Construction and Building Materials 233 (2020) 117214

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Construction and Building Materials

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

Early strength development in concrete using preformed CSH nano

crystals
Saikat Das, Sonalisa Ray ⇑, Sudipta Sarkar
Departement of Civil Engineering, Indian Institute of Technology Roorkee, Rookee 247667, India

h i g h l i g h t s

This paper focuses on application of CSH based hardening accelerator in concrete.

Preformed CSH nano particles developed out of bagasse ash effectively reduce the induction period by 60–75%.

Acceleration in the strength gain process is achieved with the addition of CSH seeds.

Improved microstructure in the presence of preformed CSH seeds is achieved.

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

Article history: The pace of production of pre-cast elements are dependent on the formwork removal time and are gov-
Received 15 April 2019 erned by early strength gain process of concrete. Conventionally, the production cycle is enhanced either
Received in revised form 6 September 2019 by adopting elevated temperature curing or by the use of commercially available hardening accelerators
Accepted 10 October 2019
which often cause durability related problems in concrete. In this work, an attempt has been made to use
Available online 26 October 2019
preformed CSH nano-crystals synthesized from agricultural waste material for early strength develop-
ment in concrete. Inclusion of such seeding material in concrete can effectively eliminate the nucleation
Keywords:
period in the hydration process and can accelerate the early strength development without compromis-
Concrete
Hardening accelerator
ing in the ultimate strength and durability properties. The effectiveness of these preformed CSH seeds on
Early strength the early age strength gain process has been verified and confirmed by measuring setting time, compres-
CSH crystals sive strength, heat of hydration and by performing X-ray diffraction and thermal analysis. With the addi-
Induction period tion of CSH seeds, relatively faster precipitation of hydration products and early strength development
Heat of hydration have been observed.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction degradation. Moreover, such curing process increases the localized

Recently, there is an increase in demand for the use of pre-
fabricated structural elements by the construction industries for
minimizing time and cost of construction. In order to meet the
demand, precast industries are under pressure to enhance the pro-
duction rate. Acceleration in the production rate is dependent on
the early removal of formwork which in turn depends on the early
strength gain of fresh concrete. Therefore, the production rate can
be enhanced only when fresh concrete develops early strength as
fast as possible. The rate of gain of strength is generally maximized
by curing at elevated temperature or by using conventional hard-
ening accelerators. Elevated temperature curing requires high
energy input and emits greenhouse gas that creates environmental
⇑ Corresponding author.
E-mail address: sonarfce@iitr.ac.in (S. Ray).
sulphate concentration and decreases the aluminium concentra-
tion [1,2] resulting into reduction of the ultimate strength. Further,
at elevated temperature the hydration products are more unevenly
distributed and form dense inner shell around the particles [3]
developing a coarser porosity [4], denser CSH, and a more equant
morphology of ettringite [1] compared to ambient temperature
curing. To overcome such problems, commercially available hard-
ening accelerators are generally used as admixtures to achieve
early hardening. Presence of such chemicals alter the kinetics
and mechanisms of cement hydration resulting in reduction in set-
ting time and acceleration in the strength gaining process [5]. It is
well known that the hydration process of Portland cement (OPC) is
divided into five distinct stages namely, period I (the initial period
of hydration), period II (the dormant period), period III (the accel-
eration period), period IV (deceleration period), period V (transi-
tion to diffusion control) based on the heat flow [6]. A typical

https://doi.org/10.1016/j.conbuildmat.2019.117214
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
2 S. Das et al. / Construction and Building Materials 233 (2020) 117214
Nomenclature
D Gbulk
N bulk free energy
DGinterficial surface free energy
N
CSH calcium silicate hydrate
heat flow diagram of OPC representing various stages of hydration
are shown in Fig. 1. According to Paulini [9], the action of conven-
tional hardening accelerators occur in the period I and II. Chloride
based accelerators act as catalysts to accelerate the rate of the
hydration of C 3 S and C 2 S or lower the alkalinity of the pore solution
to promote the hydration. Presence of such an accelerator results
in faster rate of hydration [10,11] and modifies the chemical com-
position of the silicates in CSH [12]. In the presence of reactive
aggregates, the chloride-based admixtures promote alkali-silica
reaction leading to deterioration of concrete [12,13]. Besides, chlo-
ride ion breaks down the passive oxide layer of steel and promotes
the corrosion of reinforcement inside the concrete matrix [14–16].
Chemicals present in the accelerator may also hinder the normal
hydration kinetics and lower the final strength of concrete. Phos-
phoric acid-based accelerators significantly hinder the alite ðC 3 SÞ
hydration process [17,18] while formic acid-based accelerators
retard the final setting time and reduce 12 h compressive strength
by about 50% [5]. Galobardes et al. [19] have reported that pres-
ence of such accelerators also adversely affect the ultimate
strength and modulus of elasticity by approximately 20%. On the
other hand, sodium aluminate based accelerator rapidly exhausts
sulphate ions from aqueous phase leading to under sulphated
C 3 A reaction and finally resulting into decrease of C 3 S hydration.
A special type of cement called Sulphoaluminate cement (SAC)
has the capability to reduce the setting time and to achieve high
early strength due to the early hydration of C 4 A3 S [20]. However,
use of such cement causes expansion in the volume during the
Fig. 1. Typical diagram of rate of heat evolution of cement [7,8].
lb chemical potential at b phase
la chemical potential at a phase
hydration. Now a days the accelerators used to develop early
strength in concrete are either alkaline or alkali-free types depend-
ing on their chemical composition [21,22]. The primary component
of alkaline based accelerators are sodium aluminate or sodium sil-
icate. Generally, after application of aluminate based accelerators,

Naþ and ½AlðOHÞ4  ions get adsorbed around the cement grain.

Then, ½AlðOHÞ4  ions react with Ca2þ and SO2 4 ions present in the
pore water of the cement paste resulting into precipitation of
(Al-) ettringite [ðCaOÞ6 Al2 O3 ðSO3 Þ3 H32 ] (i.e AFt) and monosulfoalu-
minate [Ca4 Al2 ðSO4 ÞðOHÞ12 :6H2 O](i.e AFm) phases. The precipita-
tion of AFt and AFm phases takes place due to their lower
solubility product and this leads to a shorter setting time of the
concrete matrix. After depletion of SO2
4 ions, further C 3 A hydration
continues with limited sulphate and CAH might also precipitate
[21,23]. Maltese et al. [24] have described the development of
sodium-calcium aluminate hydrated phases (U-phases) based on
Naþ concentration. In general, the use of alkali based accelerators
is restricted due to the presence of high alkaline elements which
may cause safety issues for the workers. Galobardes et al. [19] have
reported about alkali-free accelerators which can be effectively
used to obtain higher ultimate strength and improved mechanical
properties. Bagasse, an agricultural waste has been used as supple-
mentary cementitious material in concrete after following appro-
priate processing techniques [25–28,52,53]. However, it has been
observed that such an application generally produces a lower ini-
tial strength in concrete. Attempts have been made by various
 S. Das et al. / Construction and Building Materials 233 (2020) 117214
researchers to develop and use hardening accelerators without
compromising in durability properties [29–31].
Recently, calcium silicate hydrate (CSH) nano-crystals are being
considered to be one such potential additive and are being used in
concrete. Thomas et al. [29] have prepared and used a pure form of
dispersed CSH in triclinic (C 3 S) paste. Through calorimetry study,
increase in both early hydration and total amount of hydration
during nucleation as well as the growth period have been
observed. With the addition of CSH, large number of nuclei become
available on the surface as well as pore space between the cement
particles from the beginning for the growth thereby eliminating
the induction period.
According to the classical theory of nucleation, the total energy
for the formation of new phase is assumed to consists of bulk free
energy (DGbulk
N ) and interfacial free energy (DGN
interficial
) which are
responsible for phase transformation and surface formation
respectively [32]. The energy change due to the formation of clus-
ter of b phase from a phase can be written as [32]
DGN ¼ DGbulk
N þ DGinterficial
N ð1Þ
DGN ¼ Nðlb  la Þ þ gN2=3 c
In the above expression, DGbulk
N is negative while DGinterficial
N is positive
as it is directly proportional to surface tension (Refer Appendix).
Due to the presence of positive interfacial energy term, DGN
achieves a maximum value before it becomes negative as presented
in Fig. 2. It is well known that hydration of cement is a dissolution-
precipitation process [33]. In the normal hydration process, the sys-
tem has to overcome the critical free energy (DGC ) as shown in Fig. 2
for the nucleation to begin. Presence of external sites lowers the
critical free energy of nucleation [32]. Therefore, the external supply
of preformed CSH overcomes the energy barrier for crystallization
process.
Present research focuses on the performance of tiny preformed
CSH crystals in Portland cement paste synthesized from bagasse
ash. Addition of such preformed CSH nano particles in the cement
Fig. 2. Free energy versus particle radius [32].
Table 1
Oxide composition of Portland cement.
Oxides SiO2 Al2 O3 Fe2 O3
Concentration (%) 40.903 11.270 0.164
3
paste provides extra sites for nucleation and growth of hydration
products. The objective of this work is to investigate the influence
of preformed CSH seed-based hardening accelerator on the early
strength development and microstructure of concrete. To achieve
this, series of experiments have been conducted by utilizing CSH
based accelerator in cement paste and concrete. Comparative stud-
ies of cement paste/concrete without and with CSH based acceler-
ator have been carried out by investigating setting time,
compressive strength, heat of hydration, X-ray diffraction, thermo-
gravimetry and SEM analysis. Further, the mechanisms of strength
development with the addition of preformed CSH have been pro-
posed inline with the obtained results.
2. Materials and characterization
2.1. Characterization of Portland cement (OPC)
In this work, Portland cement (OPC-43) was used to investigate
the effect of freshly prepared CSH on early hydration of cement
paste. Therefore, characterization of OPC material is necessary
and are described in the following subsections.
ð2Þ
2.1.1. X-ray fluorescence (XRF) analysis
Chemical oxide composition of OPC was determined through
XRF analysis and the results are presented as in Table 1.
2.1.2. X-ray diffraction (XRD) Analysis
XRD analysis was carried out to determine the crystalline
phases present in cement before hydration. In XRD analysis, each
major peak refers to a specific crystalline phase present in cement
[34]. The positions of the peaks are determined by the spacing of
the crystallographic planes according to Bragg’s law as provided
below [35].
nk ¼ 2d sin h ð3Þ
where n is an integer or order of diffraction, k is the wavelength of
the radiation used, d the spacing of the crystal planes and 2h the
angle of the diffraction peak. X-ray diffracted spectrum is analyzed
to identify the phases corresponding to significant diffracted peaks.
The parameters used in XRD analysis are presented in Table 2.
The XRD spectrum of OPC is presented in Fig. 3. It can be
observed that the cement used in this study mainly consists of
crystalline phases of di-calcium silicate ðC 2 SÞ and tri-calcium sili-
cate ðC 3 SÞ respectively.
2.2. Characterization of preformed calcium silicate hydrate (CSH)
In this study, abundantly available bagasse was used to prepare
the preformed CSH nano-crystals through a chemical process.
Bagasse ash was chemically treated with calcium bearing salt in
the aqueous phase in the presence of suitable dispersing agent to
prevent agglomeration immediately after the formation of CSH
gel. Field emission scanning electron microscope (FE-SEM) charac-
terization on freshly synthesized CSH nano crystals was performed
and the results are presented in Fig. 4. X-ray photoelectron spec-
troscopy (XPS) analysis was carried out to investigate about the
presence of various elements on the surface CSH nano-crystals.
The elemental composition obtained through XPS analysis is pre-
sented in Table 3. From Table 3, it can be observed that CSH nano
CaO MgO Na2 O TiO2 K2O
37.559 1.471 2.551 0.607 0.242
4 S. Das et al. / Construction and Building Materials 233 (2020) 117214

Table 2 3. Test methods

Parameter for XRD analysis.

The range 2h 20—70 In this section, preformed CSH crystals were used in cement
Step size 0.028829 paste and concrete to investigate the effects of external seeding
Copper K a radiation 1.54 Å
on setting time, rate of hydration and compressive strength. Fur-
Scanning rate 0:5 = min
Tube voltage 40 kV ther, more insights about the precipitation of hydration products
Tube current 30 mA in the presence of CSH seeds were investigated through various
advanced techniques namely, X-ray diffraction analysis, thermo-
gravimetry analysis (TGA) and FE-SEM studies.

3.1. Measurement of setting time of cement paste

Preliminary investigation on hardening performance of cement

paste in the presence of CSH nano crystals was carried out by mea-
suring setting time in accordance with IS 4031-Part5 [36]. Before
measuring the setting time, consistency limit was determined
and has been found to be 26%. Freshly prepared CSH crystals were
used to investigate the accelerating effects. The dosage of solution
containing CSH material was varied between 0 and 200 ml/kg of
OPC to the achieve optimum result with the measurement of initial
and final setting time.

3.2. Heat of hydration analysis

Heat of hydration analysis was performed on cement paste with

Fig. 3. XRD spectrum of OPC cement before hydration.
crystals contain very less amount of chloride on the surface indi-
cating negligible contribution towards corrosion. Further, as shown
in Fig. 4, the size of preformed CSH crystals fall in the nano scale
range and therefore could provide high surface area for early pre-
cipitation of hydration products.
and without CSH seeds using isothermal calorimetry. In this anal-
ysis, the effect of adding CSH seeds can be understood through the
measurement of the rate of heat evolution. An internal mixing pro-
cedure in accordance with ASTM 1702 [37] method A was adapted
at temperature 25 °C. Influence of external CSH seeds on hydration
reaction was investigated by measuring heat release and observing
the shifts in time and the height of hydration peaks.
3.3. Compressive strength
To investigate the effect of preformed CSH on early strength,
concrete compressive strength was measured after 6 h, 12 h, 18 h
and 24 h after casting. The dosages of CSH was varied from 0 to

Fig. 4. FE-SEM micrograph of CSH crystal.

 S. Das et al. / Construction and Building Materials 233 (2020) 117214 5

Table 3
Atomic concentration of elements on the surface of CSH particle determined from XPS analysis.

Elements C1s O1s Na1s Al2p Si2p Cl2p Ca2p

Atomic concentration (%) 20.15 53.14 4.94 0.34 13.88 0.93 5.53

350 ml/kg of cement. Concrete of M30 grade was designed in 3.5. Thermogravimetry analysis (TGA)
accordance with IS 10262–2007 [38] and the compressive strength
test was carried out according to IS 516–1959 [39]. Details of mix Thermogravimetry analysis (TGA) is performed to monitor con-
design parameters are presented in Table 4. While casting, con- tinuous loss in mass due to decomposition and emission of gases
crete mixture was observed to be properly workable even with under the application of steady increase in temperature. Thermo-
the addition of CSH based hardening accelerator. gravimetry application on cement paste is presented schematically
in Fig. 5. TGA can be effectively used to measure the hydration pro-
duct Portlandite (CaðOHÞ2 ) present in the hydrated cement paste.
3.4. Crystalline phase analysis
Portlandite content can be quantified from the thermogravimetry
(TG) curve by measuring the mass loss that occurs at decomposi-
XRD analysis was performed to investigate qualitative informa-
tion temperature. Similar procedure of sample preparation as
tion about different crystalline phases developed during the hydra-
described for XRD was adopted for this analysis. TGA was per-
tion process. To prepare the sample, 95.2 ml of water with CSH at a
formed for cement paste with preformed CSH crystals at dosage
dosage of 150 mL/kg of cement were mixed with 400 g of cement.
In order to stop hydration after setting time and 120 min of mixing,
the samples with and without preformed CSH were immersed in
ethanol solution. The parameters considered during analysis was
according to Table 2. XRD along with Retveld analysis is widely
accepted method for identifying the crystalline hydrated phases
present in concrete matrix [40] and the same was performed in
this study.

Table 4
Design mix of concrete.

Grade of concrete M 30
Water cement ratio 0.45
Cement content 492.2 kg=m3
Water content 197.16 kg=m3
Fine aggregate content 677.224 kg=m3
Coarse aggregate content 963.29 kg=m3
Cement: Fine aggregate: Coarse aggregate 1:1.37:1.95

(a) Initial setting time

Fig. 5. Schematic representation of expected decomposition taking place in a

cement paste during TG analysis.

(b) Final setting time

Fig. 6. Photograph of cement pellets prepared without (blank) and with preformed
CSH seeds. Fig. 7. Setting time of cement paste at different dosages of CSH seeds.
6 S. Das et al. / Construction and Building Materials 233 (2020) 117214
varying between 0 and 150 ml/kg of cement. Analysis was carried
out after 1 day, 3 days and 7 days of preparing the specimens. The
powdered samples in a ceramic crucible were heated up to 1000 °C
at a rate of 10 °C/min in nitrogen atmosphere. Alumina powder
was used as the reference material during TGA experiment. Ther-
mogravimetry curves for OPC describing the percentage of mass
present versus temperature are represented in Figs. 13–15 for
1 day, 3 days and 7 days respectively. Sudden change in slopes in
TG curve correspond to a specific temperature range and specific
phase. Change in slopes in temperature, ranging between 25–
100 °C, 100–350 °C, 430–460 °C, 700–900 °C occur mainly due to
evaporation of surface adsorbed water, dehydration of CSH and
ettringite [41] and calcium aluminate hydrate, decomposition of
CaðOHÞ2 [42] respectively. Decarbonation of calcium carbonate
takes place between temperature 700 and 900 °C [42].
3.6. FE-SEM analysis
Cement pellets with preformed CSH seeds were prepared and
cured for 24 h (Fig. 6). The same dosage of CSH seeds was used
as that of TGA samples. After the curing period, pellets were dipped
in ethanol solution to stop hydration. It is known that ethanol can
displace pore water form cement paste which is responsible for
(a) Heat flow rate by isothermal calorimetry at 250 C
(b) Energy released during the first 18 h of hydration of cement pastes at 250 C
Fig. 8. Effects of addition of preformed CSH seeds on the hydration of Portland
cement paste.
further hydration. Field emission scanning electron microscopy
(FE-SEM) analysis was carried out to examine localized morphol-
ogy at the microscopic scale. The analysis was done under an accel-
erating voltage of 20 kV and pressure of typically
1  106 —1:95  106 mbar. Results were reported after collecting
data from at least ten randomly selected sites of the cement pellets
and avoiding the overlapping areas. Secondary electron (SE) detec-
tor was used to obtain the surface morphology. This characteriza-
tion technique imparts a quick visual prediction of different phases
present on the surface of the cement paste.
4. Results and discussion
4.1. Setting time of cement
Hardening effect of cement paste due to the addition of external
CSH seeds was investigated through measurement of setting time.
The results of initial and final setting time with different dosages of
CSH seed are presented in Fig. 7(a) and (b) respectively. Initial and
final setting time of cement paste without preformed CSH are
determined to be 87 min and 225 min respectively. While the pres-
ence of preformed additives showed rapid acceleration effects in
both initial and final setting time. It can be observed that with
(a) Heat flow rate by isothermal calorimetry at 250 C
(b) Energy released during the first 24 h of hydration of cement pastes at 250 C
Fig. 9. Effects of preformed CSH seeds on hydration of fly ash based cement paste.
 S. Das et al. / Construction and Building Materials 233 (2020) 117214 7

in Fig. 1 and Fig. 2. In the presence of external CSH seeds additional

nuclei are available in the system and therefore the first energy
barrier is overcome in this process. This in turn reduces the induc-
tion period. The percentage reduction in the induction period with
the addition of CSH seeds is approximately around 60% than com-
pared with the blank cement paste i.e. without CSH. Due to such
observed reduction in the induction period, early strength develop-
ment is expected with the external seeding.
Further, variations of the total heat evolved as a function of time
from mixing are shown in Fig. 8(b) for both blank cement paste and
cement paste with CSH seeds. It is to observe that in the presence

Fig. 10. Effect of different dosages of CSH based hardening accelerator on

compressive strength of concrete after 6 h, 12 h, 18 h and 24 h of casting.

the dosages of preformed CSH as 150 ml/kg, the reduction in initial

and final setting time are 43% and 18% respectively. However, with
further increase in dosage no significant reduction in setting time
was observed. Therefore, it can be concluded that the optimum
dosage of preformed CSH based hardening accelerator is 150 ml/
kg. The reduction in setting time is attributed to early strength
development of concrete which is further verified by measuring
the compressive strength. The setting and hardening process of
concrete are mainly associated with the hydration of cement min-
erals. The results of this preliminary study reveal that addition of
CSH seeds can accelerate the overall hardening process in concrete.
(a) XRD of cement paste with and without CSH during the initial setting time
4.2. Heat of hydration analysis

Variation of heat flow with mixing time for both blank cement
paste (without CSH) and cement paste with CSH seeds are pre-
sented in Fig. 8(a). As shown in Fig. 8(a), the initial peak in the
hydration curve occurs within 30 min of mixing of water due to
the formation of ettringite [43]. This is followed by induction per-
iod or stage II in which the hydration rate is reduced for few hours
due to the formation of transient meta stable CSH layer and this
resists the ingress of water for hydration [44–46]. Beyond the
induction period, acceleration in the hydration process occurs
and the main hydration peak is observed. This is due to the con-
sumption of C 3 S phase in cement paste and precipitation of port-
landite and CSH [43]. A considerable reduction in induction
period is observed in CSH based cement paste than the blank. In
the hydration process when water is added to cement, dissolution
begins immediately and ions of calcium, silica etc. come into the
pore water phase. As the time proceeds, pore water gets supersat-
urated with ions and calcium hydroxide (CaðOHÞ2 ) starts to precip-
itate and the concrete develops stiffness. Moreover, before
precipitation, nuclei are formed and then growth proceeds. In
(b) XRD of cement paste with and without CSH after 120 minutes hydration
order to form the nuclei the pore solution system has to overcome
critical free energy. The time taken to overcome this critical free Fig. 11. XRD spectra of cement paste with and without CSH accelerator (a) after
energy is called induction period or nucleation time as depicted initial setting (b) after 120 min.

Table 5
Effect of preformed CSH on compressive strength in MPa after 3, 7 and 28 days of casting

Dosages (ml/kg) 0 50 100 150 200 250 300 350

3 day 24.558 24.055 25.07 25.667 24.78 24.91 25.98 26.28
7 day 29.45 29.5 29.5 30.12 30.33 31 30 30.834
28 day 35.01 35.00 35.95 36.10 35.99 36.89 37.12 38.1
8 S. Das et al. / Construction and Building Materials 233 (2020) 117214

of external CSH seeds more energy is released within 12 h indicat- The results of compressive strength presented in Table 5 indi-
ing accelerated hydration compared to the blank cement paste. cate that there is not much variation in compressive strength val-
Now a days fly ash based concrete is becoming more popular ues for 3 days, 7 days and 28 days of control cubes and the cubes
and is considerably used in construction due to its pozzolanic nat- with CSH seeds. Therefore, it can be concluded that the presence
ure. In the presence of fly ash, secondary hydration reaction takes of CSH based accelerator imparts early strength within 24 h
place with CaðOHÞ2 leading to formation of secondary hydration (Fig. 10) without compromising the 28 days compressive strength.
products (CSH). This helps in achieving a dense microstructure in
concrete. However, due to occurrence of secondary hydration reac-
4.4. Crystalline phase analysis
tion, the strength gain process is relatively slower than normal
concrete without fly ash (OPC). Heat of hydration analysis has been
Qualitative XRD analysis was done for blank cement paste and
carried out in the laboratory to investigate the hydration process of
cement paste with preformed CSH corresponding to the time of
fly ash based concrete. In this experiment, CSH seeds are used at a
measurement of setting time and after 120 min of mixing. XRD
concentration of 150 ml/kg and cement (OPC) is replaced by 25%
patterns for both the cases are presented in Fig. 11. The peaks of
by weigth of fly ash. Heat of hydration result presenting rate of
the crystalline phase of CaðOHÞ2 i.e. Portlandite are shown in
heat flow with time is shown in Fig. 9(a). It can be clearly observed
Fig. 11. A closer view of Portlandite peak at an angle of 34:089
that presence of CSH nano crystals shorten the induction period.
for both the cases is presented in Fig. 12 for comparison purpose.
Further, relatively higher intensity in the main hydration peak is
It is to be observed that the peak of Portlandite phase of cement
observed in the case of cement paste with CSH gel than blank fly
ash based paste. A reduction in induction period about 75% is
observed in the case of CSH based cement paste. Therefore, it is
reasonable to conclude that the addition of CSH nano crystals are
more effective in fly ash based cement paste than normal OPC
without fly ash.

4.3. Compressive strength

Early age compressive strength of concrete cubes with different

dosage of CSH based hardening accelerator was measured after 6 h,
12 h, 18 h and 24 h after casting. The measured compressive
strength values are presented in Fig. 10. In Fig. 10, the dosage 0
ml=kg represents the sample without CSH seed called as control
cubes. It can be observed that the average compressive strength
values of concrete cubes with CSH based accelerator are relatively
higher than that of the control cubes. In specific, it may be noted
that six hours compressive strength of the control cubes is almost
zero while CSH based cubes with dosage of 300 ml/kg show com-
pressive strength of 2.5 MPa. Further, it may be noticed that in
the presence of CSH based accelerator concrete achieves 12 h com-
pressive strength within 6 h and 18 h strength within 12 h. There-
fore, addition of CSH seed in concrete accelerates the hydration Fig. 13. Thermogravimetry analysis of cement paste with or without preformed
CSH seeds (after 1 day).
process in turn the early age strength gain process by 30–50%.
The effect of CSH based hardening accelerator on compressive
strength after 3 days, 7 days and 28 days have been investigated
and are presented in Table 5.

Fig. 12. Portlandite ðCaðOHÞ2 Þ peak of cement paste with and without CSH at Fig. 14. Thermogravimetry analysis of cement paste with or without preformed
34:0890 at initial setting. CSH seeds (after 3 days).
 S. Das et al. / Construction and Building Materials 233 (2020) 117214
Fig. 15. Thermogravimetry analysis of cement paste with or without preformed
CSH seeds (after 7 days).
paste with preformed CSH is higher than that of the blank cement
paste. It is known that the intensity of XRD peak in crystalline
phase is proportional to the quantity present in the sample [35].
Therefore, it can be stated that existence of higher peak in the pres-
ence of CSH based accelerator could cause more precipitation of
hydration products. The above conclusion falls in-line with the
results of setting time of OPC cement paste.
Fig. 16. Scanning electron micrographs of cement paste prepared with different dosages of CSH seeds after 1 day of hydration.
9
4.5. TG analysis
Quantitative analysis of both crystalline and amorphous phases
present in concrete can be done through thermal analysis. Decom-
position of Portlandite, CaðOHÞ2 at 450 °C can be expressed as
below:
CaðOHÞ2 !CaO þ H2 O ð4Þ
TGA results in terms of percentage of mass present versus tem-
perature are represented in Figs. 13–15 for 1 day, 3 days and 7 days
respectively. It may be noticed that presence of CSH seeds cause
more mass loss implying more precipitation of hydration products
which are responsible for early strength development of concrete.
Further, in Fig. 13 it can be seen that after 1 day, the concentra-
tion of CaðOHÞ2 increases with the increase in dosage of preformed
CSH seeds. Addition of CSH seeds accelerate the hydration process
thereby enhancing the precipitation of CaðOHÞ2 . Therefore, early
age (24 h) compressive strength gets improved with the addition
of CSH seeds. On the other hand, concentration of CaðOHÞ2 of
cement paste without and with CSH seeds are the same after 3
and 7 days of hydration. Similarly, not considerable difference in
compressive strength was found after 3 and 7 days in the presence
of CSH based accelerator. This is in agreement with the results
obtained from setting time, compressive strength, heat of hydra-
tion and X-ray diffraction analysis.
4.6. FE-SEM analysis
The scanning electron micrographs (SEM) of the cement paste
after 24 h of the addition of preformed CSH seeds are presented
in Fig. 16. Figs. 16(a)–(d) correspond to cement paste with CSH
seeds at dosages of 0 ml/kg, 25 ml/kg, 50 ml/kg and 125 ml/kg
10 S. Das et al. / Construction and Building Materials 233 (2020) 117214

respectively. It may be observed that the micro-structure of
cement paste in the presence of CSH seeds shows relatively lesser
voids and higher precipitation of hydration products compared to
the cement paste without external seeds. Due to the addition of
CSH seeds in the cement paste, hydration process proceeds at a fas-
ter rate and the inter space of cement grains are filled up with the
hydration products at early age. Important hydration products
namely, ettringite (needle shaped in morphology [47,22]), calcium
hydroxide (plate type crystal of hexagonal morphology), CSH gels
(flake morphology)[47] are shown in Fig. 17. In order to have con-
firmation about various hydration products, energy dispersive
spectroscopy (EDX) characterization results at selected positions
are provided along with the FE-SEM images. EDX analysis provides
qualitative information about the major elements associated with
a particular phase. EDX results presented in Figs. 17(a)–(c) confirm
the identified phases in the FE-SEM images. It can be observed in
Fig. 17 that more precipitation of plate type crystal of hexagonal
calcium hydroxide, ettringite and CSH are present in CSH based
cement paste contributing towards early strength development
in concrete.

Fig. 17. FE-SEM and EDX analysis of cement paste with CSH seeds.
 S. Das et al. / Construction and Building Materials 233 (2020) 117214
5. Conclusions
The following conclusions are drawn out of this research work.
1. Preformed CSH nano particles developed using bagasse ash
show promising results as an accelerator for early strength gain
in concrete by imparting seeding effect during the hydration
process. Presence of such nano particles reduce the initial and
final setting time of cement paste considerably. In addition,
the preformed CSH seeds have the ability to improve the early
age compressive strength of concrete to a greater extent. There-
fore, CSH based hardening accelerator can be suitably used in
concrete for early form-work removal of precast structural
members.
2. Addition of CSH seeds at dosage of 150 ml/kg and 250–350 ml/
kg have been found to provide optimum results for cement
paste and concrete respectively.
3. Results of heat of hydration analysis reveal that presence of
additional seeds significantly reduces the induction period of
Portland cement and fly ash-based cement paste and in turn
accelerates the overall hydration and strength development
process. In fact, an improved performance in terms of heat of
hydration has been observed in fly ash based cement paste than
the Portland cement. Therefore, it can be concluded that CSH
based hardening accelerator has more potential application in
fly ash based concrete for the early strength development.
4. In the presence of external seeds, relatively faster precipitation
of hydration products have been observed. Random distribution
of tiny seeds throughout the paste may lead to precipitation of
hydration products within the pore space between the cement
particles thereby may provide a dense and compact micro-
structure as compared to without CSH seeds. However, more
confirmatory studies are needed in support of this claim.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgment
The authors would like to thank National Building Construction
Corporation (NBCC) Limited, New Delhi, India for providing the
financial assistance to execute this work.
Appendix A
The total free energy ðDGN Þ to form a phase is the sum of the
bulk free energy ðDGbulk
N Þ and the surface free energy ðDGN
interficial
Þ References
which are responsible for the phase transformation and the surface
formation respectively [32]. Therefore, the total free energy for
transforming the a phase to the b phase can be expressed as [32],
DGN ¼ DGbulk
N þ DGinterficial
N ¼ Nðlb  la Þ þ gN2=3 c
where,
la and lb are the chemical potential of the a phase and the b
phase respectively. g is the shape factor. Phase transformation
inside the particle is spontaneous when la is grater than lb
[48]. Therefore DGbulk
N is negative. Considering,
E0 is the energy in volume of the phase per atom.
S0 is the entropy of the phase per atom.
Es is specific surface energy (i.e energy per unit area).
11
A is the surface area of the phase.
N is the number of atoms present in the phase.
Hs is the enthalpy.
c is the surface tension.
Then, the total energy is given by [49],
E ¼ NE0 þ AEs ð6Þ
Similarly,
total entropy is S = NS0 + A Ss
total free energy is G = NG0 + A Gs
surface free energy is Gs ¼ Hs  TSs
Now, the total free energy change dG considering the contribu-
tion from surface work can be written according to the law of ther-
modynamics as [50],
dG ¼ SdT þ VdP þ cdA ð7Þ
where, T and P are temperature and pressure respectively. At con-
stant temperature (T) and pressure (P),
dG ¼ cdA ð8Þ
The surface area can be increased by addition of a new atom on
the existing surface. Total free energy can be expressed as sum of
volumetric and surface energy part as presented below [49].
G ¼ NG0 þ AGs ð9Þ
Change in free energy during phase transformation due to the
only change in surface free energy can be obtained by differentiat-
ing the above Eq. 9 can be written as
dGT;P ¼ dðAGs Þ ð10Þ
The above Equation can be expanded as at constant T; P.
@ðGs AÞ @Gs
dGT;P ¼ ð Þ dA ¼ ½Gs þ Að Þ dA ð11Þ
@A T;P @A T;P
The specific surface free energy (Gs ) is constant and indepen-
dent upon the surface area. Therefore
@Gs
ð Þ ¼0 ð12Þ
@A T;P
Increment in surface free energy in new phase due to addition
of new atom from the above equation can be written as
dGT;P ¼ Gs dA ð13Þ
Combine the Eqs. 8 and 13 to get dGT;P ¼ G dA ¼ cdA [51]. s
Therefore Gs ¼ c.
Therefore, the surface free energy is always positive as surface
tension is positive.
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