Construction and Building Materials 181 (2018) 487–494

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Construction and Building Materials

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Geopolymerization behavior of ferrochrome slag and fly ash blends

S.K. Nath
CSIR-National Metallurgical Laboratory, Jamshedpur 831 007, India

h i g h l i g h t s

 Geopolymerization behavior fly ash and ferrochrome slag has been studied.
 Low reactivity of fly ash at ambient condition can be overcome by addition of FCS.
 FCS addition results better compressive strength and well bridged microstructures.
 Geopolymer gel and C,M-A-S-H gel coexist in blended samples and improves strength.

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

Article history: This study highlights on the development of blended geopolymer cement by utilization of two industrial
Received 25 January 2018 wastes namely ferrochrome slag (FCS) and fly ash. Geopolymer cement with 100 wt% FCS is considered as
Received in revised form 7 May 2018 control batch. Then FCS is gradually replaced by introducing fly ash. The result obtained by isothermal
Accepted 8 June 2018
conduction calorimetry shows that higher heat of reaction with intensified peak in slag rich specimens.
Available online 15 June 2018
The appearance of SiAOASi/Al bond vibration at lower frequency in slag dominated reaction indicates the
structural alteration and formation of new calcium and magnesium rich gel. The main reaction product in
Keywords:
blended geopolymer samples is identified as N-A-S-H and C,M-A-S-H (where, N = Na2O, A = Al2O3,
Ferrochrome slag
Fly ash
C = CaO, M = MgO, S = SiO2, H = H2O) based heterogeneous hydrated gel with varying Si/Al, and Na/Ca
Geopolymer ratios. Higher compressive strength is attained in slag based reference sample due to its higher degree
Reactivity of reaction, formation of more gel phases and development of compact microstructure.
Microstructure Ó 2018 Elsevier Ltd. All rights reserved.
Compressive strength

1. Introduction
The term ‘‘geopolymer” is coined by Joseph Davidovits to
describe an alumino-silicate binder materials consisting of tetrahe-
dral aluminate and silicate units formed by the alkali activation of
alumino-silicate bearing source materials such as calcined clay, fly
ash [1]. Geopolymer production is more environmental friendly
and the resultant products are more durable than Portland cement
binder [2–4]. Fundamentally any alumino-silicate powder material
can be used for geopolymer synthesis. Therefore, a large number of
naturally occurring and synthetic solids are being tried for
geopolymer production [5–9]. Additionally, it has the potential to
valorize the industrial waste materials and to immobilize the
heavy and toxic elements inside the structure [6–9]. Thus, there
is a paradigm shift in the research trend for geopolymer synthesis
from naturally occurring and pure material to waste and
by-products [6,7].
Ferrochrome slag (FCS), a byproduct is produced during the
production of ferrochrome alloy steel in submerged electrical arc
E-mail address: snath@nmlindia.org
furnace. Around 1.1–1.6 ton slag is generated in per ton of fer-
rochrome production depending on feed materials [10]. Globally,
ferrochrome production is estimated about 8.9 million tons in
the year 2011 [10,11]. Using this data, the annual generation of
FCS is calculated around 12.5 million tons which is also increasing
by 2.8–3.0 wt% in every year. A small percentage of produced slag
is being used for road construction and rest part is simply dis-
carded. Accumulation of such material in huge quantity requires
large surface areas which is rather un-favourable in economic
aspects. Additionally, dumping of such waste on the open land
causes severe environmental problems such as leaching by water
and pollution of nearby water sources, chemical degradation, envi-
ronmental pollution and lack of aesthetics. Due to stringent envi-
ronmental regulatory and sometimes local community pressures,
simple storage of such slag may no longer be considered a sustain-
able practice. Therefore, it is necessary to examine this waste
material in appropriate ways of utilization. Thus research signifi-
cance for bulk utilization of such type of material is increasing
rapidly. Very limited research data is available on FCS used as road
construction, cement additive and aggregate form in construction
work [12,13].

https://doi.org/10.1016/j.conbuildmat.2018.06.070
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
488 S.K. Nath / Construction and Building Materials 181 (2018) 487–494
Fly ash is the by-product powder material of thermal power
plants generated during combustion of coal. Huge amounts of fly
ash are generated day to day to meet up the requirement of high
energy throughout the world. Only a part of this are utilized and
rest is simply dumped. Unplanned dumping of such huge amounts
of fly ash are causing an environmental pollution and creating big
concern for the future. In the last two decades, many countries
have initiated to utilize fly ash as additive to cement and concrete
in building materials. Recently fly ash has become a material of
interest for the synthesis of geopolymer due to its alumino-
silicate composition, free flowing nature, low water demand and
high workability [7,8,14–16]. During geopolymerization, fly ash
particles interact with alkali solution and leads to the formation
of structurally disordered, highly cross-linked alkaline alumino-
silicate-hydrate (N-A-S-H) gels [16]. Finally, these gels solidify,
bind the un-reacted particles, harden and develop strength. How-
ever, the low reactivity of fly ash and consequent slow setting
and strength development has been a limiting factor. Two different
approaches have been followed to overcome the low reactivity of
fly ash at ambient condition- (a) by addition of high reactive mate-
rial such as granulated blast furnace slag (GBFS), granulated corex
slag (GCS), granulated lead smelter slag (GLSS), granulated silico-
manganese slag (GSS) etc. [17–19] and (b) by mechanical activa-
tion of fly ash [20]. Mechanical activation is an energy intensive
process. Therefore, blending with high reactive powder is more
favorable. Mainly CaO bearing high reactive materials are mixed
to improve the reactivity. It is recognized that CaO participates into
activation process and produces C-S-H/C-A-S-H gel along with
geopolymer gel which results adequate strength development
[17–19]. It is also expected that the reactivity of the blends to be
improve due to incorporation of significant amount of glassy
phases which are more vulnerable to react than stable crystalline
phases.
Air cooling is the normal industrial practice for liquid FCS solid-
ification. In this process solid slag is generated in lumpy form with
negligible glass content [21]. It normally contains lower amount of
reactive CaO compare to other reported slags used for blending
[22,23]. Thus its applications are limited as inert coarse aggregate
in concrete structures [23,24]. The utilization potential of ferro-
chrome slag into geopolymer system has been studied only by Kar-
akoc et al. [22]. These authors reported that this slag is suitable for
geopolymer binder at ambient temperature curing. Though, it is
not clear whether they have used air cooled or water quenched
granulated slag. This slag as a blended component with fly ash in
geopolymer system is yet to be explored. The purpose of above
blending can be justified with the geopolymerization behavior
and availability of both materials. Fly ash is easily available at
everywhere and its generation volume is much higher (100 times
higher only in India) than FCS. Therefore by blending, total volume
of the resource material for geopolymer synthesis is augmented. In
addition, this research work has the great potential to overcome
the low reactivity of fly ash and to utilize more fly ash with FCS
into geopolymer binder at ambient conditions.
2. Materials and methods
Ferrochrome slag (FCS) used for this study was collected from an Alloy Steel
Plant, Durgapur, India. Slag was received in lump form with wide variation of size.
The lumpy slag was crushed in jaw crusher then milled into ball mill for 2 h for
obtaining median particle size, D50  25 mm. Class F fly ash was obtained from Tata
Power Co Ltd., Jamshedpur, India. The chemical analysis of slag powder and fly ash
was carried out by using Inductive coupled plasma optical emission spectrometer
(ICP-OES) (Make: Varian Inc.) and further verified in X-ray florescence (XRF, Make:
Bruker, US). Loss on ignition (LOI) was measured by calculating the weight loss
upon heating. Pycnometer bottle was used to determine specific gravity of slag
powder and fly ash, following Archimedes principles. Particle size distribution
(PSD) of powder raw materials was measured in Laser particle size analyzer (Make:
Malvern, UK). The mineralogy of raw materials and geopolymer samples were
analysed by using D8 Discover X-ray diffractometer (XRD, Make: Bruker, US) in
10 to 70° 2h range, a scan speed of 0.2 s/step with step size of 0.02°. The CuKa radi-
ation (=1.5418 Å) was generated at 40 kV and 40 mA. Table 1 shows the oxide con-
tent and physical characteristics of the raw materials.
Table 2 shows the mix proportion used for this study. The sample with 100 wt%
FCS is considered as control batch. Then gradually fly ash percentage was increased
to replace FCS. Sample nomenclature has two parts, alphabetic presents initial of
the slag and numerical represents their respective percentage. Alkali solution of
6 M was prepared by dissolving analytical grade sodium hydroxide flakes (purity
97%, Merck, Germany) into required amount distilled water and used for ICC
study. Powder blend was mixed manually with alkaline solution in the ratio of
2:1, into calorimeter bottle. Then the bottles in sealed condition were loaded into
calorimeter channels. The time elapsed was around 2–3 min between mixing and
loading into calorimeter. Isothermal conduction calorimeter (ICC, Make: TA instru-
ment) was used to monitor the geopolymerization by measuring the heat of reac-
tion with time, at ambient (27 °C) temperature.
Microstructural analysis of the reaction products was carried out with Fourier
transforms infrared spectroscopy (FTIR), X-ray diffraction (XRD), and Scanning elec-
tron microscope with Energy dispersive X-ray spectroscopy (SEM-EDX). For FTIR,
pellet samples were prepared by mixing with KBr powder. FTIR (Make: Thermo
Electron Corporation) in transmittance mode was used to measure the absorption
spectra of the bonds in the range of 400–4000 cm 1. Field emission gun-scanning
electron microscope (FEG-SEM, Make: FEI, Netherlands) fitted with energy disper-
sive X-ray spectrometer (EDX) operated at 15.0 KV was used for morphological
analysis of reacted samples, after gold or silver coating on fractured surface.
Cube (50  50  50 mm) specimens were made for compressive strength test-
ing. 6 M NaOH and sodium silicate (SS) solution in 1:1 vol ratio was taken as acti-
vator solution. The SS solution contained around 7.5 to 8.5 wt% Na2O, 25 to 28 wt%
SiO2 and rest amount of water with a modulus ratio (Ms = n(SiO2)/n(R2O)) of about
3.45. Sodium silicate solution was used to get sufficient strength at the initial stage.
The same reason has been reported in published literatures [17,25]. The powder
mix was mixed with alkali solution (around 26 wt%) in a mechanical mixer to make
a homogenous and consistent paste, then casted in cube shaped moulds made with
alkali resistant steel. The casted samples were de-moulded after hardening and kept
in plastic cover at 27 ± 2 °C temperature for curing and testing at different age.
AIMIL equipment (ACTM) was used for compression test after 7, 14 and 28 days
curing.
3. Results and discussion
3.1. Raw materials characterizations
Silica and alumina is present abundantly in both raw materials.
The ratio of SiO2/Al2O3 is 1.06 and 1.79 in FCS and fly ash respec-
tively. The studied slag also contains CaO and MgO as major oxide
component and iron oxide and chromia as minor. The other minor
oxide content of fly ash is iron oxide and CaO. Particle size distribu-
tion (PSD) of ground FCS and fly ash is shown in Fig. 1. Compare to
fly ash, FCS is coarser with larger median particle size, though the
maximum size is similar. Both crystalline peaks and glassy hump
are detected in XRD analysis of both raw materials, as shown in
Fig. 2(a, b). The broad diffused hump is present at 20–30° 2h range
corresponding to glassy or amorphous phase in fly ash. Similarly,
FCS is characterized with the presence of a broad diffuse halo in
between 15 and 40° 2h. The major crystalline phases in fly
ash are identified as quartz (JCPDS 85-0796) and mullite (JCPDS
Table 1
Chemical analysis and physical properties of raw materials.
Chemical Analysis
Constituents (Wt.%) FCS Fly ash
SiO2 27.70 51.20
Al2O3 26.05 28.60
CaO 12.55 2.15
MgO 25.30 0.75
Cr2O3 4.15 NF
FeO + Fe2O3 2.20 8.10
LOI 0.70 2.70
Physical properties
Specific gravity 3.01 2.3
Median particle 18.36 9.67
size (mm)
 S.K. Nath / Construction and Building Materials 181 (2018) 487–494 489

Table 2
Mix proportion used for the study.

Name FCS Fly ash Si/Al Ca + Mg/Si

100FCS 100 00 0.937 1.867
80FCS 80 20 1.075 1.303
60FCS 60 40 1.208 0.882
40FCS 40 60 1.335 0.556
20FCS 20 80 1.459 0.295
00FCS 00 100 1.578 0.083

74-4143). The detected major crystalline phases of FCS are as com-

bination of different oxide components of such as frosterite (JCPDS
87-2038), magnesium aluminate spinel (JCPDS 86-0091), magne-
sium cromate (JCPDS 87-1176) etc.

3.2. Geopolymerization study

The rate of heat evolution (dQ/dt, mW/g) with time (h), as

recorded by ICC, is plotted in Fig. 3. A sharp peak (I) with high heat
flow is appeared in all samples immediate after the start of record-
ing, which is due to initial wetting and faster dissolution of fly ash
and slag particles into alkali solution [26,27]. At 27 °C tempera-
ture with 6M NaOH solution fly ash containing sample (00FCS)
does not show any more peaks except the vertical line at initial.
Thereafter the vertical line converged into a horizontal one which
represents its extremely low reactivity at said condition [16,28].
There is no significant change observed upto 60 wt% fly ash (or
40 wt% slag) containing samples because the reaction is domi-
nated by fly ash. The difference in reaction heat profile is observed
after peak I with the samples bearing more than 40 wt% FCS. The
samples with 60 wt% FCS, a prominent peak (II) with acceleration
and deceleration step is appeared after the induction period. This
peak corresponds to the initiation of gel product formation and
its continuation. The induction period with lower heat flow is the Fig. 2. XRD analysis of (a) FCS and (b) fly ash.
consequence of low reactivity which increases with fly ash incor-
poration. The peak intensity is decreased and peak position is
shifted towards right (Fig. 3) with fly ash addition attributes lower products, which consumes more Ca from solution phase and ren-
reactivity of fly ash compare to FCS, at the studied condition. The dering a driving force for continuing reaction. As a result, the FCS
variation in peak intensity can be associated with degree of disso- dissolves much faster rate and successive reaction towards gela-
lution and the amount of CaO, SiO2 and Al2O3 available after disso- tion is started earlier.
lution. This can be related to oxide constituents and mineralogy of At the deceleration step of the main peak (II), a new hump is
both the raw materials. Slag contains higher amount of CaO and appeared in 80 wt% FCS containing samples. This can be attribu-
MgO which are more susceptible to dissolve than Al2O3 and SiO2 ted with more reaction of FCS with alkali activator. The reactivity
under the polarization effect of OH [29]. Further the dissolution of slag rich mixes enhances due to increase in reactive content,
of FCS is magnified by the initial formation of Ca bearing hydrated in consistent with previous studies where high reactivity is
obtained by addition of granulated slags such as GBFS, GCS, GLSS,
GSS etc. [17–19]. Finally the heat evolution has been started to
decrease with time and reaches to a steady state. At this step,
the polymerization and condensation reaction probably has been
continued for a longer duration with minimal amount of heat
release. Due to faster rate of reaction, FCS100 sample is reaching
steady state earlier than other. The cumulative heat (Q) of reaction
(Fig. 4) enhance with higher slag content is suggesting higher reac-
tivity of FCS with higher heat evolution. The initial flatter region is
due to induction phase before the start of main peak (II). Thereafter
it rapidly increases with time of reaction. This peak is more flat in
fly ash rich samples, indicates fly ash dominated reactions are
occurring at very slow pace. The reaction kinetics of the blend is
found to be controlled by their corresponding higher amount of
composition, either FCS or fly ash.

3.3. Fourier transform infrared spectroscopy (FTIR) analysis

Fig. 5 presents the FTIR spectrums of geopolymer samples and

Fig. 1. Particle size distribution of FCS and fly ash. corresponding bands are indexed in Table 3. The Si-Al framework
490 S.K. Nath / Construction and Building Materials 181 (2018) 487–494
Fig. 3. Isothermal conduction calorimetry showing heat of reaction of FCS, FCS-fly
ash blends and fly ash with alkali.
related bands are appeared at about 460 cm 1 and 560 cm 1 wave-
numbers. The peak at 460 cm 1 corresponds to bending vibration
of SiAOASi and OASiAO. The symmetric stretching band of
AlAOASi at 560 cm 1 is resulted from crystalline mullite of un-
reacted fly ash. This band is more prominent in fly ash rich samples
due to presence of more remnant mullite.
A strong peak at around 685 cm 1 is appeared in slag based
geopolymer only. This peak is attributed with symmetrically
stretching vibration of Si-O bond. Though fly ash also contains sig-
nificant amount of silica, but this peak is not recorded. This can be
explained with the change in nature of silicate and their corre-
sponding bond structure after alkali activation. The strongest band
is centered at about 990–1030 cm 1, corresponding to the SiAOAT
(where T is Si/Al) asymmetric stretching. This band is recorded at
about 990 cm 1 with slag based reference and shifted towards
higher frequency when slag is replaced with fly ash. This can be
explained with the structural modification of the Si-Al network
and change of Si/Al ratio due to geopolymerization [26,27]. In slag
dominated system, substitution of Si by Al during alkali activation
is more. This substitution has an effect on the intra-molecular
bonding strength and bond energy. The bond angle and bond
Fig. 4. Cumulative heat of reaction of FCS, FCS-fly ash blends and fly ash with alkali.
energy is decreased with Al inclusion in the silicate network.
Therefore, the bond vibration is recorded at lower frequency with
slag rich samples. The narrower shape SiAOAT bond in slag dom-
inated system corresponds with the formation of ordered struc-
ture, which is basically Ca and Mg containing C,M-A-S-H type
gel/product formed via alkali activation of FCS. The N-A-S-H gel
which is formed by activation of fly ash with alkali is relatively
more disordered structure. The bending vibration of carbonate
bond is detected at around 1450 cm 1 [27,29]. This band is more
prominent and appeared in narrow shape in the control sample.
This can be associated with chemical species of FCS and fly ash
and their interaction with alkaline solution. During alkali activa-
tion Si, Al, Mg and Ca species are formed after dissolution. Calcium
and magnesium is more in basic and increases the total basicity of
the slag rich mixture. Any system has a natural tendency to come
in neutralize condition by interacting with its surroundings. There-
fore, the basic components are reacting with atmospheric CO2 dur-
ing the reaction and/or at the time of curing. Sharper shape of this
band with 100FCS sample is due to presence of hydrotalcite (mag-
nesium aluminium hydroxide carbonate hydrate), a layered, crys-
talline carbonate mineral, which is formed in MgO rich alkali
activated slag system, reported by Ben Haha et al. [30]. The AOH
bending and AOH stretching vibration is appeared at about 1650
cm 1 and 3440 cm 1 respectively. This confirms the presence of
structural water in gel and entrapped water inside the porous net-
works [17,26].
3.4. X-ray diffraction (XRD) analysis
Fig. 6 shows the X-ray diffraction pattern of geopolymer sam-
ples. Two different features (crystalline peak and hump) are mainly
detected in XRD analysis. The diffuse halo peak of both raw mate-
rials disappears or intensity reduces after geopolymerization. This
indicates structural alteration of these glassy materials after
geopolymerization and finally hardening into another amorphous
or semi-crystalline hydrated phases. The structural change is sup-
ported by FTIR analysis with the shift of TAOAT (T = Si/Al) bond.
The remnant phases of slag and fly ash are the main identified crys-
talline phases in geopolymer samples. After geopolymerization, the
intensity of all crystalline phases of the slag reduces, probably due
to transformation into poorly crystalline phases. Whereas, fly ash is
very less reactive at 27 °C temperature with 6 M alkali and crys-
talline phases are remaining mostly unchanged even after 28 days
Fig. 5. FTIR analysis of geopolymer cement paste samples.
 S.K. Nath / Construction and Building Materials 181 (2018) 487–494 491

Table 3 3.5. Scanning electron microscope-energy dispersive X-ray

FTIR species of geopolymer cement paste samples. spectroscopy (SEM-EDX) analysis
Band Wavenumber Species Remarks
(cm 1) The SEM micrographs of the fractured surface of geopolymer
1 460 Bending vibration Common in all samples. samples are shown in Fig. 7(a–d). The following common features
of SiAOASi and Position not changed with are observed under SEM analysis. 1. The microstructure is hetero-
OASiAO decreasing slag content. geneous composite consist of reacted gel and un-reacted or par-
2 560 Symmetric More prominent in fly ash rich
stretching sample
tially reacted fly ash and slag particles, 2. formation of gel as a
AlAOASi reaction product on the surface of slag and/or fly ash particles, 3.
3 685 Symmetric Strongly appeared in 100FCS particles are diffused due to reaction on the surfaces; small parti-
stretching cles are more diffused due to faster dissolution into alkali solution
vibration of SiAO
and bigger particles are mostly stable or un-reacted, 4. in fly ash
bond
4 990–1020 Asymmetric Shifted towards higher rich batch reaction is limited on the upper surface of the particles
stretching of frequency with introduction of (Fig. 7c, d), 5. mostly non-homogeneous reaction with scattered gel
SiAOAT (T = Si/Al) fly ash formation and more un-reacted particles are observed in 20FCS
5 1450 Carbonate band Carbonate formation with free and 00FCS (Fig. 7c, d), 6. the order of uniformity increases with
alkali and ambient CO2
higher slag content, and the particles are bridged together by reac-
6 1650 AOH bending Confirming structural and
entrapped water tion product, 7. different type gels (different chemical composi-
7 3440 AOH stretching do tion) are developed by activation of fly ash and slag, and
coexisted without any discrete boundary. Only fly ash sample
(Fig. 7d) is predominant with un-reacted fly ash particles with
partly diffused surfaces. Various size pores from micron to submi-
of curing. Quartz and mullite is detected as major crystalline peaks cron are observed in the reacted matrix. The un-reacted and non-
from non-activated part of fly ash. Similarly frosterite and spinel is bridging particles are found to increase with increasing fly ash con-
the main remnant phases as identified in FCS activated geopolymer tent. This finding is further supported by ICC study, where high
[22]. heat of reaction is recorded with slag rich samples. A twisted string
The poorly crystalline gel phases with variable composition like object or fibrous like secondary features rich with Na are
such as C-A-S-H, C-(N)-A-S-H, C,M-A-S-H, N-(C)-A-S-H, N-(M)-A- appeared in the sample 20FCS (Fig. 7c). This is probably due to con-
S-H and N-A-S-H are formed as reaction product in the FCS, FCS- densation of sodium silicate. At ambient temperature and moder-
fly ash blends and fly ash based geopolymers. Most likely these ate alkalinity the dissolution of alumina may not be sufficient.
hybrid gels are formed by alkali activation of both slag and fly Therefore, the chances of sodium silicate condensation are more
ash and coexist in the blended samples. The fly ash derived gel with fly ash rich samples because availability of higher amount sil-
which is also known as ‘geopolymer gel’ (N)-A-S-H cannot be ica, in agreement with published literature [16]. EDX analysis was
traced by XRD because of its amorphous nature; however change carried out on reacted matrix of at least six different points of any
in degree of amorphosity is observed [26,31]. Hydrotalcite (JCPDS feature to minimize the error due to heterogeneity of samples, and
89-0460), a secondary phase is identified with very low intensity non-uniform reaction. Reacted dense gel has a wide variation in
at about 40° 2h and probably overlapping with frosterite at 2h of their chemical composition. This can be related to the different
36° in FCS rich mixes. The formation of hydrotalcite is due to chemical species, mineralogy and particle size and shape of fly
presence of high MgO in FCS [30], and supported by FTIR result. ash and slag which finally lead to the difference in reactivity and
The weak peaks of carbonate phases (Na2CO3, H2O and calcite, their reaction product formation. These reacted gels and secondary
CaCO3) which bonds are detected in FTIR mostly overlapping with zeolites are intermixed so intimately which probably bar to detect
other phases are traced [26]. their separate identification on a microstructural or bulk composi-
tional level. Sodium alumino-silicate hydrate (N-A-S-H) with neg-
ligible trace of calcium and magnesium is identified as main
reaction product in the fly ash dominated reaction, coherent with
previous findings of fly ash and slag blended geopolymer [26,32].
The Na/Ca ratio is increasing with fly ash introduction is due to for-
mation of more (N)-A-S-H gel. A compact microstructure contain-
ing Ca and Mg rich gels, C, M-(A)-S-H along with small amount of
Na incorporation, C-(N)-A-S-H is detected in FCS activated binder
via SEM-EDX analysis (Fig. 7a). Such hybrid gels may result from
either (a) Na substitution by Ca and Mg into N-A-S-H (with Q4
framework silicate structure) or, (b) Na inclusion in chain silicate
C-A-S-H type gels [33,34]. The FCS which is rich with Ca and Mg
along with Si and Al results to form additional calcium and magne-
sium containing hydrated products, which enhances the binding
capability, and improves the physical and mechanical properties
of the resultant geopolymer.

3.6. Mechanical properties

Fig. 8 represents the compressive strength result of hardened

geopolymer cement paste samples. The compressive strength
decreases with FCS replacement. This observation is further sup-
ported by calorimetry result and microstructural observation.
Fig. 6. XRD analysis of geopolymer cement paste samples. The highest strength is obtained with 28 days cured 100FCS
492 S.K. Nath / Construction and Building Materials 181 (2018) 487–494

Fig. 7. SEM image of fractured surface of geopolymer cement paste samples; (a) 100FCS, (b) 60FCS, (c) 20FCS and (d) 00FCS.

sample. This can be related to the higher reactive component of

FCS, which undergoes faster hydration and forms additional Ca
bearing gel along with the geopolymeric, aluminosilicate hydrated
(N-A-S-H) gel [26,27,32,35]. These additional gels help to build up
high strength of the slag rich blends. A significant strength drop is
recorded when 40 wt% slag is replaced with fly ash. The strength
development is very negligible in fly ash (00FCS) and fly ash rich
blended samples (20FCS and 40FCS) due to low reactivity of fly
ash at room temperature (27 ± 2 °C), consistent with other fly
ash-slag blended geopolymer studies [17,26]. The measured
strengths are increasing with the duration of curing. This incre-
ment is due to the continual formation of binder from alkali activa-
tion of both FCS and fly ash. Both initial and final strength is
significantly high in slag rich mixtures due to faster hydration of
slag constituents (ICC result), which leads to formation of more
gel phases and builds compact microstructure (SEM). This can be
attributed with more reactive oxide components of the slag which
are more vulnerable to alkali attack than fly ash, and produces an
adequate amount of reaction product which improves the binding
capability and achieves higher strength. The presence of substan-
tial amount of MgO in FCS can improve the strength of the mortar Fig. 8. Compressive strength of geopolymer cement paste samples.

due to formation of hydrotalcite type products [30]. Although,

hydrotalcite is not a strength giving binder phase but its formation
leads to an enhancement of strength may be associated to a reduc-
tion level of Al intake into the C-A-S-H gel, anticipated by numer-
ous authors [36,37].
The strength of the geopolymer mortar is associated with the
dissolution of oxides such as alumina, silica, CaO etc. from powder
precursor into alkali solution [38]. The higher alkali concentration
provides a higher mechanical strength due to sufficient dissolution
and formation of higher amount of geopolymer gels [39]. However,
an optimal alkali concentration is required to accelerate the
polymerization reaction and to achieve the superior mechanical
 S.K. Nath / Construction and Building Materials 181 (2018) 487–494
properties. Beyond the optimum concentration, the coagulation of
silica increases at higher pH, which can adversely affect on the
strength development [39,40]. In addition, at higher alkali concen-
tration C-A-S-H tends to disintegrate and Ca prone to precipitate
[41].
The main focus of this study is to check the suitability of FCS
and FCS-fly ash different mix proportion into geopolymeric prod-
uct. Thus, a moderate alkali concentration (6 M) is used throughout
the study. Sodium silicate solution is added selectively to provide
extra soluble silica which can result a better binding and signifi-
cant strength gain at the initial age, consistent with previous
researches [17,20]. Higher sodium silicate to NaOH ratio can pro-
duce better compressive strength [42], but it may reduce the work-
ability. Thus, extra water or more activator solution is added
further to achieve the desired workability. This increases the water
to binder ratio which results to reduce the compressive strength
[32]. Based on the author’s experience, sodium silicate to NaOH
ratio is optimized at 1.
With increasing curing temperature the mechanical properties
of geopolymers improve significantly at early stage [43]. Although,
the strength of 28 days ambient cured samples are comparable
with elevated temperature [32]. It has also been reported that
the elevated temperature curing has negative effect on strength
gain due to evaporation of water from gel structure [22,42]. Addi-
tionally, the heat curing is not a feasible process in view of huge
construction site, and ambient condition curing has certain
advantages such as low energy consumption and easier to handle.
Therefore, in this work only ambient condition is considered for
curing.
4. Conclusions
The following chief conclusions are deduced from this study:
1. FCS is a by-product of ferrochrome alloy production and its
major oxide components are SiO2, Al2O3, MgO and CaO. The
air cooled slag is mostly crystalline which can be utilized for
geopolymer binder development.
2. Compare to FCS, fly ash is less reactive at ambient condition
with moderate alkali concentration. The rate of heat evolution
and total heat of reaction decreases with fly ash incorporation
due to reduction of calcium oxide, magnesium oxide and reac-
tive phases. The shortening of induction period indicates faster
reaction in slag-rich mixes. The mechanism of reaction of each
sample is dominated by the respective mix composition.
3. The structural alteration of the resultant binder is evident from
shifting of FTIR main spectra. This shifting towards higher fre-
quency with fly ash addition attributes lower Al sorption in
alumino-silicate network structure. The appearance of broader
shape SiAOASi/Al bond in fly ash dominated reaction attributes
with the formation of more disordered N-A-S-H gel via alkali
activation of fly ash.
4. The structural reorganization of the mix after geopolymeriza-
tion is confirmed by XRD analysis, with the reduction of crys-
talline peak intensity of FCS and change of amorphous hump
nature.
5. Hybrid C,M-A-S-H and N-A-S-H gels are detected via SEM-EDX
analysis as main reaction product in blended geopolymer. Basi-
cally, C,M-A-S-H is formed by alkali activation of FCS which also
incorporates little Na into structure. N-A-S-H gel is readily pro-
duced by alkali activation of fly ash and Ca substitution is
occurred when Ca is available in the system. These gels are
intermixed without having any distinct boundary in the reacted
geopolymer matrix.
6. The highest compressive strength is achieved with FCS based
control sample. The higher reactivity (ICC result) of slag and
493
formation of more Ca and Mg rich hydrated phases is the key
factors of higher strength development. With the inclusion of
fly ash the strength is reduced due to slow rate of reaction of
fly ash at ambient condition and presence of more un-reacted
and non-bridged particles in the composite matrix.
7. According to the obtained result from the present study, FCS
can be a potential material for synthesis of geopolymer binder
cured at ambient conditions. Further, the limitation of fly ash
bulk utilization into geopolymer cement at room temperature
can be overcome by blending with FCS.
Declaration of interest
There is no conflict of interest.
Acknowledgements
The authors are grateful to the Director, CSIR-National Metal-
lurgical Laboratory, Jamshedpur, India for his kind permission to
publish this paper. I would like to thanks Tata Power Ltd., Jamshed-
pur, India and Shyam Ferro Alloys Ltd., Durgapur, India for sending
fly ash and ferrochrome slag respectively. The support from CSIR-
NML technical staff is acknowledged.
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