 18. The relationship between the
Ca/Si ratio and density of C-S-H is linear, whereas an
inversely proportional relationship is observed between
the Ca/Si ratio and specific surface area of C-S-H. The
specific surface area calculated from Eq. (9) gives the
y=0.232x temporal and spatial mean of C-S-H generated from the
2
R : 0.975
0.12
11% RH
(g/g of C-S-H dried at 0% RH)
Amount of adsorbed water
0.10 22% RH
11% RH 33% RH
y=0.254x
2 0.06
R : 0.977
0.04
0.02
33% RH
0.00
0 20 40 60 80 100 0.6
1.0 1.2 1.4 1.6 1.8 0.8
Reaction ratio (%) Ca/Si ratio (mol/mol)
Fig. 17 Relationship between Ca/Si ratio and amount of
adsorbed water at different relative humidities.
Y. Suda, T. Saeki and T. Saito / Journal of Advanced Concrete Technology Vol. 13, 275-290, 2015 287

Table 8 Distribution range of Ca/Si ratio and mean Ca/Si ratio from the literature.
Author(s) Materials, mixture and curing age Range of Ca/Si Mean Ca/Si Measurement method
Stucke and Majumdar Pure C3S, W/C: 0.6, 30 days 1.47-2.49 1.91 SEM-EDS
Diamond Pure C3S, W/C: 0.4, 3 1/2 years 1.54-2.57 1.88 SEM-EDAX
FA-CH, 50:50 CH/FA,
Williams et al. 1.33-1.48 1.43 SEM-EDS
W/C: 0.8, 78 days
C3S, W/C: 0.4, 3 days 2.08-2.89 2.35
C3S, W/C: 0.4, 91 days 2.07-2.15 2.12
C3S-white clay, 60:40 C3S/clay,
Ogawa et al. 1.61-2.92 2.47 FESEM-EDX
W/C: 0.4, 3 days
C3S-white clay, 60:40 C3S/clay,
1.57-1.96 1.77
W/C: 0.4, 91 days
White cement-FA-KOH, 70:30 ce-
Girão et al. 0.72-2.40 1.10 TEM-EDX
ment/FA, W/C: 0.5, 28 days
OPC-GGBS, 90:10 OPC/GGBS,
1.18-2.19 1.60
W/C: 0.4, 20 years
OPC-GGBS, 50:50 OPC/GGBS,
Taylor et al. 1.03-1.72 1.33 TEM-EDX
W/C: 0.4, 20 years
OPC-GGBS, 25:75 OPC/GGBS,
1.22-1.67 1.31
W/C: 0.4, 20 years

beginning of hydration until a specified curing time. In
addition, the relationship between the Ca/Si ratio and
specific surface area in Eq. (9) cannot calculate the local
specific surface area of C-S-H with various Ca/Si ratios.
This is because the relationship was expressed as a
nonlinear equation. However, the specific surface area
calculated from Eq. (9) agrees well with the experimental
results obtained for synthesized C-S-H shown in Fig. 18.
To investigate the engineering applicability of Eq. (9),
SC-S-H calculated using Eq. (9) from the mean Ca/Si ratio
of C-S-H was compared with SC-S-HxD calculated using Eq.
(10) from the distribution of various Ca/Si ratios in
C-S-H as follows:
1
SC − S − H ⋅D =
n
∑ S C − S − H ⋅i
SC-S-Hxi is calculated using Eq. (9) from the local Ca/Si
ratio in C-S-H, and n is the number of local Ca/Si ratios
of C-S-H. The distribution of local Ca/Si ratios in C-S-H
in cement paste was compared with reported results
(Stucke et al. 1977; Diamond 1976; Williams et al. 2002;
Ogawa et al. 1980; Girão et al. 2010; Taylor et al. 2010),
as shown in Table 8. The results in this table were chosen
to represent different combinations of materials, mix
proportions and curing times.
Figure 19 compares SC-S-H calculated using Eq. (9)
with the mean Ca/Si ratio of C-S-H and SC-S-H calculated
using Eq. (9) from the distribution of Ca/Si ratios in
C-S-H. As shown in this figure, SC-S-H calculated using
Eq. (9) from the mean Ca/Si ratios of C-S-H agreed well
with that considering the distribution of Ca/Si ratio in
C-S-H. Therefore, the specific surface area of C-S-H can
be evaluated from the mean Ca/Si ratio in engineering.
3.2.5 Evaluation of specific surface area of ce-
ment paste
(10) To verify the applicability of Eq. (9) and the accuracy of
the specific surface area of each hydration product, the
specific surface areas of cement paste were compared
with calculated values, which were determined from the
integrated values of the amount and specific surface area
of various hydration products in cement paste. The
300
calculated by distribution of

Stucke and Majundar

Diamond
500
(m /g of C-S-H dried at 0% RH)
Specific surface area of C-S-H

Williams et al.
250
Ogawa et al.
Ca/Si ratio (m2 /g)

400 Girao et al.

Tay lor et al.

300 200

200
150
100 Eq. (9)
C-S-H·D

Synthesized C-S-H 100

S

0
2

100 150 200 250 300

0.6
1.0 1.2 1.4 1.6 1.8 0.8 SC-S-H calculated by average Ca/Si ratio (m2 /g)
Ca/Si ratio (mol/mol) Fig. 19 Comparison of SC-S-H calculated from mean
Fig. 18 Relationship between Ca/Si ratio and specific Ca/Si ratio of C-S-H and that calculated from distribution
surface area of C-S-H. of Ca/Si ratio of C-S-H.
Y. Suda, T. Saeki and T. Saito / Journal of Advanced Concrete Technology Vol. 13, 275-290, 2015 288

amounts of hydration products in cement pastes were Ca/Si ratio in C-S-H increases its specific surface area.
calculated from the mass balance shown in Fig. 4 and A decrease of H2O/Si ratio cause the water content in
Table 6. Therefore, the specific surface area of C-S-H C-S-H to decrease. As a result, the density of C-S-H was
was calculated considering the change in Ca/Si ratio expected to increase by the decreased water content
shown in Fig. 6. It was assumed that the specific surface (Thomas et al. 2010). Therefore, the reason for the de-
area of C3FH6 was the same as that of C3AH6. creased density with decreasing Ca/Si ratio can be de-
The calculated and experimental specific surface areas termined by considering the composition of C-S-H dried
of cement paste are compared in Fig. 20. The calculated at RH of 0% and 11%.
and experimental results agreed. Therefore, Eq. (9) can The relationship between the Ca/Si ratio and compo-
be used to evaluate the mean specific surface area of sition of C-S-H is shown in Fig. 21. In this study, the
C-S-H with Ca/Si ratio of 1.0–2.0, which should be of water in C-S-H dried at 0% RH is assumed to be
use in engineering. The ability of Eq. (9) to accurately chemically combined. The difference between the com-
calculate the specific surface area of each hydration bined water at 11% RH and that at 0% RH is assumed to
product was confirmed. Furthermore, an equation for the be the gel water in C-S-H. A decrease of Ca/Si ratio
relationship between the Ca/Si ratio and specific surface causes the water content (chemically combined water
area of C-S-H was determined. and gel water) in C-S-H to decrease. However, the gel
water in C-S-H increases as the Ca/Si ratio decreases.
4. Discussion This is because the decreased Ca/Si ratio increases the
specific surface area of C-S-H. Therefore, the decrease of
This study investigated the relationship between the density is caused by the decreased Ca/Si ratio, which
composition and physical properties of C-S-H. The re- increases the amount of gel water in the sample.
sults show that as the Ca/Si ratio in C-S-H decreases, so
do the H2O/Si ratio and density of C-S-H. A decrease of 5. Conclusions
The relationship between the composition (Ca/Si and
200 H2O/Si ratios) and physical properties (density and spe-
Specific surface area (m2 /g) -test-

NC
MC
cific surface area) of C-S-H was investigated. The
LC H2O/Si ratio of C-S-H at each RH was proportional to the
150 BFS Ca/Si ratio independent of the mix proportion, curing
FAA temperature and type of binder. An equation for the re-
lationship between the Ca/Si and H2O/Si ratios of C-S-H
100 was proposed. A linear relationship was observed be-
tween the Ca/Si ratio and density of C-S-H that was
independent of mix proportion, curing temperature and
50 type of binder, allowing an equation relating these factors
to be determined. An inversely proportional relationship
R: 0.973 that was found between the Ca/Si ratio and specific sur-
0 face area of C-S-H was recognized. A decrease of Ca/Si
0 50 100 150 200 ratio increased the amount of gel water in the sample,
Specific surface area (m2/g) -calculated- which increased the specific surface area of C-S-H. As a
Fig. 20 Comparison of calculated and experimental spe- result, the density of C-S-H at 11% RH decreases as the
cific surface area. Ca/Si ratio decreases.

100 Acknowledgments
H2O (Gel water)
(wt% of C-S-H dried at 11% RH)

The authors thank Dr. T. Sagawa for his advice about the
Composition of C-S-H

90 XRD/Rietveld and heat-treated XRD/Rietveld methods.

C-S-H dried at 11% RH

H2O (Combined water) This study was financially supported by a Grant-in-Aid

C-S-H dried at 0% RH

for Scientific Research (24360168) from JSPS.

80
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