Construction and Building Materials 102 (2016) 943–949

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Construction and Building Materials

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

Studies on early stage hydration of tricalcium silicate incorporating silica

nanoparticles: Part II
L.P. Singh a,⇑, S.K. Bhattacharyya a, S.P. Shah b, G. Mishra a, U. Sharma a
a
CSIR-Central Building Research Institute, India
b
Center for Advanced Cement-Based Materials Northwestern University, IL, USA

h i g h l i g h t s

 SNPs shows its maximum nucleation effect at 8 h when the rate of product formation is high than the control.
 Maximum pozzolanic effect of SNPs observed at 24 h when the quantity of CH was lower than the control.
 25% addition C-S-H formed in the presence of SNPs at 24 h.
 More polymerized and well ordered crystalline C-S-H is formed in presence of SNPs.
 SNPs formed more compact and dense microstructure at 24 h which is responsible for the higher early age mechanical strength.

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

Article history: The beneficial role of silica nano-particles (SNPs) during the early stage hydration of tricalcium silicate
Received 4 December 2014 (C3S) has been investigated. ICP results show that SNPs significantly accelerate the hydration rate as well
Received in revised form 13 April 2015 as the growth of hydrated products, by providing additional nucleating sites. XRD results also show a
Accepted 2 May 2015
dominant nucleation effect of SNPs up to 10 h. While, at later stage i.e. from 15 to 24 h, the pozzolanic
Available online 26 May 2015
effect of SNPs was dominant. Further, TGA results reveal that, in SNPs incorporated samples, quantity
of CH is higher (61% at 8 h) up to 10 h, and lower (32% at 24 h) from 15 to 24 h than the control, show-
Keywords:
ing the nucleation and pozzolanic effect of SNPs respectively. FTIR and XRD results further reveal an
Tricalcium silicate
Hydration
accelerated formation of crystalline C-S-H (jennite and tobermorite) with SNPs. All these results i.e.
Silica nano-particles accelerated hydration, crystalline C-S-H formation and lower C/S (1.9) lead to enhanced durability of
C-S-H cementitious materials.
Ó 2015 Published by Elsevier Ltd.

1. Introduction
Recently, nanotechnology based applications have gained wide-
spread interest and concrete technologists are exploring different
nano-materials such as SiO2, TiO2, Fe2O3, Al2O3, CNT and etc., to
improve the performance of cementitious materials [1–7]. Precise
understanding of hydration products formed as result of the addi-
tion of these nano-materials is essential for the strategic modifica-
tion of conventional cementitious materials. These nano-materials
accelerate the hydration process by providing additional
nucleating sites and showing their maximum effects during induc-
tion & acceleration period of hydration [8–10]. The chemistry of
nano-particles incorporated in cementitious materials at this stage
⇑ Corresponding author. Tel.: +91 1332 283442; fax: +91 1332 272272.
E-mail addresses: lpsingh@cbri.in, lpsingh@cbri.res.in (L.P. Singh).
is still not well established, in fact, the hydration chemistry in pure
system (Portland cement) is itself a complex process. There are
four main stages that occur during the hydration i.e.
pre-induction, induction, acceleration and deceleration period
[11–13]. On contact with water, C3S undergoes an intense and
short-lived reaction, known as the pre-induction period. Oxygen
ions from the surface of the C3S lattice react with protons in the
water and form hydroxide ions, which in turn combine with
Ca2+ leading to form calcium hydroxide (CH) [14]:
O2 ðlatticeÞ þ Hþ ðaqÞ ! OH ðaqÞ
Ca2þ ðlatticeÞ þ OH ! CaðOHÞ2
At the same time, silicate material from the ‘C3S’ lattice surface
enters into the liquid phase:
4 ð4nÞ
SiO4 ðlatticeÞ þ nHþ ðaqÞ ! Hn SiO4 ðaqÞ

http://dx.doi.org/10.1016/j.conbuildmat.2015.05.084
0950-0618/Ó 2015 Published by Elsevier Ltd.
944 L.P. Singh et al. / Construction and Building Materials 102 (2016) 943–949

A complete reaction may be represented as:

The coupled dissolution and precipitation reactions that occur

when C3S grains comes in contact with water, determine a number
of practically important properties, such as setting time, rate of
heat release and etc. Thermodynamic studies consider that a meta-
stable C-S-H is formed during the initial stage of hydration exhibit-
ing a greater solubility than that of final stable C-S-H and lesser
solubility than C3S. At the end of induction period, this metastable
C-S-H is converted to a more stable C-S-H [15–18]. In contrast of
this, Scrivener et al., 2008–2012 [19–23] have reported that the
slowdown in the initial reaction of C3S is caused by the changes
in ionic concentration in the solution and not by the presence of
Fig. 2. Schematic of the hydration process. (a) Normal unseeded paste after a few
inhibiting layers formed on the surface of C3S grains. Further, minutes of mixing. (b) Nucleation and growth. (c) Paste with C-S-H seed, a few
Scrivener et al., 2012 [24] have reported that the hydration of alite minutes after mixing. (d) After several hours the overall extent of early hydration is
is well simulated by two mechanisms, namely: Solution Controlled greater, and there is much less capillary porosity (39).
Dissolution (SCD) up to the end of the induction period and
Nucleation with Densifying Growth (NDG) to capture the main
nucleation. Applications of the Avrami model to isothermal
heat evolution peak. They also proposed a scheme for an early
calorimetry or QENS data require assuming an induction period
stage hydration and according to that, as C3S grains come in con-
of at least 1 h prior to any C-S-H nucleation to obtain good fits
tact of water, some primary hydrates are precipitated on the sur-
[34,35]. But Thomas’s, 2007 [36] application of a boundary
face of C3S grains, but they do not form a continuous layer [25].
Nucleation and Growth (BNG) model to fit isothermal calorimetry
Onset of acceleration is still a point of discussion because at this
data and its application in by Scherer et al. [37,38], to fit chemical
time two main reactions occur simultaneously: precipitation of CH
shrinkage data indicate that initial C-S-H nucleation occurs close to
and rapid growth of C-S-H. The role of precipitation of CH as a key
the time of mixing.
mechanism was dismissed, because CH cannot act as a seed, since
Thomas et al. reported that a stable C-S-H nucleation as a con-
it quickly dissolve as soon as it comes in contact with water.
trolling factor in the early-age hydration of C3S, wherein C3S was
However, the CH precipitation decreases the calcium hydroxide
seeded by adding a reactive form of C-S-H. In these experiments,
concentration contributing a rise in the rate of reaction, Fig. 1
the induction period was essentially eliminated and hydration pro-
[26,27].
gressed to nucleation and Growth (N + G) kinetics immediately and
According to C-S-H nucleation theory, the growth of C-S-H,
at a higher rate than in an unseeded paste, Fig. 2 [39]. Without
plays an important role during the acceleration period, which is
seeding, more time was required for the natural nucleation and
more gradual and prolonged than any other cementitious system
growth process to provide enough C-S-H surface area for apprecia-
i.e. calcium aluminate hydrate, ettringite and calcium sulpho alu-
ble growth rates to be observed.
minate etc. Earlier reviews on cement hydration have concluded
In previous study [40] we focused the preinduction and induc-
that after the formation of a metastable C-S-H layer on C3S sur-
tion period of hydration, and observed that in the presence of SNPs,
faces, a stable form of C-S-H is formed which nucleate the hydra-
additional C-S-H is formed and the supersaturation stage of Ca2+
tion process [28–32]. Garrault and Nonat [33] use the slow
was found to be delayed by 30 min. In the present study, influence
dissolution hypothesis and interpreted a decrease in silicate con-
of SNPs on hydration during acceleration and deceleration period
centrations in the beginning of hydration, as a result of C-S-H
of C3S was examined using ICP, XRD, FTIR and SEM/EDX
techniques.

2. Materials and methods

2.1. Sample preparation of pure and SNPs incorporated C3S for hydration studies

To study the effect of SNPs during hydration, 10% (w/w) of SNPs (30–70 nm)
was added to the laboratory prepared powder C3S [40]. For the aqueous phase study
the mixture was hydrated with a w/b 5.0. The hydrated mixtures were stirred con-
tinuously in a magnetic stirrer. These hydrated mixtures were filtrated at different
time intervals starting from 1 to 24 h. For the paste study the mixture was hydrated
with a w/b ratio 0.4. Hydration was stopped at different time intervals starting from
4 to 24 h covering the acceleration and deceleration period of hydration.

2.2. Characteristics techniques

Fig. 1. Heat evolution rate curves for the C3S hydration in lime saturated solutions
with different solution to C3S ratios. The portlandite precipitation revealed by an
endothermal peak in the curve, occurs later and later when the w/c increased
[26,27].
In the present study, influence of SNPs on hydration during the acceleration and
deceleration period have been studied. The techniques, Inductive Couple Plasma
(ICP) (model Prodigy XP, Teledyne Leeman lab, USA) for the determination of ionic
concentration, Powder X-ray diffraction (model DMax-2200, Rigaku, Japan) was
used for the study of different phases formed during the hydration at early stage.
All the experiments were carried out at room temperature using copper radiation
(Cu-Ka) at 40 kV/40 mA. Scanning was performed with a step width of 0.02° 2h over
an angular range from 5° to 80° with a scanning rate of 0.5°/min throughout the
 L.P. Singh et al. / Construction and Building Materials 102 (2016) 943–949 945

experiments. FTIR (model NEXUS (1100), Thermo Nicolet, FTIR, USA) used for the
study of chemical bonding in hydrated phases. TGA (model: Diamond, Perkin a
Elmer; USA) studies were performed at a heating rate of 5 °C/min under nitrogen
flow. Morphological changes were observed using Scanning Electron Microscope
(model LEO 438 VP, Carl Zeiss AG, Oberkochen, Germany) at an accelerating voltage

Intensity(Counts)
C3S (24h)
of 15–20 kV and the samples were analyzed under variable pressure mode. For
elemental analysis, Energy Dispersive X-ray (model X-Flash Detector 5010,
Bruker, Nano GmbH, Germany) attached with SEM was used. C3S (15h)

C3S (8h)
3. Results

C3S (6h)
3.1. ICP

The concentration of Ca2+ samples at early stage of hydration C3S (0)

was measured in pure and SNPs incorporated C3S through ICP,

Fig. 3. Results of these studies reveal that Ca2+ ion concentration 2-Theta(0)
is increased rapidly during acceleration period (8–10 h). At the
end of this period the concentration of Ca2+ is decreased due to Fig. 4a. Intense peak of CH in hydrated C3S at various time intervals.
the crystallization of CH in pore solution of pure C3S. In the
presence of SNPs a decrease in Ca2+ concentration around 4–6 h
of hydration, is observed, showing the acceleration in hydration
rate due to the nucleation effect of SNPs. In the presence of SNPs, b
Ca2+ concentration is decreased, because of the regular consump- C3S +SNPs (24h)
tion of Ca2+ by SNPs leading acceleration in growth of hydrated
Intensity(Counts)
products [41]. C3S +SNPs (15h)

C3S +SNPs (8h)

3.2. XRD

XRD is a well known technique for the mineralogical analysis of C3S +SNPs (6h)
cement based material. Detailed XRD studies were carried out for
pure and SNPs incorporated hydrated C3S system. In pure C3S sam- C3S (0)

ples the intensity of crystalline CH peak at 2h = 18.02 [42] is regu-

larly increased with the hydration up to 24 h, Fig. 4a showing the 2-Theta(0)

growth of hydrated products during acceleration and deceleration Fig. 4b. Intense peak of CH in SNPs incorporated hydrated C3S at various time
period. In the presence of SNPs the intensity of CH peak is higher intervals.
than that of pure samples up to 10 h, Fig. 4a and 4b showing the
nucleation effect of SNPs which accelerate the growth of hydrated
products. At later stage i.e. from 15 to 24 h the intensity of CH peak
is lower than that of control sample, Fig. 4b showing the pozzolanic
effect of SNPs [43]. Further, the peak at 2h = 50.7 was carefully ana-
C3S(24h)
lyzed and was found to be a characteristics peak of crystalline
Intensity(counts)

C-S-H (jennite and tobermorite) [39]. In case of pure C3S samples

C3S(15h)
this peak appeared at 15 h and the intensity remains constant up
to 24 h, Fig. 5a, while in the presence of SNPs this peak appeared C3S(8h)
at 8 h and the intensity of this peak is continuously increases up
to 24 h, Fig. 5b. This indicates that in presence of SNPs a well C3S(6h)
ordered crystalline C-S-H is formed.
C3S(0)

2-Theta(0)

Fig. 5a. Incremental appearance of C-S-H peak with time (up to 24 h) in C3S
Ca2+ concentration

hydration.

3.3. FTIR
C3S
In this study, the hydration process of pure and SNPs incorpo-
rated C3S for first 24 h was monitored using FTIR. The spectra of
C3S+SNPs hydrated pure C3S and SNPs incorporated C3S at different time
intervals starting from 4 to 24 h, are shown in Fig. 6a and 6b. A
broad peak in the region 850–950 cm1 shows a characteristics
peak of unhydrated C3S [44,45]. A shift in this peak, towards higher
Time(h)
region, shows polymerization in silicate chain. This shift occurs at
Fig. 3. Ca2+ concentration in pure and SNPs incorporated C3S at different time 18 h, Fig. 6a in pure hydrated samples while, a quite intense Q2
intervals. (1101 cm1) [46] peak is observed at 6 h, Fig. 6b in SNPs
946 L.P. Singh et al. / Construction and Building Materials 102 (2016) 943–949

b
1
C3S+SNPs(24h)
2
Intensity (counts)

Transmittance(%)
3
C3S+SNPs(15h)

C3S+SNPs(8h)
Q3
C3S+SNPs(6h)
1. C3S(0)
C3S(0) 2. C3S+SNPs(6h)
Q2 3. C3S+SNPs(24h)

2-Theta(0)
Wavenumber(cm-1)
Fig. 5b. Incremental appearance of C-S-H peak with time (up to 24h) in C3S
hydration incorporating SNPs.
Fig. 6b. FTIR of SNPs incorporated hydrated C3S at different time intervals.

incorporated samples. A hump of Q3 peak (1214 cm1) [46] is Table 1

observed at 24 h, Fig. 6b showing higher polymerization in silicate Quantification of C-S-H in pure and SNPs incorporated C3S system.
chain in the presence of SNPs.
Time Quantification of C-S-H (%) in Quantification of C-S-H (%) in SNPs
(h) pure hydratedC3S incorporated C3S
3.4. TGA
1 0.60 1.14
3 0.76 1.9
Quantification of C-S-H in the pure and SNPs incorporated C3S 4 1.42 3.0
systems at different time intervals of hydration was carried out 6 2.64 8.80
using following Eq. (1) by TG analysis [47]: 8 3.42 10.25
10 6.39 11.15
C-S-H ð%Þ ¼ Total LOI  LOI ðCHÞ  LOI ðCCÞ ð1Þ 15 7.53 12.75
24 10.80 14.54
where, LOI (CH) is the dehydration of calcium hydroxide around
400–500 °C and LOI (CC) is the carbon dioxide release around
600–800 °C. Table 1 shows the amount of C-S-H in pure and SNPs
incorporated hydrated C3S systems at different time intervals
(1–24 h). The amount of CH is calculated directly from the TG
C3S
curves using the following Eq. (2) [48]:
MWðCHÞ
CH ð%Þ ¼ WLCH ð%Þ  ð2Þ
CH(%)

MWðHÞ C3S+SNPs

where WL(CH) corresponds to the weight loss attributable to CH

dehydration and MW(CH) and MW(H) are the molecular weights of
CH (74 g/mol) and water (18 g/mol), respectively. Results of these
studies reveals that nucleation effect of SNPs was predominant up
to 10 h because of the higher amount of CH is higher (61% at
8 h) than the control showing the acceleration in growth of Time(h)

hydrated products. While at later stage i.e. 15–24 h pozzolanic

Fig. 7. Amount of CH in pure and SNPs incorporated C3S at various time intervals.
effect of SNPs is predominant because the quantity of CH was lower
(32% at 24 h) than the control, indicating the pozzolanic effect of
SNPs, Fig. 7. In SNPs incorporated C3S system, the amount of
(Table 1) due to formation of secondary C-S-H gel through nucle-
C-S-H was significantly higher (25% at 24 h) than control
ation and pozzolanic reaction both.

3.5. SEM/EDX
a
1
SEM micrographs of hydrated C3S and SNPs incorporated C3S
Transmittance(%)

samples at different stage of hydration are presented in, Fig. 8a–

2
c. SEM micrographs show the microstructural changes occurred
during first 24 h of hydration. The fibrous C-S-H formed around
surface grain of C3S, converts into a compact gel like morphology
at 24 h. In pure C3S samples, at 15 h the hydration activity is pre-
dominant around the surface of C3S grain, Fig. 8b only, and at
24 h, a thin porous gel like structure is formed, Fig. 8c. However,
1.C3S(0) in the presence of SNPs, predominant hydration activity around
2. C3S(24h) the C3S grain is observed up to 4 h only, Fig. 9a. A thick hydrated
layer is formed at 15 h which converted into the denser and com-
Wavenumber(cm-1) pact structure at 24 h, Fig. 9c. These results are clearly showing the
acceleration in growth of hydrated products in the presence of
Fig. 6a. FTIR of hydrated C3S at different time intervals. SNPs which lead a dense and compact microstructure. EDX
 L.P. Singh et al. / Construction and Building Materials 102 (2016) 943–949
Fig. 8. SEM/EDX micrographs of hydrated C3S (a–c) at 4, 15 and 24 h, respectively.
analysis of these hydrated products show that in pure C3S samples
C/S ratio was high during acceleration stage (3.1 at 4 h), Fig. 8a
and followed by a decrease up to 24 h (2.5), Fig. 8c indicating
the growth of polymerized C-S-H, Fig. 8. While in the presence of
SNPs incorporated samples, C-S-H have low C/S ratio (2.9 at
4 h, and 1.9 at 24 h), Fig. 9a–c showing the higher polymerization
in C-S-H structure.
4. Discussion
The reaction chemistry of hydration during acceleration and
deceleration period is very important because during this time
the hydration rate reaches to its maximum level and growth of
stable hydrated products starts. The role of SNPs during accelera-
tion and deceleration period of hydration has been focused in the
present study. ICP analysis show that in pure C3S samples the con-
centration of Ca2+ increases during acceleration period (up to 10 h)
and followed by a decrease at the end of this period (10–12 h).
While in the presence of SNPs, Ca2+ concentration is increased up
to 4–6 h and then decreases at 6–8 h, showing the acceleration in
hydration rate due to the nucleation effect of C-S-H seeds formed
during pre-induction and induction period. The C-S-H seeds
formed in the presence of SNPs provide additional nucleating sites
947
C/S rao – 3.1
C/S rao – 3.0
C/S rao – 2.5
which accelerates the hydration rate and the growth of hydrated
products [39]. XRD results also show the existence of nucleation
effect at early stage of hydration (up to 10 h). The intensity of crys-
talline CH peak at 2h = 18.02 [42] increases regularly up to 24 h
show the natural nucleation effect of hydrated products formed
in pure samples. In SNPs incorporated C3S samples the intensity
of CH peak is observed to be higher than that of pure C3S up to
10 h, Fig. 4a and 4b showing a significant increase in growth of
hydrated products. At later stage (15–24 h), the intensity of this
peak was found to be lower than that of control due to the poz-
zolanic effect of SNPs [43]. Further TGA results also show the
nucleation and pozzolanic effect of SNPs. The amount of CH in
SNPs incorporated samples formed up to 10 h was higher (61%
at 8 h) than the control indicates its nucleation effect, while from
15 to 24 h the quantity of CH is lower ( 32% at 24 h) than the con-
trol showing the pozzlanic effect of SNPs, Fig. 7. The available SNPs
react with the portlandite formed during hydration and formed
additional C-S-H gel. At 24 h, TGA quantified 25% additional
C-S-H is formed, Table 1 through the pozzolanic and nucleation
reaction in SNPs incorporated Samples. Further, XRD results reveal
the crystalline nature of C-S-H in the presence of SNPs. As
discussed by Taylor [41], XRD pattern from ordered jennite and
tobermorite have maxima at 1.8 Å (2h = 50.7) [41,42]. In pure
C3S hydrated samples this peak appeared at 15 h and remains
948 L.P. Singh et al. / Construction and Building Materials 102 (2016) 943–949
Fig. 9. SEM/EDX micrographs of SNPs incorporated hydrated C3S (a–c) at 4, 15 and 24 h, respectively.
constant up to 24 h, Fig. 5a, while in the presence of SNPs this peak
appeared at 8 h and the intensity of this peak continuously
increases up to 24 h, Fig. 5b indicating the formation of crystalline
C-S-H in SNPs incorporated C3S samples. The crystalline nature of
C-S-H in SNPs incorporated samples also observed in FTIR spectra.
Intense Q2 peak ( 1101 cm1) of silicate chain [46] is observed at
6 h, Fig. 6b of hydration and Q3 peak (1210 cm1) was appeared
at 18 h which become more intense at 24 h, Fig. 6b showing the
crystalline nature of C-S-H having high polymerization in silicate
chain at the early stage. While in case of pure C3S samples there
is only a slight shift in the peak of C3S (937 cm1) towards higher
frequency at 18 h, showing the formation of C-S-H but up to 24 h,
Q2 and Q3 peak has not been observed, Fig. 6a, indicates the amor-
phous nature of C-S-H. Further, the SEM micrographs also show the
higher rate of hydration in the presence of SNPs. In pure C3S sam-
ples the hydration activity is prominent around the C3S grain up to
15 h (formation of fibrous C-S-H around the C3S grain) while, in
SNPs incorporated samples predominant hydration activity around
C3S grain has been observed up to 4 h only, showing the accelera-
tion in hydration rate. At later age (up to 24 h) in pure samples a
thin gel like hydrated layer has been observed which enclosed
whole C3S grains while in SNPs incorporated samples, highly
compact microstructure observed which responsible for lower
permeability. EDX analysis of these hydrated paste shows that
C/S rao – 2.9
C/S rao – 2.4
C/S rao – 1.9
the C-S-H formed during hydration have lower C/S ratio in the
SNPs incorporated samples because the calcium ions generated
during dissolution of C3S grains consumed by SNPs which lead to
the formation of more polymerized C-S-H.
5. Conclusions
Incorporation of SNPs into the cement slurry gives enhanced
mechanical property, lower porosity and permeability, which are
the important properties for enhanced durability. However, the
role of SNPs during hydration is not well established. The chem-
istry of hydration in the presence of SNPs is an interesting area
from the point of research, especially in the first 24 h. To under-
stand various mechanism during hydration, in the previous study
[40] we focused first 4 h of hydration and in the present studies
we have presented the first 24 h of C3S hydration in the presence
of SNPs. Main findings may be briefly summarized as follows:
 XRD results showed predominant nucleation effect up to 10 h
while predominant pozzolanic effect of SNPs in C3S is from 15
to 24 h.
 Crystalline C-S-H peak (2h = 50.7) was observed in SNPs incor-
porated C3S samples corresponding to jennite and tobermorite
structure.
 L.P. Singh et al. / Construction and Building Materials 102 (2016) 943–949
 FTIR results revealed that in presence of SNPs, crystalline C-S-H
(presence of Q2 peak at 6 h and Q3 peak at 24 h) is formed.
 ICP results showed that the maximum concentration of Ca2+ in
pore solution of control samples is observed at 10 h, while in
the presence of SNPs this stage was observed at 6 h showing
the nucleation effect of SNPs which accelerates the hydration
rate.
 TGA results revealed that 25% additional C-S-H is formed in
the presence of SNPs and also show the nucleating effect of
SNPs up to 10 h because the amount of CH formed at this time
is higher (61% at 8 h) than that of control samples. However, at
later age i.e. from 15 to 24 h, the amount of CH formed in SNPs
incorporated samples is lower (32% at 24 h) than the control
samples indicating the pozzolanic effect of SNPs.
 SEM/EDX results showed the formation denser C-S-H with low
C/S (1.9) ratio than the control samples (2.5) in the presence
of SNPs.
Acknowledgments
Author (U. Sharma) is grateful to UGC, New Delhi for the Grant
of Senior Research Fellowship. Author (G. Mishra) is thankful to
CSIR-CBRI, Roorkee for financial support.
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