Construction and Building Materials 394 (2023) 132173

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Construction and Building Materials

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Hydration of Portland slag cement in the presence of nano silica

Raju Goyal a, Vinay K. Verma a, N.B. Singh a, b, *
a
Department of Chemistry and Biochemistry, Sharda University, Greater Noida 201310, India
b
Research Development Cell, Sharda University, Greater Noida 201310, India

A R T I C L E I N F O A B S T R A C T

Keywords: The cement industry accounts for nearly 7% of carbon dioxide (CO2) emissions globally and is facing tremendous
Cementitious pressure to reduce the emission intensity. Supplementary cementitious materials (SCM) are a quick and effective
Nano SiO2 lever to lower CO2 emissions. The cement hydration process is a sensitive mechanism and is greatly influenced by
Hydration
many factors such as hydration environment, type of SCM, and the amount used in the cement, which affect the
Heat Evolution
Strength
cement’s physical and mechanical performance. The SCM adversely impacts cement performance, especially
Carbon Dioxide prolonged setting and slow initial compressive strength development, compared to ordinary Portland cement
Microstructure (OPC). The importance of nanomaterials has been known for decades; their usage in cementitious materials is
Blended cement now accelerated as they can play an essential role by offsetting the adverse effects of the high usage of SCMs in
cement. They help in reducing the intensity of CO2 and offer value-added features. A lab experiment is carried
out to understand the role of nano SiO2 at different dosages on the Portland slag cement (PSC) hydration by
studying heat evolution profiles, compressive strengths, TG-DTA, XRD, and SEM images. Results have revealed
that 1% nano SiO2 accelerates early settings time and compressive strength compared to OPC. It will promote
slag-based blended cement (PSC) and replace ordinary Portland cement in the construction industry to reduce
the CO2 footprint of the cement and construction industry. A model of NS’s role during PSC hydration is also
given.

1. Introduction
Cement, an important concrete component, is manufactured by
heating large quantities of limestone at high temperatures and then
milling it with gypsum and other additives to produce ordinary Portland
cement (OPC) [1]. Production of One ton of OPC produces about 0.80 t
CO2, severely affecting the environment [2,3]. Given the focus and need
on sustainability and reducing CO2 emission, the cement industry is
exploring various options, such as using green power and switching to
alternative energy sources, including carbon capturing storage and uti­
lization, to get net zero emission targets. However, blended cement is an
immediate and effective alternative to reduce CO2 emissions in the
cement and construction industry. Blended cement is produced using the
by-products from the industrial and agriculture sectors, such as fly ash,
slag, rice husk, limestone, and others. However, a significant drawback
in using blended cement is mainly prolonged initial and final setting
time, delayed early strength development, and prolonged later strength
compared to OPC. To overcome such problems, producing less clinker-
based modified concretes with lower levels of CO2 emission became a
challenge in the building sectors. In recent years various nanomaterials
(NMs) such as nano-SiO2 (NS), nano-Al2O3, nano-TiO2, nano-CaCO3
(NC), nano-Fe2O3, carbon nanotubes (CNT), and graphene have been
incorporated in mortars and concretes in order to attain the sustain­
ability objectives in the civil engineering field [4–6]. Despite a lot of
interest in using NMs in cement mortar and concrete, little work has
been done on blended cement and mortars [7–9].
The use of NS in concretes has now become a research hotspot [10].
NS has a fine particle size (10–100 nm) and high surface area, which can
act as a seeding nuclei for nucleation and formation of hydrates [11,12].
Besides, the particles in the nanoscale can directly fill pores in cement
particles or other larger particles [13]. Nano-silica can also consume CH
and generate C–S–H gel [14]. Thus, NS can markedly enhance the
properties of cement mortars and concrete, especially at an early hy­
dration period [15,16].
Portland Slag Cement (PSC), because of its lowest carbon footprint
compared to other commercially available cement such as OPC,

Abbreviations: CH, Calcium Hydroxide; C-S-H, Calcium silicate hydrate; NS, Nano SiO2; OPC, Ordinary Portland Cement; PSC, Portland Slag Cement; SCM,
Supplementary cementitious materials.
* Corresponding author.
E-mail address: n.b.singh@sharda.ac.in (N.B. Singh).

https://doi.org/10.1016/j.conbuildmat.2023.132173
Received 25 March 2023; Received in revised form 13 June 2023; Accepted 14 June 2023
Available online 20 June 2023
0950-0618/© 2023 Elsevier Ltd. All rights reserved.
R. Goyal et al. Construction and Building Materials 394 (2023) 132173

Table 1
Mix proportion of PSC and OPC blends with NS.
Sample ID NS, % OPC, %

OPC 0 100
PSC-NS0 0 100
PSC-NS1 1 99
PSC-NS2 2 98
PSC-NS3 3 97
PSC-NS5 5 95

2. Materials and methods

2.1. Materials

The cement commercially available in the market used in this study

was OPC-53 Grade as per code IS 269:2015 and PSC as per code IS
455:2015 and purchased locally. The NS was purchased from Reinste
Fig. 1. PSC share in total cement production in 2020. Nano Ventures Pvt. Ltd., India. The lab-grade chemicals and standard
materials are used to test and measure PSC performance with and
Portland Pozzolan Cement, Portland composite cement, Portland without NS.
Limestone Cement, and others, can be considered as an appropriate
cement in the present scenario. PSC is produced when granulated blast
2.2. Methods
furnace slag (GBFS) is mixed during the milling of OPC as per code IS
455:2015. Over 400 million tons of iron and steel slag is produced each
2.2.1. Preparation of samples
year worldwide, and approximately 60 million tons produced in India
Different cement samples were prepared with varying dosages of NS
are expected to double in the next decade. PSC has CO2 emissions up to
in PSC and intermixed adequately using a turbo mixer of 10-liter ca­
70% lower than OPC in the cement industry. Although PSC has a lower
pacity to achieve proper mixing and homogenize the sample, as
CO2 footprint, its consumption is still limited; as per the report on
described in Table 1.
reducing cement sector emissions (Fig. 1). Only 9% of PSC was produced
in 2020.
2.2.2. Characterization of materials
The use of GBFS in the PSC offers several advantages, such as
The chemical composition of the OPC, PSC, and NS was determined
enhanced resistance to aggressive environments, lower heat of hydra­
using a Panalytical Axios Max model X-Ray fluorescence (XRF) spec­
tion, minimizing the risk of alkali-silica reaction, better ultimate
trometer on the fused bead, and results are given in Tables 2 and 3. The
strength of cement and concrete, and improved rheological properties of
cement used in this study met the code specifications, IS 269:2015 and IS
fresh mortar and concrete [17]. However, it has disadvantages such as
455:2015, respectively. NS composition indicated that the material was
longer setting time, lower early compressive strength, and delayed
of very high purity with 99.32% silica content and a loss on ignition of
strength development.
0.20%. See (Table 4).
The cement performance mainly depends on the hydration rate and
The particle size distribution (PSD) of OPC and PSC was measured,
its environment, which modifies the calcium silicate hydrate crystal size,
and it was found that PSC has finer particles than OPC (Table 5).
one of the major products formed in the cement hydration process, and
Mineralogical composition by XRD was determined using TOPAS
is responsible for the densification of the matrix and strength. NMs have
software based on the Rietveld refinement method (Table 6).
a very high surface area and reactivity; thus, various nanoparticles have
The XRD analysis of the OPC and PSC was carried out. The results
been reported to modify the performance of cementitious materials
indicated the presence of C3S, C2S, C3A & C4AF along with Gypsum &
[18,19].
Bassanite from the added gypsum (Fig. 2). PSC shows the presence of
NS improves the properties of the cement by generating an addi­
distinct amorphous pattern due to the presence of granulated blast
tional amount of C-S-H and modifies the structure of hydration products,
furnace slag (GBFS) in PSC as shown in Fig. 3a, and Fig. 3b. The XRD
which gives distinctive physical and chemical properties. The very high
pattern and a hump in the range of 2-theta = 18––36, indicate the
surface area, along with the pozzolanic activity of NS, induces an
amorphous content. The concentration of GBFS in the PSC is estimated
accelerated hydration process of the cement [20–22] by consuming
to be 55%, and the rest 45% is made of clinker and gypsum. [35]. The
calcium hydroxide produced during the primary hydration process of
GGBS content is estimated by carrying out the XRD analysis followed by
C3S and C2S minerals and produces additional secondary C-S-H gels
quantification of the crystalline minerals using the TOPAS software,
which leads to lower permeability as well as improved strength [23–29].
wherein the amorphous part of the slag is treated as its phase and then
NS shortens the induction period, which means acceleration of the hy­
seamlessly integrated into the Rietveld analysis for the complete quan­
dration kinetics [30,31]. It has been observed that NS improves the
tification of the PSC cement. Compared to OPC, the C3S concentration in
durability of concrete and cement-based products [32–35].
PSC also shows ~ 55% GBFS replacement.
Considering the above shortcomings of PSC and the advantages of
The XRD pattern of the NS is shown in Fig. 4, which clearly shows the
NS, the present investigation was undertaken. In this research paper, the
amorphous nature of NS. The crystallite size was evaluated using
hydration of PSC in the presence of different amounts of NS and the
Scherer’s equation.
absence of a superplasticizer has been studied, and a mechanism has
been proposed. 0.94λ
D= (1)
βCos [03B8]

where D-the average crystallite size of the particle, λ- wavelength of X-

ray, β, full width at half maximum, θ- Bragg’s diffraction angle. The
crystallite size of NS was calculated. to be 35 nm.
The SEM analysis of NS was carried out (Fig. 5). It is observed that

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R. Goyal et al. Construction and Building Materials 394 (2023) 132173

Table 2
Chemical composition of the cement - OPC and PSC (%).
Cement LOI SiO2 Al2O3 Fe2O3 CaO MgO Na2O K2O SO3

OPC 53G 3.07 20.68 5.42 4.22 61.80 0.87 0.30 0.38 2.92
PSC 1.71 30.05 10.07 2.18 48.02 3.85 0.37 1.17 2.33

Table 3
Chemical composition of Ground Granulated Blast-furnace Slag (GGBS) (%).
LOI SiO2 Al2O3 Fe2O3 CaO MgO Na2O K2O SO3 Cl TiO2 P2O5

0.40* 36.5 18.61 0.33 33.95 6.84 0.13 0.73 0.62 0.010 0.45 0.12

increased due to the fineness of NS. Based on the experiment, a higher

Table 4 water-binder ratio was applied. In this study, an average value of 0.45 as
Chemical composition of NS (%). w/c without superplasticizer was used as reported earlier [36].
LOI SiO2 Al2O3 Fe2O3 CaO MgO Na2O K2O SO3

0.20 99.32 0.08 0.05 0.18 0.03 0.02 0.03 0.01 2.2.4. Heat evolution
The TAM AIR isothermal calorimeter from TA instruments was used
to study the heat evolution, which has an air-based thermostat and
easily interchangeable 8-channel standard volume offering high sensi­
Table 5
tivity and long-term temperature stability for detecting and character­
Particle Size Distribution of OPC and PSC.
izing heat production from different mixes of PSC with 0%, 1%, 2% 3%
Parameters OPC PSC
and 5% NS, for a period of 72 h at a fixed w/c of 0.45 at 27OC.
d10, micrometres 7.98 2.76
d50, micrometres 22.15 14.92 2.2.5. Setting times
d90, micrometres 50.89 38.01
The initial and final setting times of OPC and PSC with 0%, 1%, 2%,
Avg diameter, micrometres 26.29 18.16
+ 45 µm, % 14.67 4.89 3%, and 5% NS at w/c 0.45 were determined using Vicat apparatus as
per the method mentioned in the code IS:4031 (Part 5):1988.

the average particle size is in the range of 30–50 nm.
2.2.3. Standard consistency
The standard consistency was determined per IS 4031 (Part 4):1988
for PSC with 0%, 1%, 3%, and 5% as 33%, 36%, 42%, and 57%,
respectively. It is observed that with an increase of NS%, water demand
2.2.6. Compressive strength
The compressive strength of mortar of OPC and PSC with 0%, 1%,
2%, 3%, and 5% NS at fixed w/c of 0.45 at different ages viz, 1, 3, 7, and
28 days were measured by using the automatic compressive strength
testing machine, CTM-314E of AIMIL India, in accordance with the
method mentioned in code IS 4031(Part 6): 1988.

Table 6
Mineralogical composition of OPC and PSC (%).
Cement C3S C2S C3A C4AF f-CaO Gypsum Bassanite Anhydrite Quartz Calcite GGBS

OPC 57.58 16.41 3.97 11.72 0.70 0.60 1.71 0.21 0.92 5.2 NIL
PSC 24.48 4.95 1.67 5.10 0.23 0.77 1.62 1.35 0.12 1.63 55

Fig. 2. XRD of OPC indicating the main minerals.

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R. Goyal et al.
Fig. 3a. XRD of PSC.
Fig. 3b. XRD of GGBS.
2.2.7. Water penetration test
The Karsten tube penetration test, which is a non-destructive method
for obtaining useful information about the condition of PSC cement
mortar cubes with and without the addition of NS at different dosages,
was conducted on cubes cured for 28 days in the standard condition. The
amount of water absorbed by the cement mortar cubes was measured at
different time intervals. Tests were repeated three times in selected areas
of the cement mortar specimen, and the volume of water absorbed was
plotted against the time for PSC mixes with 0%, 1%, and 3% NS dosage.
Fig. 4. XRD of NS.
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Construction and Building Materials 394 (2023) 132173
2.2.8. XRD studies
The XRD patterns of PSC with 0%, 1%, 2%, 3%, and 5% NS dosage
hydrated for 1 and 28 days were recorded between 2θ = 8◦ to 75◦ in
order to identify the hydration products.
2.2.9. Thermogravimetric analysis
The thermal stabilities of PSC is hydrated with 0%, 1%, 2%, 3%, and
5% NS dosage for 1 day and 28 days were studied using a Simultaneous
thermal analyzer (STA), STA 449 Jupiter from Netzsch. The thermal
analysis was carried out in a Nitrogen atmosphere with a flow of 60 ml/
min at a heating rate of 10 ◦ C/min from ambient to 1000 ◦ C.
2.2.10. SEM studies of hydrated PSC
SEM images of PSC hydrated with 0%, 1%, and 3% NS dosage for 1
and 3 days at w/c 0.45 were recorded with Nova Nano SEM 600 FEG
scanning electron microscope equipped with a field emission gun and an
energy-dispersive X-ray analyzer. Samples were gold coated for a
duration of 120 s using a sputter coater to prevent the charging of the
samples.
2.2.11. Analysis of solution during hydration for Ca2+ and Si(IV) ions
Concentrations of Ca2+ and Si(IV) ions were measured at w/c of 1, by
using Microwave Plasma Atomic Emission Spectroscopy (MP-AES) in
PSC in the presence of 0%, 1%, and 3% NS at intervals of 5, 10, 20, 30,
40, 50, and 60 mins. After the given time interval, the cement solutions
were filtered using Whatman No.42 filter paper. To measure the calcium
and silica ions released, MP-AES was set at the wavelengths of 616.2 nm
and 251.6 nm, respectively.
2.2.12. Durability in acids
The durability of PSC with 0%, 1%, and 3% NS was studied by
immersing the mortar cubes in 5% sulphuric acid (H2SO4) and 5% hy­
drochloric acid (HCl). The mortar cubes were cast at 27 ◦ C and water
cured for 28 days. The immersed cubes in the respective acid solutions
after 3 and 7 days duration were taken out and washed with normal
water, and then the residual compressive strength of the cubes was
determined.
3. Results and discussions
3.1. Heat evolution
The normalized heat flow and the total cumulative heat released as a
function of time for the hydration of PSC in the presence of 0, 1, 2, 3, and
5% NS are shown in Figs. 6 and 7. The PSC’s normalized heat flow curves
R. Goyal et al.
Fig. 5. SEM picture of NS.
Fig. 6. Normalized heat flow curves for the different PSC blends.
indicate an additional third peak on the shoulder of the second promi­
nent peak, confirming that the aluminate reactions from slag occur
during hydration [32]. The total cumulative heat flow curves confirm
that NS accelerates the hydration reaction [35]. However, with the
higher dosage of NS at 5%, the normalized heat flow curve shifted to the
left side significantly (Fig. 6). The total cumulative heat flow curves of
PSC with 5% NS show that after the early hydration period, the total
heat of hydration starts declining after 60 h (Fig. 7). It could be due to a
lack of water in the cement paste because of the very high surface area
from NS, which constrains the cement hydration further at a higher NS
%. It is indicated that using NS with slag can effectively control the total
cumulative heat of hydration of cement [35].
When enlarging the normalized heat flow curves, it can be observed
that as the dosage of nano-silica increases in the PSC, the induction
period decreases, and the acceleration period increases, as indicated in
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Construction and Building Materials 394 (2023) 132173
Fig. 8; this can be related to reducing setting times and enhancing early
compressive strength.
3.2. Setting times
The setting times were measured at w/c = 0.45 to examine the effect
of NS in PSC with 0, 1%, 2, 3, and 5 dosages without a superplasticizer.
The initial setting time (IST) and final setting time (FST) gradually
decreased with increasing dosage of NS in the PSC [35] (Fig. 9). The
PSC, IST, and FST are higher than OPC by 10% and 5%, respectively,
because GBFS has less chemical reactivity than cement. The higher
amount of GBFS significantly reduces hydrate phases, such as C–S–H and
C-A-S-H, and because of this, IST and FST are prolonged in PSC. With a
1% NS addition in PSC, the IST and FST were reduced by 20%, which can
help reduce the construction project completion time and save the
R. Goyal et al.
Fig. 7. Total cumulative heat flow curves for the different PSC blends.
Fig. 8. Schematic representation of the induction and the acceleration period
in the PSC mix.
project cost. It is noticed that with 5% NS in PSC, IST, and FST reduced
drastically, it can be due to the higher surface of cement with high NS,
and water was not sufficient for the completion of the reaction. There­
fore, a higher dosage of NS is not favorable to use in PSC. However, it can
be concluded that the setting times can be modified in PSC by optimizing
Fig. 9. Setting times of OPC and PSC with various concentrations of NS.
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Construction and Building Materials 394 (2023) 132173
the NS % and achieving the required workability like OPC.
3.3. Compressive strength
When the compressive strength of OPC is compared with PSC
without NS, PSC strength is significantly lower by 38, 28, 18, and 1% at
1, 3, 7, and 28 days respectively, as measured, ascribed due to lesser
chemical reactivity of GBFS and dilution effect [35]. It is seen that the
early strength of PSC is significantly lower than OPC, but at a later age,
strength is comparable to OPC due to the pozzolanic reactivity of GBFS.
The addition of NS, which has a very high specific surface area and
pozzolanicity, modifies and changes the hydration process, hydration
rate, and formation of larger amounts of hydration products and changes
the morphology and porosity of the PSC mortar. The nucleation and
seeding effects of NS may be responsible for enhancing the physical
properties of the cement. The compressive strengths of PSC with 0, 1, 2,
3, and 5% dosages of NS were measured at a fixed water-to-cement ratio
of 0.45 without using a superplasticizer. The compressive strength re­
sults indicated that adding 1% NS in PSC increases the strength of PSC by
49, 28, 16, and 4% at 1, 3, 7, and 28 days, respectively (Fig. 10). It
confirms that NS in the PSC modifies the overall hydration rate,
enhancing the early compressive strength significantly. However, more
than 1% NS in PSC shows a declining trend of compressive strength at all
ages. It may be due to the dilution of active cement mineral phases and
agglomeration of NS, which affects the hydration process and has no
positive influence. It is seen that the compressive strength of PSC with
1% NS was found to be lower by 16% than OPC at 1 day but higher by
R. Goyal et al.
Fig. 10. Compressive strengths of OPC and PSC cement blends.
Fig. 11. Water penetration trends of PSC in the presence of NS.
4% than OPC at 28 days (Fig. 10).
Rheological tests on cementitious pastes containing GBFS and 3% NS
have been carried out by Bouali et al. (2020) [37]. Cementitious pastes
with 3% NS without GBFS were the least viscous and have a lower shear
stress with acceptable workability compared to other cement pastes.
However, in the presence GBFS the cement pastes become more viscous,
which makes the flow more difficult with higher shear stress at the flow.
Results also showed that a small amount of NS in the cement, in the
presence of GBFS, increased the compressive strength remarkably.
3.4. Water penetration test
Karsten tube test on the mortar cubes of the cement blends indicates
that with the addition of NS in the PSC, water penetration decreases
(Fig. 11). It is due to the increased densification and filling of the pores
by the hydration products formed during PSC hydration. It can help
increase cement’s durability and prevent steel bar corrosion in the
concrete structure, prolonging its life.
3.5. XRD analysis of hydrated cement pastes
XRD patterns of the hydrated PSC in the presence of 0, 1, 2, 3, and 5%
NS at 1 and 28 days were recorded. Results showed that the intensity of
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Construction and Building Materials 394 (2023) 132173
the peak due to Calcium Hydroxide (CH) decreased, and that of Calcium-
Silicate-Hydrate (CSH) increased with the lowering of the C3S / C2S
peaks. It is due to the acceleration of the hydration (Figs. 12 and 13). The
indicated peak is due to increased C-S-H formation, as evident from the
peak broadening. XRD pattern suggests that the peak of C3S and C-S-H
lie in very close proximity (Fig. 14). The GBFS containing oxides (SiO2,
Al2O3, CaO, MgO, SO3) forms, ettringite, hydrotalcite, and C-S-H as the
typical hydration products. Hydrotalcite may be in very low quantity
compared to C-S-H and Ettringite and is not visible in the XRD pattern.
In the presence of 5% NS, the calcium hydroxide is very small, indicating
that it is almost consumed in the secondary reaction and forms addi­
tional CSH products. It also supports the findings that the addition of NS
in PSC accelerates the hydration process, which improves the early
setting time and compressive strength of PSC and offsets the adverse
effect of GBFS in PSC, leading to compressive strength development
close to OPC.
3.6. Thermogravimetric analysis
The TG and DTA curves of the hydrated PSC mix in the presence of 0,
1, 2, 3, and 5 of NS for 1 and 28 days are plotted in Figs. 15 and 16. The
TG curves show four distinct mass losses in different temperature ranges.
The first mass loss occurs between 5 and 105OC due to the elimination of
R. Goyal et al.
Fig. 12. XRD patterns of PSC hydration for 1 day in the presence of NS.
Fig. 13. XRD patterns of PSC hydration for 28 days in presence of NS.
Fig 14. Peaks due to C3S and C-S-H phase.
the adsorbed water; the second mass loss occurs between 110 and 170OC
due to dehydration of C-S-H and Ettringite, the third mass loss occurs
between 400 and 550OC due to the decomposition of calcium hydroxide,
and the final and fourth mass loss occurs due to the decomposition of
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Construction and Building Materials 394 (2023) 132173
calcium carbonate, which may be formed because of carbonation of the
calcium hydroxide. The CH amount is calculated from the curves based
on the weight loss in the hydrated samples in the temperature range of
400–500 ◦ C. At 800-900OC, a small peak is observed, indicating an
exothermic effect. It may be due to the recrystallization of some new
phases from hydrated cement minerals.
Percent CH in the PSC mixes with 0, 1, 2, 3, and 5% of NS are plotted
in Fig. 17. CH decreased with NS and time. It confirms that the addition
of NS actively participates in the hydration process. It is observed that
effective filling of the pores by nanomaterial particles prevents diffusion
and movement of chloride ions to the surface of the rebar and thereby
maintaining the passivity of the thin iron oxide layer around the steel
rebar. Hence, nano silica, which is known to have the pozzolanic effect
and leads to hydration acceleration, may maintain the passivity of
reinforcing steel [38].
R. Goyal et al. Construction and Building Materials 394 (2023) 132173

Fig. 15. TG-DTA curves of different PSC cement mix hydrated for 1 day.

3.7. SEM studies
The SEM images of PSC mix with 0, 1, and 3% of NS and OPC hy­
drated for 1 and 3 days are shown in Figs. 18 and 19. In OPC (Fig. 18 a
and 19 a), predominantly CH formation, AFt, and some un-hydrated
cement particles are seen. In the PSC without NS (Fig. 18 b and 19b),
other than AFt and C-S-H formation, small amounts of CH are seen due
to lesser clinker. In the case of PSC, at 1d of hydration in the absence of
NS, fewer C-S-H with coarse pores are formed. This is responsible for
lower early strength. However, in the presence of NS (Fig. 18c and 18d),

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R. Goyal et al.
Fig. 15. (continued).
C-S-H is seen to be formed, but the amounts are much higher in the
presence of 3% NS at 3d of hydration (Fig. 19 d), and because of this, the
structure is more compact leading to high compressive strength.
3.8. Calcium and silicon ions in solution
The variations of concentration of Si(IV) and Ca2+ ions with time in
PSC in the presence and absence of NS are shown in Figs. 20a and 20b,
respectively. Fig. 20a shows that Si(IV) is maximum in the presence of
3% NS at 20 min, and after that, it decreases. It is minimum in the
absence of o% NS. It appears that apart from GBFS, Si(IV) also comes
from NS. On the other Ca2+ concentration is maximum in the absence of
NS and minimum in the presence of 3% NS. It appears that Ca2+ ions
immediately after release combine with NS forming C-S-H.
Thus, the early formation of C-S-H in the presence of NS is respon­
sible for reducing setting time and increasing compressive strength.
3.9. Durability
The durability of cement mortar cubes of PSC mixes with 0, 1, and
3% NS was evaluated by keeping cubes in the solution of 5% sulfuric
acid (H2SO4) and 5% hydrochloric acid (HCl). Results showed that
cement cubes in the presence of 0, 1, and 3 of NS, when exposed to 5%
hydrochloric acid for 3 days, lost compressive strength by 30, 27 and
18%, respectively, whereas exposed to 5% sulphuric acid solution,
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Construction and Building Materials 394 (2023) 132173
compressive strength decreased by 24, 20 and 16% respectively. It can
be inferred that in the presence of a high amount of NS, the PSC cube is
more durable in the presence of H2SO4 as compared to that in HCl at an
early age, up to 3 days (Fig. 21 a). It is also observed that the same
cement cubes at 7 days lost compressive strengths 22, 25, and 32% in
HCl, whereas 37, 39, and 41%, respectively in H2SO4. Thus, it can be
said that in the presence of high NS in PSC is more durable in the
presence of HCl than H2SO4 at 7 days, as shown in Fig. 21 b.
From Fig. 22, it is very much visible that the deterioration in the
presence of the hydrochloric acid is less than sulphuric acid at 7 days
with the addition of NS.
It is observed that there was a formation of a white layer on the outer
surface of PSC mortar cubes when immersed in H2SO4 for 3 days with 0,
1, and 3% NS. The white layer coating was separated and examined by
XRD, and it found that it was gypsum formed by the reaction of calcium
leached from the mortar cube and SO42- ions obtained from H2SO4
(Fig. 23). However, no such formation of the coating was observed in the
mortar kept for the same duration in HCl since most of the chloride salts,
including Calcium Chloride, are soluble.
4. Environmental impact assessment - carbon dioxide (CO2)
reduction analysis
The PSC has a lower amount of clinker compared to OPC; the esti­
mated composition of OPC and PSC used in the experiment are given in
R. Goyal et al. Construction and Building Materials 394 (2023) 132173

Fig. 16. TG-DTA curves of different PSC cement mix hydrated for 28 days.

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Fig. 16. (continued).

Fig. 17. CH content in PSC hydrated for 1 and 28 days in the presence of NS (400-500OC).

Fig. 24 (a) and (b), respectively. As per code IS 269–2015, in the OPC than OPC.
performance improver (PI) is allowed to use, and in the PSC maximum, To estimate the carbon footprint (kgCO2/t cement), 860 kgCO2/t for
70% GBFS is allowed as per code IS 455:2015. However, the PSC used in OPC, 8300 kgCO2/t for NS [33], and zero kgCO2/t for performance
this experiment has 55% GBFS; hence PSC has a lower CO2 footprint improver (PI) and gypsum are considered. The kgCO2/t for GBFS is also

12
R. Goyal et al.
Fig. 18. SEM microphotographs for OPC and PSC blend for 1 day hydration period.
taken as zero, as it is waste from the steel industry. The calculated
carbon footprint of OPC and PSC is shown in Fig. 25. It can be observed
that PSC, which is used in this experiment with 55% GBFS, has a 46%
lower kgCO2/t than OPC. The PSC is produced per code IS 455–2015,
with a maximum of 70% GBFS (as std PSC); kgCO2/t can be reduced up
to 61% than OPC.
5. Mechanism of hydration of PSC in the presence of NS
The hydration mechanism of OPC, PSC, and PSC in the presence of
NS are summarised in Fig. 26. After the water is added to OPC, cement
particle reacts with water immediately, producing AFt and CH and
forming forms C-S-H and which is responsible for setting and compres­
sive strengths. In the case of PSC, produced CH from OPC is consumed by
GBFS, and it is a secondary reaction that delays the hydration and the
early setting and compressive strength development.
When NS is added to PSC, the hydration reaction enhances due to
NS’s high fineness and pozzolanic characteristics, and available CH
13
Construction and Building Materials 394 (2023) 132173
forms a higher amount of C-S-H. The NS provides the seeding and
nucleation effect, helps the growth rate of hydration products, and de­
velops dense matrics, which shorten the setting time and accelerate the
early compressive strength development.
6. Challenges and benefits of using nano silica
Incorporating NS in PSC reduces the leaching of calcium by forming
C-S-H, reducing pores and setting times, and increasing mechanical
strength. Apart from these advantages, there are two major challenges in
adopting NS in cement manufacturing, First, NS is a costly material, but
at the same time, the carbon footprint is reduced significantly in PSC.
When considering the carbon tax or penalty of 15–25 US$/t CO2 for a
higher carbon footprint of cement, the additional cost of NS will be
offset, and using PSC in construction will promote green building con­
struction and infrastructure for sustainability. Secondly, being smaller in
size, homogeneous dispersion in the system at the site will be difficult.
During mixing on the site, there is a possibility that NS may come into
R. Goyal et al. Construction and Building Materials 394 (2023) 132173

Fig. 19. SEM microphotographs for OPC and PSC mix for 3 days hydration period.

the environment, and the person handling it may inhale. So, it can be
dangerous for human health and the environment. As the construction
industry is advancing and adopting new technologies, on-site and
manual mixing activities are reducing. The industry is moving to precast
concrete, which is produced under a controlled environment and
mechanized mixing; it will solve the concern of proper dispersion and
health risks in construction applications.

7. Conclusions

The due to the high amount of GBFS in PSC, setting time delays and
lower early compressive strength development because of the less
reactivity of GBFS and lesser cement content. The results of the lab
research work indicate that the addition of NS to the Portland slag
cement with a higher amount of GBFS led to the improvement in early
age strengths and setting times because the addition of an optimal
Fig. 20a. Change in Si(IV) ion concentration with time in PSC in presence amount of NS 1% to the Portland slag cement provides a nucleation site
of NS. for hydration reactions and accelerating pozzolanic reactions

14
R. Goyal et al. Construction and Building Materials 394 (2023) 132173

Fig. 20b. Change in Ca2+ ion concentration with time in PSC in the presence of NS.

Fig. 21. Strength losses of mortar cubes of PSC blends in the acid solutions.

Fig. 22. Photographs of the mortar cubes immersed in acid solutions for 7 days.

15
R. Goyal et al. Construction and Building Materials 394 (2023) 132173

Fig. 23. XRD pattern of the white layer formed on PSC mortar cubes immersed in H2SO4 for 3 days (G-Gypsum and Q-quartz).

Fig. 24. Composition of OPC (a) and PSC (b).

concrete as it minimizes the corrosion of steel in the structure. Disso­

lution studies indicate that higher amounts of calcium and silica ions
were released at 5 mins and 10 mins, respectively, and subsequently,
their concentration decreased with reference to time, clearly indicating
the reaction of silica with calcium ions in the hydration process. The
optimum addition of NS for the PSC cement was found to be 1%. Using
PSC with NS helps to reduce the CO2 footprint by 61% compared to OPC
to drive carbon neutrality and sustainability.

CRediT authorship contribution statement

Raju Goyal: . Vinay K. Verma: Conceptualization. N.B. Singh: .

Declaration of Competing Interest

Fig. 25. Carbon Footprint kgCO2/t of OPC, PSC, and Std PSC. The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
subsequently producing more C-S-H gel which fills and refines the pores the work reported in this paper.
in the microstructure. Further addition of more than 1% NS leads to
reduced compressive strength due to agglomeration of nanoparticles Data availability
and lack of CH availability due to lack of cement mineral phases C3S and
C2S in the paste. Participation of NS in hydration reactions is corrobo­ No data was used for the research described in the article.
rated by an increase in early age strengths, faster setting times, and
improved water penetration resistance which enhance the durability of

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R. Goyal et al. Construction and Building Materials 394 (2023) 132173

Just after adding water Hydration after 3 days

OPC Hydration
PSC Hydration
PSC Hydration in presence of
NS

Fig. 26. Hydration mechanism of OPC, PSC, and PSC in the presence of NS.

Acknowledgments
We thank Sharda University, Greater Noida, and UltraTech Cement
Limited, Mumbai, for allowing this study. We are grateful to our col­
leagues; without their help, this work would not have been completed,
and they are always supportive and cooperative, even during odd hours.
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