Materials Today: Proceedings 33 (2020) 5001–5006

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Synthesis and characterization of a new class of geopolymer binder

utilizing ferrochrome ash (FCA) for sustainable industrial waste
management
Jyotirmoy Mishra a,⇑, Shaswat Kumar Das b, R.S. Krishna b, Bharadwaj Nanda a, Sanjaya Kumar Patro a,
Syed Mohammed Mustakim b
a
Veer Surendra Sai University of Technology, Burla, Sambalpur 768018, India
b
CSIR-Institute of Minerals and Materials Technology, Bhubaneswar 751013, India

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

Article history: Sustainable use of industrial wastes for the production of new age eco-friendly construction materials can
Received 9 December 2019 effectively solve the growing environmental concern over landfills and also provide an integrative indus-
Received in revised form 17 February 2020 trial waste management strategy. Geopolymers are comparatively a new class of aluminosilicate inor-
Accepted 24 February 2020
ganic polymer which has gained wide recognition due to its remarkable physicochemical and
Available online 27 March 2020
mechanical properties. Various industrial wastes such as fly ash, slag, rice husk ash, ferrochrome ash,
etc. rich in alumina and silica can serve as suitable precursors for the production of geopolymer binders.
Keywords:
This paper presents the experimental investigations on the utilization of ferrochrome ash (FCA), and
Ferrochrome ash
Geopolymer
waste from the ferrochrome industry as a primary precursor having considerable amounts of alumina,
Concrete silica, magnesium oxide, potassium oxide for preparation of geopolymer concrete having partial replace-
Industrial solid waste ments of ground granulated blast furnace slag and lime. The fresh and hardened geopolymer concrete
Sustainability properties: workability and compressive strength are thoroughly investigated. The particle size distribu-
tion, the chemical composition, mineralogy, microstructure of binder particles were analysed with
advanced analytical techniques such as XRF, PSA, XRD, SEM/EDS. The results of this study not only sug-
gest the effective utilization of ferrochrome ash for the synthesis of a new class of geopolymer binders but
also provide a sustainable route for the management of ferrochrome waste currently generated in various
countries worldwide.
Ó 2019 Elsevier Ltd. All rights reserved.
Selection and Peer-review under responsibility of the scientific committee of the 2nd International Con-
ference on Processing and Characterization of Materials.

1. Introduction considerably less energy with lower carbon emissions when com-
pared with Portland cement [1]. Easy availability of source materi-
1.1. Geopolymers als i.e. wastes from industries and lower production costs have
made geopolymer a significant area of research. Geopolymer con-
In the pursuit of alternate binder materials that will match the crete (GPC) which can be produced at ambient or elevated temper-
properties of Portland cement, research works on geopolymers are atures generates 80% less carbon dioxide and is found to have
of immense importance. Geopolymer binders are an innovative improved strength and durability properties than conventional
class of inorganic polymers manufactured by the activation of alu- cement-based concrete. In geopolymer concrete, the strength
minosilicate industrial by-products such as fly ash, ground granu- development is mainly due to the formation of chained Si-O-Al-
lated blast furnace slag (GGBFS), rice husk ash (RHA) with alkaline O- networks and generation of Sodium Aluminate Silicate Hydrate
solutions of sodium and/or potassium-based hydroxides and (N-A-S-H) and Calcium Aluminate Silicate Hydrate (C-A-S-H) gels
silicates. As a result, the production of geopolymers requires where N, C, A, S, H denotes Na2O, CaO, Al2O3, SiO2, H2O respectively
[2,3]. Conventional geopolymer systems with low calcium content
are generally associated with N-A-S-H gel formation [4]. It is
⇑ Corresponding author.
reported in several studies [5,6] that N-A-S-H becomes unstable
E-mail address: [email protected] (J. Mishra).

https://doi.org/10.1016/j.matpr.2020.02.832
2214-7853/Ó 2019 Elsevier Ltd. All rights reserved.
Selection and Peer-review under responsibility of the scientific committee of the 2nd International Conference on Processing and Characterization of Materials.
5002 J. Mishra et al. / Materials Today: Proceedings 33 (2020) 5001–5006

in calcium rich geopolymer pastes due to exchange of ions 2.2. Mix design, specimen preparation, and testing
between Ca+2 and Na+2 and slowly diminishes thus converting to
C-A-S-H gels. Nevertheless, the strength and the durability proper- A combination of FCA, GGBBFS, and lime was used as binder
ties of geopolymer concrete are predominantly influenced by the materials in the present study to produce five different geopolymer
type of source material and alkali activators used in its production. concrete mixes while keeping water/ binder ratio, alkaline activa-
Effective utilization of industrial wastes in the production of tor and curing condition constant. Lime was taken 10% by wt. of
geopolymers indeed serves to be a potential solution to issues like GGBFS in each of the mixes. For the preparation of the alkaline
industrial waste management, global warming, water stress, cli- solution, the concentration of NaOH solution was taken to be
mate change, and sustainability. 12 M which is combined with Na2SiO3 solution at a ratio of 1:2 (ap-
prox.). The binder materials were thoroughly mixed with the addi-
1.2. Sustainable industrial waste management: Ferrochrome industry tion of aggregates, alkaline solution and extra water with the help
of a concrete mixture for a period of eleven minutes to produce
Industrial waste management is a growing concern for every fresh geopolymer concrete mixes. The details of the mix design
major leading country in the world. Poor management of industrial obtained for 1 m3 of the geopolymer concrete mix is shown in table
wastes can lead to serious irreversible environmental damages 1. Each of the fresh geopolymer concrete mixes was then poured
while causing human hazards. Several incidents have been into six cube molds having dimensions (150  150  150) mm3
recorded in the following years, where such incidents could have as specified by the Indian standards (IS-10086: 1982 [10] and
been easily avoided through proper handling & disposal of indus- vibrated for 2 mins before curing them in outdoor conditions
trial wastes. Various laws have also been passed in most countries (42 °C/19 °C). The workability tests and compressive strength tests
to force industries in adopting a more sustainable way for indus- at the age of 7, 14 and 28 days were done in accordance with IS-
trial waste management. The ferrochrome industry plays a vital 1199 (1959) [11] and IS-516 (1959) [12] respectively. The detailed
role in the production of stainless steel as ferrochrome imparts flowchart regarding experimental procedure for the current work
the non-corrosive property of stainless steel. Global annual pro- is presented in Fig. 1.
duction of ferrochrome is estimated to be around 6.5–9.5 million
tones which is increasing at a compound annual growth rate 2.3. Characterization techniques
(CAGR) of 3% while producing 1–1.2 metric ton (MT) of solid waste
for every MT of ferrochrome product [7]. Ferrochrome Ash (FCA) & Chemical compositions of FCA and GGBFS used in this study
Ferrochrome Slag (FCS) are the major by-products or wastes gener- were determined by means of XRF (Zetium - Malvern Panalytical).
ated from the ferrochrome industry which can be brought into play The PSA of the source materials was done with the help of a laser
as potential raw material for the construction industry. FCA can be scattering particle size distribution analyzer (HORIBA LA-960). To
partially used in place of cement for preparing normal concrete observe and analyze the morphology and microstructure of FCA
resulting in higher mechanical strength and less energy consump-
tion as well as greenhouse gas emissions [8]. To date, no work has
been reported on the utilization of FCA in the field of geopolymers.
Hence, in this study, FCA is a source of silica and alumina, has been
exploited as source material in the preparation of a new class of
geopolymer binder/concrete for sustainable industrial waste
management.

2. Experimental procedure

2.1. Material

In this present study, FCA was used as a primary source material

along with GGBFS. FCA and GGBFS were obtained Balasore Alloys
Ltd., Balasore, India and Neelanchal Ispat Nigam Limited (NINL),
Jajpur, India respectively. Sodium hydroxide (NaOH) /silicate (Na2-
SiO3), aggregates and lime were obtained from local commercial
suppliers. NaOH was used in the form of flakes with 98% purity
while Na2SiO3 had a chemical composition of 32.15% SiO2,
15.85% Na2O and 52% water H2O. Natural river sand passing
through 4.75 mm IS Sieve and crushed gravel of 20 mm downsize
were used as fine and coarse aggregates respectively to make a
uniform geopolymer binder matrix [9]. Fig. 1. Flowchart for experimental procedure of the current work.

Table 1
Mix Design.

Mix Fine Coarse Sodium Sodium Extra

Sample FCA GGBFS Lime Aggregate Aggregate Hydroxide Silicate Water
Kg/m3 Kg/m3 Kg/m3 Kg/m3 Kg/m3 Kg/m3 Kg/m3 Kg/m3
F40:G60 197.2 265.92 29.58 493 1479 73.08 154.07 14.81
F50:G50 246.5 221.85 24.65 493 1479 73.08 154.07 14.81
F60:G40 295.8 177.48 19.72 493 1479 73.08 154.07 14.81
F70:G30 345.1 133.11 14.79 493 1479 73.08 154.07 14.81
F80:G20 394.4 88.74 9.86 493 1479 73.08 154.07 14.81
 J. Mishra et al. / Materials Today: Proceedings 33 (2020) 5001–5006 5003

and GGBFS, FESEM equipped with EDX was performed by using siderable amount of silica (36.3%), alumina (20.4%) and calcium
JSM-6480LV (JEOL). X-ray diffractometer (Rigaku-Ultima-IV) was (24.1%) as observed in table 2.
used for the analysis of mineralogical phases of FCA and GGBFS. The PSA results of FCA shown in Fig. 2(a) reveals that FCA has a
mean particle size of 20.97 mm and a median particle size of
3. Results and discussions 7.29 mm which suggests its fineness. The particle size distribution
detail is as follows: d10 – 0.33 mm, d50 7.29 mm and d90 –
3.1. Characterization of source materials 63.29 mm. Correspondingly, from PSA results in Fig. 2(b), we
observe that GGBFS has a mean particle size of 68.65 mm and a
The microstructure characterization of source materials; FCA median particle size of 21.62 mm. The particle size distribution
and GGBFS used in this study for synthesizing a new class of detail is as follows: d10 – 4.6 mm, d50 21.61 mm and d90 –
geopolymer binder was investigated using advanced techniques 217.99 mm.
such as XRF, PSA, XRD, SEM/EDS. The FESEM micrographs in Fig. 3(a) exhibits that FCA contains
XRF analysis was done to characterize the chemical composi- large portions of nearly rounded and spherical shaped particles
tions for FCA and GGBFS and the results are as presented in table which will certainly enhance flowability when used to make con-
2. From table 2, we observe that FCA contains a major amount of crete like fly ash. The morphology of GGBFS displayed in Fig. 3(b)
Magnesium oxide (MgO) 23.6%, along with Silicon dioxide (SiO2) where FESEM micrograph illustrates that GGBFS comprises irregu-
19.1%, Aluminum oxide (Al2O3) 10.9%, Potassium oxide (K2O) lar and uneven shaped particles (large, medium and small). EDX
11.4% and low Calcium oxide (CaO) 3.1% which makes it a suitable spectrum at a selected spot alongside the FESEM micrograph of
choice of source material for geopolymerization. GGBFS has a con- FCA reveals the presence of magnesium (Mg), silicon (Si), alu-

Table 2
Chemicals compositions of source materials by XRF.

Materials SiO2 Al2O3 CaO MgO Fe2O3 K2O Na2O P2O5 TiO2 Cr2O3 LOI
FCA 19.10 10.91 3.14 23.60 7.84 11.42 2.46 0.07 N/A 9.892 N/A
GGBFS 36.30 20.40 24.12 8.08 6.64 1.02 0.38 0.05 0.73 0.08 N/A

Fig. 2. Particle size distribution of (a) FCA (b) GGBFS.

5004 J. Mishra et al. / Materials Today: Proceedings 33 (2020) 5001–5006

Fig. 3. FESEM micrographs and EDX spectrum of (a) FCA (b) GGBFS.

minum (Al), calcium (Ca), chromium (Cr), potassium (K). These ele- geopolymer pastes forms C-S-H gel which enhances strength and
ments as well as sodium (Na) are present in GGBFS except chro- produces a compact matrix [13]. Therefore, lime was also incorpo-
mium as shown in the EDX spectrum alongside the FESEM rated into the system at 10% by wt. of GGBFS in each of the mixes
micrograph of GGBFS. for imparting extra calcium for generation of C-S-H gel. Several
Fig. 4(a) and (b) shows the XRD powder patterns of FCA and researchers have suggested replacement of source binder up to
GGBFS obtained using Cu Ka radiation from 10 to 800 (2h). The 50% of GGBFS in preparation of geopolymer concrete [14]. Hence
diffractogram of FCA depicted in Fig. 4 (a) is dominated by this study investigates the effect of partial replacement of FCA by
reflection peaks of quartz (more intense), mullite, calcite, GGBFS up to 60% on compressive strength development of
hematite, maghemite, forsterite, and aragonite and appears less geopolymer specimens. As seen from Fig. 4, Mix F80: G20 contain-
amorphous with no significant broad humps suggesting their low ing 80% FCA, 20% GGBFS and lime (10% by wt. of GGBFS) achieved
reactivity. As observed from Fig. 4(b), the diffractogram of GGBFS the highest compressive strength of 27 MPa at the age of 28 days. It
shows the presence of quartz, calcite, magnetite, and mullite as was also observed from the Fig. 5 that as the content of FCA
major phases. increases from 40% (F40:G60) to 80% (F80:G20) of the binder, the
strength increased from 20 MPa to 27 MPa respectively. However,
3.2. Rheology and development of compressive strength a reduction in compressive strength development was noticed
when GGBFS was partially replaced up to 40% of the binder (F60:
Though there is no availability of any standard code of practice G40) which achieved the lowest compressive strength of
for conducting workability tests of geopolymer concrete mix [23], 18.8 MPa at the age of 28 days. Prior studies [13,15–18] have sug-
slump test as specified by IS-1199 (1959) [11] was performed in gested that addition of GGBFS in the matrix resulted in formation
this study. However, it was observed that all the mixes showed of C-S-H, C-A-S-H and N-A-S-H gels for which strength increased.
zero slumps even after the addition of extra water. It is probably However, the results of this study contradict the earlier findings
because of excess calcium content in the mix which is supplied based on inclusion of GGBFS. The reason for reduction of strength
by GGBFS and lime. Moreover, the silica content in the alkaline for the mix F60:G40 can be attributed to the development of
solution makes the mix more viscous leading to a zero slump. microcracks owing to excessive calcium content from GGBFS and
The compressive strength of FCA based geopolymer concrete lime [19]. Furthermore, some studies [20,21] also reported that
cubes with GGBFS and lime at the age of 7, 14 and 28 days is plot- increasing GGBFS content in the binder above 50% by wt. reduced
ted in Fig. 5. In the present experimental study, FCA was used as the compressive strength considerably. Strength loss due to addi-
the primary source material and GGBFS as secondary precursor tion of GGBFS can also attributed to formation of hybrid C-N-A-
for preparation of geopolymer concrete under outdoor curing con- S-H (Calcium sodium aluminosilicate hydrate) inside the geopoly-
ditions. Some researchers have discovered that calcium rich mer matrix [22].
 J. Mishra et al. / Materials Today: Proceedings 33 (2020) 5001–5006 5005

found to be unsatisfactory (zero slumps) hence use of appropriate

superplasticizer is recommended. Lime addition to the mix facili-
tated its fast setting behavior thus requiring no rest period after
casting. However, there is still a need to conduct some more tests
and studies to analyze the complete behavior of developed
geopolymer concrete. Therefore, future research goals include
detailed microstructural analysis of hardened concrete samples
using FESEM, XRD, FTIR, Petrographic analysis which would cer-
tainly contribute to the present understanding and development
of FCA based geopolymers.

Credit authorship contribution statement

Jyotirmoy Mishra: Conceptualization, Methodology, Visualiza-

tion, Investigation, Writing - original draft. Shaswat Kumar Das:
Investigation, Data curation. R.S. Krishna: Writing - original draft.
Bharadwaj Nanda: Writing - review & editing, Supervision. San-
jaya Kumar Patro: Supervision, Validation. Syed Mohammed
Mustakim: Resources, Project administration.

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.

Acknowledgements

Authors are thankful to Dr. Rajiv Mohapatra & Mr. Subhra-

manyu Kundu - Balasore Alloys Ltd., Balasore for supplying Fer-
rochrome Ash for this project. The authors gratefully
acknowledge Mr. Subash Sathpathy – NINL, Jajpur for supplying
GGBFS for experimentations. The authors would like to thank the
technical staff at CSIR-IMMT, Bhubaneswar for their assistance in
the experiments. The technical help under the guidance of Dr. Ajit
Fig. 4. XRD patterns of (a) FCA (b) GGBFS. Behera (XRD results), NIT Rourkela is duly acknowledged.

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