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Vol.26 No.4 HE Yongjia et al: Effect of C/S Ratio on Morphology and Structure of...
Effect of C/S Ratio on Morphology and Structure of
Hydrothermally Synthesized Calcium Silicate Hydrate
HE Yongjia
1,2
, ZHAO Xiaogang
1
, LU Linnu
2, 3
, STRUBLE Leslie J
2
, HU Shuguang
1
(1. Key Laboratory for Silicate Materials Science and Engineering (Wuhan University of Technology), Wuhan 430070, China;
2. Department of Civil and Environmental Engineering, University of Illinois at Urbana-Champaign, Urbana, IL61801,USA;
3. School of Science, Wuhan University of Technology, Wuhan 430070, China)
Abstract: The samples of the C-S-H series were synthesized by hydrothermal reaction of fumed silica,
CaO and deionized water at initial C/S ratios between 1.0-1.7. Phase composition and structural and morphology
characteristics of C-S-H samples were analyzed by XRD, IR and SEM. The experimental results showed that
the d-spacing of (002), (110) and (020) decreased, the d-spacing of (200) increased, and the d-spacing of (310)
varied randomly, the polymerization of silica tetrahedra of C-S-H decreased, and morphology of C-S-H samples
varied from sheet shapes to long reticular bers as C/S ratio increased.
Key words: calcium silicate hydrate; C/S ratio; morphology; structure; hydrothermal synthesis
Wuhan University of Technology and SpringerVerlag Berlin Heidelberg 2011
(Received: Oct. 12, 2010; Accepted: Dec. 9, 2010)
HE Yongjia(): Assoc. Prof. ; E-mail: hyj@whut.edu.cn
Funded by the National Basic Research Program of China (973
Program) (No. 2009CB623201) and the National Natural Science Foundation
of China (No.51072150))
DOI 10.1007/s11595-011-0308-z
1 Introduction
The structure and properties of calcium silicate
hydrate (C-S-H) have been the subject of considerable
research for decades
[1]
. However C-S-H is very
complicated, its composition, morphology, structure
and properties vary with raw materials, W/C ratio, age,
temperature, synthesis method, etc. So C-S-H structure
and properties remain important areas of research
[2-5]
.
C-S-H can be prepared by different methods,
including hydrothermal reaction of CaO and SiO
2
,
aqueous reaction of CaO and SiO
2
, aqueous reaction
of Ca(NO
3
)
2
.4H
2
O and Na
2
SiO
3
, and mechanochemical
reaction of CaO and SiO
2
[6-8]
. Different preparation
methods lead to variation in structure of C-S-H.
The CaO/SiO
2
molar ratio (C/S ratio) of C-S-H is
an important composition parameter that affects
nonstructural characteristic of C-S-H. Then how does
C/S ratio affect phase composition and structural
and morphological characteristic of hydrothermal
synthesized C-S-H?
In the present study, the samples of the C-S-H
series were synthesized by hydrothermal reaction of
fumed silica, CaO and deionized water at initial C/S
ratios between 1.0-1.7, and we tried to answer the
above question using XRD technique and IR and SEM
investigation on synthesized C-S-H samples.
2 Experimental
2.1 Raw materials
The fumed silica (SIGMA-ALDRICH S5505)
was amorphous silica with particle size of 0.014 m.
The calcium oxide was freshly calcined from reagent
grade CaCO
3
at 1 100 for 2 hours. Deionized water
was boiled and then topped off with N
2
gas.
2.2 Sample preparation
The samples were prepared by the hydrothermal
reaction of fumed silica (SIGMA-ALDRICH S5505),
calcium oxide and deionized water at W/S=10 and initial
C/S ratios of 1.0, 1.3, 1.5 and 1.7. Fumed silica and
calcium oxide were mixed with deionized water in high
- temperature resistant plastic bottles, which were then
sealed and agitated in a water bath at 95 for 7 days.
The solid products were obtained by vacuum
filtration using ashless filter paper (100 circles) and
then washed with deionized water and filtered again
three times. Finally, the solid products were dried
overnight in a vacuum desiccator and stored under
flowing N
2
gas at room temperature. Samples were
named using their C/S ratios (samples with C/S ratios
1.0, 1.3, 1.5 and 1.7 were named CSH10, CSH13,
CSH15, and CSH17, respectively).
3 Results and Discussion
3.1 XRD analysis
XRD results are given in Fig.1. Portlandite (CH),
Journal of Wuhan University of Technology-Mater. Sci. Ed. Aug. 2011
771
which is readily identied by its XRD peaks at 0.490
and 0.263 nm, and calcite were not observed in any of
the samples. In fact, characteristic peaks of CH were
found in the XRD pattern of unwashed C-S-H sample
with C/S ratio 1.7 although intensities of peaks were
low. It indicated there were few unreacted CH in that
C-S-H sample. However peaks of CH were not found
in the XRD pattern of C-S-H sample with C/S ratio 1.7
in Fig.1, it was because these C-S-H samples in Fig.1
were washed by deionized water to get single C-S-H
samples. CSH 10 of low C/S ratio 1.0 has unreacted
fumed silica, as evidenced by the broad peak centered
at about 21 degrees.
The XRD patterns were dominated by peaks of
semi-crystalline C-S-H(1) at 0.307 nm, 0.280 nm, 0.183
nm, and 0.167 nm, which were present for all samples.
Semi-crystalline C-S-H(1) was the only phase detected
by XRD in all the samples. Table 1 lists the XRD
peaks of C-S-H observed in these samples and how
the peak positions varied with C/S. From Table 1 we
can see the XRD spacings of the C-S-H samples vary
systematically with C/S ratio, although the variation
is small. And the d-spacing of (002), (110) and (020)
decreased, the d-spacing of (200) increased, and the
d-spacing of (002) and (310) varied randomly as C/S
increased. Congs XRD results of C-S-H synthesized
at room temperature also indicated the d-spacing of
(002), and (020) decreased and the d-spacing of (200)
increased as the C/S ratios increased, however, the
d-spacing of (110) varied randomly as C/S increased
[9]
.
3.2 SEM analysis
SEM images of C-S-H samples are shown in
Fig.2. Prominent differences in morphology were
observed between the different C-S-H samples. The
C-S-H with C/S 1.0 exhibited a leafy or sheet shape in
a dense, laminar pattern. The C-S-H with C/S 1.3 was
a mixture of small leaves and short bers. The C-S-H
with C/S 1.5 exhibited longer bers (laths) in a reticular
pattern. The C-S-H with C/S 1.7 exhibited even longer
fibers in a loose reticular pattern. Thus the C-S-H
changed from dense leafy shapes to long reticular bers
as C/S ratio increased from 1.0 to 1.7.
3.3 IR results
The IR spectra of all C-S-H samples are shown
in Fig. 3. Table 2 shows the infrared absorption peaks
assigned to Si-O.
All C-S-H samples had a characteristic band
near 970 cm
1
due to Si-O stretching vibrations in Q
2

sites
[10]
. The intensity of this band decreased as C/S
increased, indicating that C-S-H with high C/S has less
Q
2
sites in its structure than C-S-H with low C/S. Fig.3
and Table.2 also show that the position of this Si-O
Q
2
shifted to lower wavenumbers as C/S increased,
indicating that the degree of polymerization decreased
as C/S increased in this range of C/S. Yus spectra also
showed the similar behavior that the dominant Si-O Q
2
stretch at about 970 cm
1
shifted to lower wavenumber
as C/S increased up to C/S 1.2, which they attributed to
decreasing polymerization in this range of C/S.
All C-S-H samples had characteristic bands near
816 cm
1
due to Si-O stretching vibrations in Q
1
sites.
As C/S increased, the positions of these characteristic
bands shifted to lower wavenumbers, but rather
subtle. The Si-O Q
1
stretch at about 816 cm
1
is much
sharper than Yu et al observed
[10]
, which indicated
order is higher than Yu et al synthesized. It is mainly
because their C-S-H samples were synthesized at
room temperatures, whereas our C-S-H samples were
hydrothermal synthesized. High temperatures caused an
increase in order. They showed a rather subtle increase
in intensity of this peak as C/S increased, but no
systematic change in wavenumber
[10]
. As C/S increased,
it cannot be seen an obvious systematic change in
intensity from Fig.3.
The Si-O-Si band at about 670 cm
1
was seen
by Yu et al to decrease in intensity and increase in
width at C/S >1.19, which they attributed to decreased
polymerization and decreased order at these higher C/S
values
[10]
. Fig.3 also shows a decrease in intensity of
this peak, and increase in width but the change in width
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Vol.26 No.4 HE Yongjia et al: Effect of C/S Ratio on Morphology and Structure of...
Journal of Wuhan University of Technology-Mater. Sci. Ed. Aug. 2011
773
is not obvious.
All C-S-H samples had characteristic bands near
460 cm
-1
due to Si-O-Si bending vibrations
[11]
. As C/S
increased, the position of the band shifted to lower
wavenumber. The change indicated polymerization
degree decreased as C/S increased.
I n addi t i on, al l t he C- S- H sampl es had
characteristic bands near 1 450, 1 650, and 3 440 cm
1
.
Their positions of band did not shift as C/S increased.
The fact that all the C-S-H samples had the similar
characteristic IR band indicates that they all had the
similar chemical structure. The characteristic band
near 1 650 cm
1
is due to H-O-H bending vibration of
molecular H
2
O in C-S-H, and the characteristic band
near 3 440 cm
1
is due to the stretching vibration of the
-OH bonds.
4 Conclusions
a) Samples of C-S-H were synthesized by
hydrothermal reaction of fumed silica, CaO and
deionized water at initial C/S 1.0-1.7.
b) Semi-crystalline C-S-H(1) was the only phase
detected by XRD in all the samples. The d-spacing of
(002) , (110) and (020) decreased, the d-spacing of (200)
increased, and the d-spacing of (310) varied randomly
as C/S increased.
c) Prominent differences in morphology were
observed between the different C/S C-S-H samples.
Morphologies of C-S-H samples vary from sheet to
long reticular bers as C/S increased.
d) The infrared spectra had peaks attributed to
(Si-O-Si), v
s
(Si-O-Si), v (Si-O) Q
1
, v (Si-O) Q
2
, -OH
and H-O-H. The polymerization degree, the content of
(Si-O)Q
2
decreased as C/S increased.
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