Performance Assessment of Graphene Oxide–Reinforced

Sustainable Geopolymer Concrete

Bavita Bhardwaj 1 and Pardeep Kumar 2
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Abstract: Geopolymers, known as the next generation binder, are gaining the interest of contemporary researchers due to their superior
strength and durability properties compared with ordinary portland cement (OPC). The current investigation aims to develop a greener
geopolymer concrete (GC) containing waste materials as a replacement to fine and coarse aggregates. Waste foundry sand (WFS), an
industrial waste, has been used as partial replacement to normal sand, whereas natural coarse aggregates were partially to fully replaced
by recycled concrete aggregates (RCA). In addition, indigenously synthesized graphene oxide (GO), in the laboratory, was added to GC by a
small proportion of 0.05% by weight of binder to compensate for the performance loss in GC due to addition of waste materials. The strength
and durability properties were studied up to 90 days of curing age. The microstructure was also studied by conducting scanning electron
microscope (SEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FT-IR) to support the strength and durability
results. The test results are promising and indicate enhanced performance of GC produced using waste materials with GO addition.
DOI: 10.1061/(ASCE)MT.1943-5533.0003942. © 2021 American Society of Civil Engineers.
Author keywords: Geopolymer concrete (GC); Waste foundry sand (WFS); Recycled concrete aggregates (RCA); Graphene oxide (GO);
Fly ash; Ground granulated blast-furnace slag (GGBS).

Introduction and in the presence of aggressive chemical environments

Concrete continues to be the backbone of most construction and
development projects around the world. But harmful environmental
effects associated with the production of conventional concrete and
its ingredients necessitate switching to other environment friendly
and sustainable substitutes. Geopolymers, the new age binders, are
considered as prospective substitutes for conventional ordinary
portland cement (OPC), owing to their superior performance in
concrete (Singh et al. 2015). A geopolymer is an inorganic alumi-
nasilicate polymer structured around tetrahedral coordinated Si4þ
and Al3þ forming a polymer chain. These geopolymer precursors
chemically bind and form oligomers, leading to the formation
of aluminosilicate polymers (Thapa and Waldmann 2018). Geo-
polymer binders completely replace OPC by utilizing binding
properties of aluminosilicate source materials such as fly ash,
metakaolin, and blast-furnace slag, making concrete less energy-
intensive and more environment friendly (Davidovits 1999; Thapa
and Waldmann 2018).
Binder developed using Class-F fly ash (FA) is most appropriate
for developing geopolymer concrete (GC) as the resulting product.
Although FA GC can utilize FA, a by-product of coal combustion
from thermal plants, in large quantity, it also exhibits superior
mechanical (Albitar et al. 2015; Hardjito and Rangan 2005; Chi
and Huang 2013) and durability properties under thermal loading
1
Research Scholar, Dept. of Civil Engineering, National Institute of
Technology Hamirpur, Hamirpur, Himachal Pradesh 177005, India (corre-
sponding author). ORCID: https://orcid.org/0000-0001-9307-1059. Email:
bavita.bhardwaj@gmail.com
2
Associate Professor, Dept. of Civil Engineering, National Institute of
Technology Hamirpur, Hamirpur, Himachal Pradesh 177005, India. Email:
pardeepkumar.nit@gmail.com
Note. This manuscript was submitted on July 27, 2020; approved on
March 19, 2021; published online on September 7, 2021. Discussion period
open until February 7, 2022; separate discussions must be submitted for
individual papers. This paper is part of the Journal of Materials in Civil
Engineering, © ASCE, ISSN 0899-1561.
(Davidovits 1991; Van Deventer et al. 2012; Shi et al. 2011).
But the drawback of delayed setting associated with curing at am-
bient temperature has led to study its properties only under
elevated-temperature curing conditions. Inclusion of some propor-
tion of calcium-rich source materials can accelerate the setting time
when adopting an ambient curing regime.
Notable studies have been reported on the addition of other ma-
terials in variable proportions such as OPC, CaO, CaOH, ground
granulated blast-furnace slag (GGBS), silica fume, and metakaolin,
among others, as a replacement to FA in GC (Deb et al. 2016;
Dombrowski et al. 2007; Khan et al. 2016; Nath et al. 2015; Nath
and Sarker 2015; Nuruddin et al. 2010). The presence of calcium
oxide in GGBS has been found to increase the compressive
strength of GC based on low-calcium FA. Studies have suggested
the possibility of coexistence of geopolymeric aluminosilicate hy-
drate (N=K-A-S-H) gel along with calcium silicate hydrate gel
(C-S-H gel) formation within a single binder (Yip et al. 2005).
Fly ash, the by-product of coal combustion in thermal power
plants, is abundantly available worldwide, but to date only limited
quantities are being utilized. The utilization of FA in production of
cement and concrete has, to some extent, solved the problem of its
disposal. It is estimated that, if fully industrialized, geopolymer ce-
ment will have 80% lower embodied greenhouse gas emissions than
an equivalent amount of OPC binder (Davidovits 2015). The cost of
FA-based GC is assessed to be 10%–30% cheaper than that of OPC
concrete (Lloyd and Rangan 2010). Moreover, several investigations
have assessed the performance of GGBS as a cementitious material
in cement production since 1939 (Li et al. 2010). The use of GGBS
as cement replacement material in concrete has been found to reduce
CO2 emission by great extent (Dinakar et al. 2013).
Aggregates constitute about 60%–80% of the total concrete
volume. There is rising concern about overexploitation of natural
sand and gravels due to massive use of concrete, which is accred-
ited to the boom in urbanization and industrialization. This has
led to several harmful consequences to the environment. Moreover,
the restrictions in the extraction of sand from rivers resulted in

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 increase of the sand price, which severely affected the subsistence
of the construction industry (Dolage et al. 2013). Thus, it has be-
come imperative to look for an alternative to natural aggregates for
concrete.
Waste foundry sand (WFS), a by-product from the ferrous and
nonferrous metal casting industries, is one such promising material
that needs to be studied extensively as a substitute of fine aggre-
gates in concrete. Characteristically, WFS with subangular to round
shape and with high thermal conductivity makes it suitable for
molding and casting operations (Bhardwaj and Kumar 2017).
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Experimental Program
Materials
In this study, a combination of two source materials was used
i.e., fly ash and (GGBS). Fly ash was obtained from Ambuja
Cement Plant situated at Darlaghat, Solan (HP), India. Fly ash used
was of Class F grade (ASTM Class F) conforming to Indian stan-
dard IS 3812 (Part 1) (BIS 2013). Slag used in the study was pro-
cured from Astrra Chemicals, Chennai, India, conforming to Indian
standard IS 12089 (BIS 1987). Chemical composition and loss on

Metal-alloy casting industries only produce several million tons

of WFS as its by-product throughout the world. The US discards ignition (percent by weight) of source materials, as provided by
about 6–10 million tons of WFS every year, which goes into land- supplier, is given in Table 1. Specific surface area of fly ash and
GGBS was 260 and 390 m2 =kg, respectively.
fills (Noumowé et al. 2009; Winkler and Bol’shakov 2000). The
A combination of two alkaline solutions, i.e., a sodium silicate
Indian foundry industry, ranked as third largest casting manufac-
solution and sodium hydroxide, was used in the study in the ratio
turer in the world after China and the US, is estimated to discard
of 2.5∶1 by weight for activation of source materials. Both alkalis were
nearly 1.71 million tons of WFS per annum (Siddique and Singh
of commercial grade procured from a local producer. Sodium silicate
2011). In an effort to use the WFS in large volumes, research is
(Na2 SiO3 ) was a clear, colorless, and viscous solution with SiO2 to
being carried out for its possible substantial utilization as partial
Na2 O ratio of 2.1 and water content of 52%. The sodium hydroxide
replacement of fine aggregate in concrete. (NaOH) solution of desired molarity, i.e., 12 M, was prepared by mix-
Furthermore, the rapid urbanization rate is not only increasing ing 98% pure pellets in regular tap water. The concentration of NaOH
the consumption of natural and nonrenewable resources but is was kept constant for all geopolymer concrete mixes and was pre-
also responsible for the generation of an enormous quantity of pared by mixing 361 parts of solids with 639 parts of water.
construction and demolition (C&D) waste, leading to related envi- Two types of sand were used as fine aggregate in the GC,
ronmental concerns. As per reports, 860 million tons of C&D i.e., regular sand made of crushed aggregates (NS) and WFS. Regular
waste was generated across the EU in 2014 (Ramboll 2019), sand was procured locally. Waste foundry sand was green sand (i.e.,
516 million tons in the US in 2017 (EPA 2019), 75 million tons comprising bentonite as a binder) procured from one local foundry, a
in Japan, more than 1.4 billion tons in China (Huang et al. 2018), manufacturer of ferrous automobile parts. Crushed aggregates were
and 12–15 million tons in India (BMTPC 2016). The C&D waste used as coarse natural aggregates (NCA) along with recycled concrete
often represents the most significant proportion of the total solid aggregates (RCA) of nominal size 12.5 mm. Recycled aggregates
waste generated in several countries. Using the recycled concrete were acquired after sieving the aggregates obtained from crushing
aggregates extracted from C&D waste in concrete mixtures as the concrete specimens in the concrete technology laboratory of
partial to full replacement to natural aggregates is a way to make the institute i.e., National Institute of Technology Hamirpur. Grada-
concrete more sustainable along with reductions in the burden on tions of both coarse aggregates were deliberately kept similar.
the environment. Tables 1 and 2 present some chemical and physical properties of
Nowadays, nanotechnology has an important role to play in the aggregates used in the study, respectively. The fine aggregates have
field of construction industries. It has been seen that several proper- been categorized under different zones, according to their fineness,
ties of cement-based concrete are affected by different nanomate- as per Indian standard IS 383 (BIS 2016). Fig. 1 depicts the grading
rials. Graphene oxide (GO), a form of graphene nanosheet, in curves of fine and coarse aggregates. Modified polycarboxylic
particular, has shown high potential in modifying the microstruc- ether–based superplasticizer was added to the GC to improve its
ture of a cementitious matrix owing to presence of surface function- workability. The superplasticizer had relative density of 1.08 
alities and high dispersibility in water (Compton and Nguyen 2010; 0.01 and pH ≥ 6 at 25°C with chloride content <0.2%.
Muthu et al. 2021b). However, little research has been conducted
to investigate the performance and compatibility of GO in GC. The
Graphene Oxide Sheets: Synthesis and Structural
alkali-activated fly ash binder or geopolymer is distinguished from
Characterization
the cement by its higher initial alkalinity and less availability of
Ca2þ ions. Also, the hydration products tend to form Ca(Na, K)- Graphene oxide was synthesized in the institute laboratory, i.e., at
A-S-H (aluminosilicate hydrate) gels instead of C-(A)-S-H National Institute of Technology Hamirpur, using modified
(aluminate-substituted calcium silicate hydrate) gels. As such, the
behavior of GO in the alkali-activated fly ash binder or geopolymer Table 1. Chemical properties of fly ash, GGBS, and WFS
can be different from that in case of OPC-based concretes; hence, it
Constituent Fly ash (%) GGBS (%) WFS (%)
needs to be studied.
This study investigates the possible role of laboratory- SiO2 59.87 33.06 78.5
synthesized GO incorporation in the strength gain, durability, and CaO 5.06 35.37 2.44
Al2 O3 23.96 22.29 5.50
microstructure of chemically activated low-calcium fly ash-GGBS
Fe2 O3 3.70 0.9 4.45
binder GC, constituting waste materials as fine and coarse aggre- MgO 0.48 7.61 2.76
gates. The authors hypothesized that GO dispersed in the GC can Na2 O 0.17 — 0.79
be employed as growth points to facilitate the fly ash hydration and SO3 0.16 0.38 0.22
modify the structure of hydration products at molecular level, K2 O 1.20 — 0.52
which in turn may improve the mechanical performance as well MnO — 0.12 —
as microstructure of GC and compensate for the strength and TiO2 1.27 — 0.15
performance loss in GC due to addition of waste and recycled P2 O5 0.28 — —
Loss on ignition 2.00 0.26 4.65
materials as fine and coarse aggregates.

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 Table 2. Physical properties of fine and coarse aggregates of oxygen (O) in GO signifies the presence of oxidative functional
Fine aggregate Coarse aggregate groups.
X-ray diffraction (XRD) analysis was carried out using an X-ray
Property NS WFS NCA RCA
diffractometer (PANalytical X’Pert PRO, PANalytical, Almelo,
Specific gravity 2.65 2.18 2.74 2.47 Netherlands). Fig. 4(a) shows the XRD pattern of GO. A broad
Fineness modulus 2.50 0.94 6.62 6.62 peak was observed at 2θ value of 9.5°, with an interplanar spacing
Zone [IS 383 (BIS 2016)] II IV — — of 9.302 Å, attributed to the characteristic diffraction peak of GO
Water absorption (%) 0.55 1.5 0.68 5.30 (001). This broadening in XRD patterns of GO signifies the in-
crease in interplanar spacing due to the incorporation of functional
groups. These functional groups are set between the layers of gra-
phitic sheets, and hence increase the spacing between the adjacent
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100
90
NS sheets.
80 FT-IR was obtained using a Perkin Elmer Spectrum RX-I
WFS
70 Fourier transform infrared spectrophotometer (Perkin Elmer, Wal-
% Passing

60 tham, Massachusetts). Fig. 4(c) shows measured Fourier transform

NCA &
50
RCA
40
30
UL IS-383
20
LL IS-383
10
0 sp2 hybridization (Devi and Khan 2020). The medium and broad
0.1 1 10
Particle size
Fig. 1. Grading curves of fine and coarse aggregates.
Hummer’s method (Hummers and Offeman 1958) (Fig. 2). The
suspension, a GO solution [Fig. 2(b)], obtained using the method
was left undisturbed for 24 h [Fig. 2(c)] and then filtered by vacuum
suction along with repeated washings with tap water to wash out
SO2−4 from the GO [Fig. 2(d)]. The residue GO was then vacuum
dried at temperature 100°C for 10 h, then ground to obtain pow-
dered GO [Fig. 2(e)] and stored in an airtight container for using
in concrete.
Synthesized GO was further characterized using different tech-
niques. Scanning electron microscope/energy dispersive X-ray
spectroscopy (SEM/EDX) was done using a Quanta FEG 450
(FEI, Hillsboro, Oregon). Figs. 3(a and b) show the scanning elec-
tron microscopy images and the EDX spectra of graphite powder
and powdered synthesized GO, respectively. scanning electron mi-
croscope (SEM) micrograph of graphite, i.e., the precursor for GO
synthesis, indicates its flaky nature. Fig. 3(b) depicts the crumpled
surface of GO nanosheets. This wrinkling of the surface of GO oc-
curs due to the attachment of various functional groups over its
surface in the course of oxidative treatment of the precursor
(Sharma and Kothiyal 2015). The large surface area of GO
nanosheets knitted with weak Van der Waals bond appears to be
wrinkled (Devi and Khan 2020). The elemental composition of
the near-surface of graphite powder and synthesized GO is given
in Table 3, as obtained from their EDX analysis. A high percentage
infrared spectroscopy (FT-IR) for synthesized GO. From the spec-
tra, it is evident that treatment of precursor graphite with oxidizing
agents leads to surface functionalization of graphite flakes. This is
due to the disruption of oxygen-containing functional groups on the
peaks at 3,159 and 2,770 cm−1 are attributed to the presence of
hydroxyl group (-OH), and the peak at 1,712 cm−1 signifies the
presence of carbonyl/carboxyl group (C═O), hence confirming
the presence of the carboxylic (-COOH) group. A C─O stretch
is confirmed at 1,154 cm−1 . A strong absorption peak at
1,035 cm−1 signifies S═O stretching. The absorption peak at
1,615 cm−1 confirms the presence of aromatic double bonds
(C═C). Hence, the FT-IR results confirm the presence of assimi-
lated oxygen functional groups in the synthesized GO nanosheets.
Mix Details, Preparation, and Curing
The concrete mixes were proportioned as such to study the influ-
ence of WFS and RCA addition on strength properties and micro-
structure of GC and hence the effect of GO addition by 0.05% of
the weight of powdered binder (FA+GGBS) on the performance
of developed GC mixes. A total of six GC mixes were studied.
The control GC mix, i.e., G00W00R, was designed assuming den-
sity as 2,420 kg=m3 , and other calculations were made based on the
density of concrete as per the mix design procedure given by Junaid
et al. (2015) to obtain compressive strength of more than 35 MPa.
The mix was finalized after conducting trials. The combined weight
of aggregates was taken as 76% with coarse aggregate and fine ag-
gregate in the ratio of 65∶35. In the specimen notation of the GC
mixes, W denotes WFS whereas R denotes RCA and is preceded by
their percentage contents in the mixture as a replacement to respec-
tive natural aggregates. A superscript asterisk denotes the addition
of 0.05% GO. Total binder (FA + GGBS + alkaline solutions) was
24% by weight of GC. The ratio of alkali solution to powdered
binder (FA+GGBS) was kept constant as 0.45 for all mixes.

(a) (b) (c) (d) (e)

Fig. 2. Stages of graphene oxide preparation: (a) after completion of reaction; (b) GO suspension; (c) precipitated GO after 24 h; (d) residue GO after
filtration; and (e) vacuum oven-dried GO powder.

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(a)

(b)

Fig. 3. SEM image and EDX spectra: (a) graphite powder; and (b) synthesized GO.

The total water to geopolymer solid ratio was kept constant as 0.35 RCA were finalized based on already reported studies (Arora and
for all mixes. Superplasticizer, mixed in extra water, was added Singh 2018, 2019). As reported in previous studies, a small pro-
after 50% of mixing of GC was done. It was added 1% by weight portion of GO (0.01–0.08) has been found to enhance strength sig-
of the powdered binder. nificantly, durability as well as microstructure of concretes (Devi
The control mix constituted only natural aggregates as coarse and Khan 2019; Lu and Ouyang 2017). Based on these studies,
and fine aggregate. WFS was added as a partial replacement to as well as, keeping the economy of concrete in mind, an in-between
regular sand, 40% by weight, and RCA replaced NCA by two pro- proportion was chosen i.e., 0.05% of weight of binder (FA
portions, i.e., 50% and 100%, by weight. Two replacement levels of +GGBS). The mix proportions of different GC mixes are presented
in Table 4.
Activator solutions of desired quantity were prepared and mixed
Table 3. Chemical composition of graphite powder and synthesised GO about 24 h before mixing in the solution. This was done in refer-
ence to previous studies so that the solution cools down to room
Weight (%)
temperature beforehand and also to enhance its reactivity (Nath and
Element Graphite GO Sarker 2014). Coarse and fine aggregates, prepared in saturated
C 97.32 52.72 surface-dry condition, were mixed first in rotary pan mixer for
O 2.68 40.44 2 min. Powdered binder, thoroughly mixed beforehand until a uni-
S 0 4.84 form color was obtained, was then added in the aggregates and
N 0 1.58 mixed for another 2 min.
Mn 0 0.42 After that, premixed alkaline activator solution was poured
Total 100 100
gradually. When about 50% mixing was done, then superplasticizer

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 GO GO
9.50

2770
3159
Transmittance

1712
1615
Intensity

42.49

1154
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1035
4000

3500

3000

2500

2000

1500

1000

500
0 20 40 60 80
2
(a) (b) Shift, cm-1

Fig. 4. Synthesized GO: (a) XRD spectra; and (b) FT-IR spectra.

Table 4. Proportion of constituents of GC concrete

Quantity (kg=m3 )
Mix label FA GGBS NS WFS NCA RCA SSa SHb EWc GO (%)
G00W00R 240 160 644 0 1,196 0 128.6 51.4 68 0
G40W00R 240 160 386.4 234.2 1,196 0 128.6 51.4 68 0
G40W50R 240 160 386.4 234.2 598 539.1 128.6 51.4 68 0
G40W100R 240 160 386.4 234.2 0 1,078.2 128.6 51.4 68 0
G40W50R* 240 160 386.4 234.2 598 539.1 128.6 51.4 68 0.05
G40W100R* 240 160 386.4 234.2 0 1,078.2 128.6 51.4 68 0.05
Note: Asterisk in mix name indicates mixes containing graphene oxide.
a
Sodium silicate solution.
b
Sodium hydroxide solution.
c
Extra water added to the mix.

mixed in extra water was added. In case of GO mixes, aqueous GO
dispersion was prepared simultaneously in half of the extra water
along with the dosage of superplasticizer and stirred with the help
of high-speed magnetic stirrer for 1 h for each mix and then added
in concrete along with the remaining extra water. Mixing was con-
tinued for another few minutes until a uniform mix was obtained.
Slump cone testing was performed, as per Indian standard IS 1199
(BIS 1959a), immediately after mixing. Concrete was then poured
in the specified concrete molds and compacted with the help of a
table vibrator. After 24 h of casting, all specimens were demolded
and then kept in the laboratory for dry ambient curing [temperature
30°C  5°C and relative humidity (RH) = 80%  10%] until testing
ages of 28, 56, and 90 days.
Tests Performed
Workability of the fresh GC mixes was assessed by performing
slump cone test according to Indian standard IS 1199 (BIS
1959a). Tests on hardened concretes were performed at the age
of 28, 56, and 90 days. Cube specimens of size 100 × 100 ×
100 mm were cast to test compressive strength, whereas beam
specimens of size 100 × 100 × 500 mm were used for testing
flexural strength, and cylinder specimens of size 100-mm diameter
and 200-mm height were used to assess the split tensile strength of
GC mixes. Compressive strength and split tensile strength tests
were performed on automatic compression testing machine (CTM)
with a load capacity of 3,000 kN as per Indian standards IS 516
(BIS 1959b) and IS 5816 (BIS 1999), respectively. Flexural
strength of concrete beams was assessed by four-point bending us-
ing flexure testing machine as per Indian standard IS 516. An aver-
age of three samples were tested to obtain the strength value at a
particular age, for all mixes.
Sorptivity testing as per ASTM standard [ASTM C1585-04
(ASTM 2004)], was performed on cylindrical discs of size 100-mm
diameter and 50-mm thickness cut from cast cylinders of size
100-mm diameter and 200-mm height. Three disks were cut from
each cylinder for testing, and average of three values was used for
each curing age. Before testing, the samples were conditioned and
prepared as per the procedure given in the mentioned standards.
The bulk electrical resistivity of GC samples was calculated by us-
ing Wenner’s four-probe method. For the test, cubes of size 100 mm
were cast with copper strips of size 1.5 × 15 × 60 mm embedded
up to 50 mm in the fresh concrete immediately after leveling the
surface of concrete.
Concrete pieces taken from the fractured cube samples of age
28 days were also studied for their microstructure. SEM imaging

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 was done to get an idea about the surface morphology of GC mixes
to know the compactness of matrix, geopolymer gel formation, and
presence of pores and cracks, among others. XRD patterns of GC
mixes were acquired to study various crystalline phases in the
mixes. A FT-IR study was performed to identify the molecular
structure and composition of the GC.
The SEM imaging was conducted on a Quanta FEG 450 using
secondary as well as backscatter electron detectors. The different
X-ray diffraction patterns of FA, GGBS, and GCs were obtained on
a PANalytical EMPYREAN diffractometer (PANalytical, Almelo,
Netherlands) using Cu Kα radiation (λ ¼ 1.54056 Å) with fixed
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divergence slit of size 0.2177°, generator settings at 40 mA and
45 kV, and measurement temperature of 25°C. Analytical range
was between 5° and 80° (2θ) with a step of 0.008° for one single
continuous measurement for each sample. The crystalline phases
present in the materials were identified by comparison with the
standard powder diffraction files of International Centre for Dif-
fraction Data. The FT-IR data were obtained using a Perkin Elmer
Spectrum RX-I Fourier transform infrared spectrophotometer (Per-
kin Elmer, Waltham, Massachusetts).
Results and Discussion
Workability
Alkaline solutions, due to the high viscosity, produced sticky and
cohesive concrete mixes of thick consistency. Presence of finer slag
also supplemented in gaining cohesiveness. The mixes were able to
flow under the effect of gravity. Because the rheology of GC is not
similar to conventional OPC concrete, the workability tests such as
slump and flow test results of GC do not impart the same level of
workability as OPC concrete mixes (Nath and Sarker 2014). How-
ever, the results do provide an adequate idea regarding their work-
ability (Nath and Sarker 2014). To improve the workability of
mixes in current research, extra water and superplasticizer were
added to achieve the workability of concrete mixes in the desired
range (75–100 mm). Because RCA was used in saturated surface
dry condition, increasing in its proportion had no adverse effect on
the workability of GC mixes.
Strength Properties
Low-calcium GC has one drawback of delayed setting when cured
in ambient temperature (Nath and Sarker 2014). Available literature
on geopolymer concrete mostly constitutes studies on its properties
when cured under elevated temperatures (Singh et al. 2015). Never-
theless, under elevated-temperature curing conditions, GC shows
better performance, but application of heat curing limits its use
to precast purposes only. So, in the current study, GGBS has been
used as source material along with FA to achieve early initial setting
at ambient temperature.
Fig. 5 depicts the results of strength tests performed on GC
mixes at 28, 56, and 90 days of curing age. An average of three
values was taken to get the average strength values of mixes at all
ages. From strength values, it can be observed that the replacement
of 40% NS by WFS led to an increase in compressive strength of
GC in the range of 4.77%–6.65% with respect to the control mix.
However, the replacement of NCA by RCA in two proportions,
i.e., 50% and 100%, decreased the strength.
Replacement by 50% RCA led to strength loss in the range of
1.75%–4.46% in Mix G40W50R at all ages. Whereas 100% RCA
replacement led to further strength loss in the range of 12.89%–
17.77% in Mix G40W100R at all ages. It can be observed from
the figures that 0.05% GO addition helped in covering up the
© ASCE 04021322-6
J. Mater. Civ. Eng., 2021, 33(11): 04021322
strength loss in GC mixes due to RCA addition significantly. Mix
G40W50R* achieved compressive strength superior even to the
control mix, i.e., in the range of 15.15%–18.42% more than control
mix. Furthermore, Mix G40W100R*, with 100% RCA content,
achieved strength less than the control mix, but it showed enhance-
ment in strength in comparison with its respective mix without GO,
i.e., G40W100R in the range of 9.58%–13.59% at all ages. Similar
trends were observed in split tensile strength and flexural strength
results.
GO has been found to enhance the rate of polymerization reac-
tions (Xu et al. 2018). Also, it can be observed that despite high
replacement of NCA by RCA in the mixes, there is not much
strength loss in the mixes. This could be attributed to unhydrated
residual binder on RCA that would have activated amid the blend-
ing progression and brought the enhanced strength. Additionally, it
has been reported in the literature that GC forms good bond with
RCA as well as with steel, compared with its counterpart OPC con-
crete, owing to its denser interfacial transition zone (ITZ) (Shaikh
2016; Shi et al. 2012). This could also be credited to outstanding
synergistic effect of FA and GGBS on the mechanical performance
of GC with recycled aggregates (Xie et al. 2019a). Presence of
GGBS in GC also improves the compactness of the GC matrix
(Xie et al. 2019b). Additionally, this could be due to presence
of finer WFS particles, which might have also assisted in compact-
ing the matrix.
Durability Properties
Fig. 6(a) shows the variation of the average initial rate of absorption
(IRA) of considered GC mixes. It can be observed that similar to
strength results, replacement of NS by WFS by 40% reduced the
IRA values of GC at all ages. Replacement by 50% RCA led to
increase in IRA value in the range of 5.29%–5.73% in Mix
G40W50R at all ages. Whereas 100% RCA replacement led
to further rise in IRA in the range of 17.46%–18.23% in Mix
G40W100R at all ages. It can be observed from the figures that
0.05% GO addition helped in decreasing the IRA in GC mixes.
Mix G40W50R* achieved significantly lower IRA than the control
mix, i.e., in the range of 19.79%–21.69% less than the control mix.
Furthermore, Mix G40W100R* with 100% RCA content achieved
higher IRA than the control mix, but it showed lower IRA in
comparison with its respective mixes without GO, i.e., G40W100R,
in the range of 12.33%–12.95%, at all ages.
It can be observed that regardless of high replacement of normal
coarse aggregates by RCA in the mixes, there is not much signifi-
cant rise in IRA in the mixes attributed to the presence of finer WFS
particles, which helped in filling up the pores. Fig. 6(b) shows the
correlation between average IRA value of mixes and compressive
strength at all ages. The sorptivity values linearly decreased with
increase in compressive strength, with a R2 value more than 0.95 at
all ages.
The electrical resistance of concrete is a volumetric property of
concrete that points out the capability to transport an electrical
charge through the material (Andrade 2014). The concrete having
fewer interconnected pores with a more tortuous path will have
a higher electrical resistivity because it would be more difficult
for ions to move across these kinds of pore networks. Even though
the pore network connectivity, as well as the moisture content in
the pore network, are the major factors influencing the electrical
resistivity of concrete, nevertheless, the existence and motion of
ions such as Naþ ; Kþ , and OH− in the pore solution should also
be considered. In concrete, electrolytic conduction is the main phe-
nomenon of electricity transport because aggregates’ conductivity
is very low (Palacky 1988). The alkali contents present in the pore
J. Mater. Civ. Eng.
 60.00 5.00
4.50
50.00

Compressive Strength, N/mm 2

Split Tensile Strength, N/mm2

4.00
3.50
40.00
3.00
30.00 2.50
28D 2.00
28D
20.00
56D 1.50
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56D
1.00
10.00 90D 90D
0.50
0.00 0.00

(a) Mixes (b) Mixes

6.00

5.00
Flexural Strength, N/mm 2

4.00

3.00

2.00 28D

56D
1.00
90D

0.00

(c) Mixes

Fig. 5. (a) Compressive strength; (b) split tensile strength; and (c) flexural strength results of GC mixes.

0.0240 0.0240

0.0220 0.0220
Average IRA, mm/Sec 1/2

Average IRA, mm/Sec 1/2

0.0200
0.0200
28D,
0.0180 R2=0.99
0.0180 28D
0.0160 56D,
56D R2=0.98
0.0160
90D 0.0140
90D,
R2=0.96
0.0140 0.0120
25.00 35.00 45.00 55.00
Compressive Strength, N/mm 2

(a) Mixes (b)

Fig. 6. (a) Average IRA values of GC mixes; and (b) correlation with compressive strength results.

© ASCE 04021322-7 J. Mater. Civ. Eng.

J. Mater. Civ. Eng., 2021, 33(11): 04021322

 14.00
cm
12.00
Electrical Resistivity, k
10.00
8.00
6.00
4.00
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2.00
28D
(a) Mixes
Fig. 7. (a) Electrical resistivity of GC mixes; and (b) correlation with compressive strength results.
solution of the concrete mainly influence the electrical resistance
values. GC is produced with highly alkaline components as acti-
vators. Therefore, lower resistance values are obtained for GC
due to the high alkali species (NAþ and Kþ ) in the pore solution
of concrete.
Browner (1982) previously studied the relationship between
corrosion rate and electrical resistivity of concrete and found
that the concrete resistivity must be kept above the range of
5–10 kΩ-cm to prevent corrosion of reinforcement steel. Gonzalez
et al. (1993) suggested that the corrosion rate was negligible when
concrete resistivity was higher than 10 kΩ-cm. Fig. 7(a) presents
the electrical resistivity values of GC mixes at all ages. It can be
observed that all GC mixes depicted low electrical resistivity val-
ues. Electrical resistivity of concretes increased as the curing age
increased.
With WFS addition, there was increase in resistivity values at all
ages. The rate of increase in resistivity value in all mixes was found
to be higher at later ages, i.e., 56–90 days (10%–41%) compared
with the initial age i.e., from 28 to 56 days (10% to 29%). This
could be due to an increase in the degree of geopolymerization
and formation of a denser microstructure at later ages, which would
result in a disconnected pore structure and reduction in ions or
electrons flow.
GO addition helped in increasing the electrical resistivity of GC,
which is in line with the strength and sorptivity results (Qureshi and
Panesar 2019). With GO addition, electrical resistivity of mixes
with 50% and 100% RCA increased by 53% and 23%, respectively,
when compared with their respective mixes without GO at a curing
age of 90 days. Fig. 7(b) shows relation between compressive
strength and electrical resistivity of GC mixes, which depicts that
results had good correlation at later ages.
Microstructure
SEM and EDX Study
There was no significant difference in the SEM images of the GC
mixes, as can be seen in Fig. 8. Mix G00W00R has a very compact
microstructure, as is visible. Presence of unreacted silica and some
FA particles can be seen in all mixes containing WFS. Because for
SEM, study samples were taken from fractured cube specimens,
cracks can be seen on the SEM samples, which are due to stress
caused in the matrix due to application of axial load; it could be due
to mechanical damage caused during the preparation of samples.
© ASCE
14.01
12.01
Electrical Resistivity, k cm
10.01
8.01
28D,
6.01 R2=0.99
56D,
4.01
R2=0.98
2.01 90D,
R2=0.96
0.01
25.00 35.00 45.00 55.00
56D 90D
Compressive Strength, N/mm2
(b)
Perhaps, the most distinguishing difference in the microstructure
was an increase in the number of pores in GC containing WFS with
the increase in RCA content. Presence of some porous RCA ad-
hered mortar can also be identified in mixes containing RCA at
some places.
In the current study, coarser gel, which is typical of geopolymer
gel (aluminosilicate gel) was observed at some places but most of
the matrix of geopolymer was fairly even. This can be attributed to
GGBS, which typically helped in accelerating the reaction but also
helped in consuming unreacted FA particles by increasing the re-
activity of FA. Besides, surface microcracking due to stress built up
in the matrix, which is characteristic of high-slag-content matrices
like alkali-activated slags (AAS), was not observed in the micro-
structure of geopolymer mixes (Bhardwaj and Kumar 2019).
The key reaction product of low-calcium FA–based geo-
polymer, which is rich in Si and Al, is N-A-S-H gel (Na2 O-Al2 O3 -
SiO2 -H2 O) with a three-dimensional (3D) framework of SiO4 and
AlO4 tetrahedra linked through shared oxygen atoms (Hardjito
et al. 2004). However, the addition of GGBS in FA-based
geopolymer results in coexistence of C-S-H gel (CaO-SiO2 -
H2 O) with a low Ca/Si ratio along with the N-A-S-H gel (Criado
et al. 2016).
Graphene oxide was not identified in the SEM images of GC
matrix. This could be due to the fact that it has been added in very
low content; also, the size of dispersed GO will be in the nanoscale,
making it difficult to identify it in concrete matrix. Liu et al. (2020)
studied the microstructure of FA-based GO-geopolymer composite
and confirmed that GO promotes geopolymerization. The amor-
phous phases in FA are dissolved rapidly in the alkaline solution
and participate in the early geopolymerization process. However,
the crystals are stable, and they are difficult to be dissolved in alkali
solution, so there are a large number of crystals exposed on the
surface of FA microspheres. GO is adsorbed on the surface of
FA microspheres or it gets embed in the crack of GC matrix and
a large number of crystal particles and pores are formed in its
vicinity (Fig. 9). GO on contact with the crystal nucleus probably
facilitates the growth of a zeolitelike phase and induces the forma-
tion of monocrystalline layer. This way GO promotes the dissolu-
tion of FA and the formation of zeolite crystals, resulting in changes
in the pore diameter distribution of the geopolymer (Liu et al.
2020).
In contrast, there is coexistence of C-S-H gel in the GC matrix
due to addition of GGBS as binder. GO nanosheets act as nucle-
ation agents for C-S-H gels and participate in the hydration
04021322-8 J. Mater. Civ. Eng.
J. Mater. Civ. Eng., 2021, 33(11): 04021322
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(a) (b)

(c) (d)

(e) (f)

Fig. 8. SEM images of GC mixes: (a) G00W00R; (b) G40W00R; (c) G40W50R; (d) G40W100R; (e) G40W50R*; and (f) G40W100R*.

reaction. This consequently increases the polymerization degree of effects of inclusion of GO were evident in the strength as well
C-S-H gels. With GO sheets filled in the gel pores of C-S-H gels, as durability study of the GC mixes in the current investigation.
the microstructure becomes compact and the cohesive forces within Two mechanisms have been identified behind the action of GO.
the matrix improves (Sharma and Kothiyal 2016).The positive First is chemical action of GO, i.e., the highly dispersed GO

© ASCE 04021322-9 J. Mater. Civ. Eng.

J. Mater. Civ. Eng., 2021, 33(11): 04021322

Downloaded from ascelibrary.org by National Institute of Technology, Durgapur on 08/28/22. Copyright ASCE. For personal use only; all rights reserved.

Fig. 9. Adhesion of GO to geopolymer matrix and FA microspheres. (Reprinted from Construction and Building Materials, X. Liu, Y. Wu, M. Li,
J. Jiang, L. Guo, W. Wang, W. Zhang, Z. Zhang, and P. Duan, “Effects of graphene oxide on microstructure and mechanical properties of graphene
oxide-geopolymer composites,” pp. 118544, © 2020, with permission from Elsevier.)

can enhance the geopolymerization of aluminosilicate precursors.
Second is the physical action, namely that GO can act as a micro-
pore or crack filler with a bridging effect (Guo et al. 2020; Muthu
et al. 2021a).
XRD Spectrum Analysis
Fig. 10 shows X-ray diffractograms of precursor source materials
used for preparation of GC i.e., GGBS and FA, plotted on same
(a) Fly Ash
Q H= Hematite
Intensity (Counts)
scale. GGBS is mostly amorphous, as evident from the broad spec-
trum in the range of 2θ values of 20°–40°. Besides, the XRD
of FA depicts a vitreous phase shown by the broad hump recorded
between 2θ values of 17°–30°. This amorphous nature of the
precursor materials accelerates the geopolymerization process be-
cause it is easy to dissolve in an alkaline solution like sodium or
potassium silicate (Panda et al. 2018). In addition to amorphous
phases, FA also constitutes crystalline phases of quartz, mullite,
and hematite.
Fig. 11 shows X-ray diffractograms, plotted on same scale, for
the developed GC mixes. In all mixes a broad hump is observed
Q= Quartz between 2θ values of 20°–38°, which is a characteristic of
M= Mullite geopolymer material. The reaction products between 2θ values
of 21°–26°, 27°–29°, and 29°–36° depict relatively smaller inten-
A= Akermanite
sities, which indicate a nearly complete amorphous structure. It
G= Gehlenite
can be visualized from the diffractograms that the main geopoly-

Q M H
Q
M H M
MM H Q
M
meric structure comprises amorphous/semicrystalline, as well as
M QM M H
Q H M
MM
M Q crystalline, phases. On comparing the XRD peaks of precursor
source materials and GCs, it can be observed that many of the crys-
(b) GGBS talline phases prevailing in the FA (quartz and mullite, among
G
A others) have not been apparently altered by the activation reactions
A but shifted slightly to lower angles by very small degree.
It is interesting to see that peaks of quartz and mullite were not
decreased but slightly increased with the addition of GGBS. This
might indicate increases in the reaction degree of FA when used in
conjunction with GGBS. Increased reactions led to more exposure
0 20 40 60 80 of the crystallization forms from inside the FA and therefore their
easier detection by XRD (Xie et al. 2019a). Besides, these strong
diffraction peaks of quartz could also be due presence of sand par-
Fig. 10. XRD spectrum of (a) FA; and (b) GGBS used in the study.
ticles in the samples (Fernández-Jiménez and Palomo 2005a).

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© ASCE
04021322-11

J. Mater. Civ. Eng., 2021, 33(11): 04021322

Fig. 11. XRD spectrum of various GC mixes.

J. Mater. Civ. Eng.

 The XRD patterns of GCs shows formations of a 3D framework
of silicate tetrahedra (aluminosilicates) groups like albite (alkali
feldspar), microcline (plagioclase feldspar), sodalite (feldspathoid
family), and chabazite-Na (zeolite family). Besides, there is also
presence of silimanite, i.e., aluminosilcate mineral of nesosilicate
group. Besides, peaks at 2θ value of 29.4° and 50° may be attributed
to calcite. Low-intensity diffraction peaks of phases such as
sodalite at 8.9°, 12.4°, 17.7°, and 19.8° and chabazite-Na at 13.7°,
23.5°, 35°, and 43° were evident as products of geopolymerization.
There was appearance of sharp peaks of phases of microcline in
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GO mixes which would have helped in gaining additional strength
in theses mixes (Kürklü 2016; Paliwal and Marua 2017). Besides,
along with this, there was rise in peak of calcite in Mix G40W50R*,
which could be the reason for the highest strength gain. Phases of
calcite, sodalite, and silimanite increased in mixes with 40% WFS
and 50% RCA.
FTIR Spectrum Analysis
In a geopolymer, the reaction zones of Si-O and Al-O can be ex-
amined in order to recognize the formation of reaction products as
well as the degree of geopolymerization (Ryu et al. 2013). Fig. 12
plots the FT-IR results of GC mixes after 28 days of ambient curing.
The band located at 900–1,200 cm−1 i.e., ∼1,000 cm−1 , is attrib-
uted to the asymmetric stretching vibration of X-O (X represents Si
or Al) present in the hydrated sodium aluminosilicate gel, i.e., the
characteristic or fingerprint of geopolymerization (N-A-S-H gel,
Q4 units) (Chindaprasirt et al. 2011; Criado et al. 2016). The band
around 990 cm−1 may be due to the formation of C-S-H gel
(Q2 and Q1 units) (Criado et al. 2016). Q1 and Q2 Si forms a chain
structure (e.g., C-S-H), whereas Q3 and Q4 Si form a network struc-
ture (e.g., N-A-S-H) (Xu et al. 2018). The magnitude of the band is
mainly attributed to the amorphous nature of the material, as well as
the short-range ordering of Si and Al tetrahedron.
The bands between 1,600 and 1,650 cm−1 correspond to the
bending vibration of the -OH groups, and the bands assigned
between 3,350 and 3,450 cm−1 correspond to the stretching vibra-
tions of H-O-H bonds of the hydrated reaction products associated
with water, present in the hydrated sodium aluminosilicate gel
(Nath and Kumar 2013). These bands, associated with water,
indicate the geopolymerization reaction and do not exist in the
unreacted FA and GGBS samples, i.e., the precursor materials used
in the study (Somna et al. 2011).
100
Transmittance, %
80
60 G00W00R
G40W00R
G40W50R
G40W100R
40 G40W50R*
G40W100R*
4000
3600
3200
2800
2400
2000
1600
1200
800
Fig. 12. FT-IR spectrum of GC mixes.
© ASCE
J. Mater. Civ. Eng., 2021, 33(11): 04021322
Apart from these, strong bands at 1,420–1,460 cm−1 are due to
presence of atmospheric carbonation (Mollah et al. 1993). The peak
at ∼440 cm−1 is ascribed to in-plane bending modes of Al-O and
Si-O tetrahedral linkages (Fernández-Jiménez and Palomo 2005b).
The sharp band at 874 cm−1 is associated with bending vibrations
of CO2− 3 (Mollah et al. 1993). Bands at 791, 776, 731, and
694 cm−1 correspond to quartz forming part of FA as well as ag-
gregates (Fernández-Jiménez and Palomo 2005a).
Furthermore, the bands appearing at 522, 567, 597, 612, and
649 cm−1 in the spectrum have all been allied with the prevalence
of zeolites (Fernández-Jiménez and Palomo 2005a). These are
known as secondary building units and the fragments of alumino-
silicate system. These bands (500–800 cm−1 ) are characteristic of
the double or single rings (depending on the structure of the
material) and/or the TO4 (T represents Si and Al) tetrahedral bonds.
The variations in the number, shape, and position of the bands in
this region of spectrum are induced by the changes caused by for-
mation of a 3D structure by the ring interconnections (Fernández-
Jiménez and Palomo 2005b).
The peak at ∼1,000 cm−1 is the main fingerprint for the
geopolymer matrix representing the fusion of both Al-O and Si-O
asymmetric stretching (Ortego et al. 1991), and the drop in the
energy of the peak or its transmittance can signify the degree of
polysialation or aluminum incorporation. High transmittance at a
frequency signifies the presence of fewer bonds to absorb that light
in the sample, whereas low transmittance indicates high strength of
bonds having vibrational energies similar to the incident light. It
can be seen that replacement of NS by WFS by 40% lead to in-
crease in intensity of IR peaks at ∼1,000 cm−1 , indicating greater
polymerization. Besides, the increase in intensity of band located at
∼440 cm−1 suggests the formation of greater number of Si-O-Si
units. It can be observed that GO addition might have led to in-
crease in polymerization, which is evident from the decrease in
transmittance at ∼1,000 cm−1 .
Furthermore, an increase in the dip of bands amid 1,420–
1,460 cm−1 signifies an increase in atmospheric carbonation, lead-
ing to the formation of calcite. The peaks decreased with the
addition of WFS but increased to some extent with addition of
GO. The calcite formation helps in decreasing the porosity by
filling up the pores of concrete (Yazdi et al. 2018). The effect of
atmospheric carbonation is fairly evident, and this could be due to
the dry ambient curing of the samples in laboratory.
Conclusions
The current study was planned as such to develop sustainable and
green concrete utilizing waste materials in large proportions in con-
crete, such as aggregates, without compromising with the quality of
concrete. The addition of GO in the GC mixes certainly enhance the
performance. The following conclusions can be drawn from the
investigation of strength and durability as well as the microstructure
study of the developed GC mixes:
• Finer particles of WFS act as filler and help in filling up the
pores, which lead to enhanced strength and durability. Replace-
ment of natural coarse aggregates by 50% and 100% RCA led to
loss in compressive strengt,h but it was not very drastic due to
presence of finer WFS particles.
• The addition of GO lead to increase in all the mechanical prop-
erties of GC. The addition of 0.05% GO led to rise in compres-
400
sive strength in the range of 20.53%–21.55% in 50% RCA mix
and in the range of 9.58%–13.59% in mix with 100% RCA in
comparison with similar mixes without GO at all ages. Similar
04021322-12 J. Mater. Civ. Eng.
 trends werre observed in split tensile strength and flexural
strength results of GC mixes.
• Sorptivity of the GC mixes depicted results in line with strength
results. Addition of 40% WFS depicted similar or better results
than the control mix. Addition of GO refined the microstructure,
which led to a decrease in IRA values for mixes with GO. It
was found that 0.05% GO addition resulted in a decrease in
IRA value by 22.12%–25.63% in 50% RCA mixes and by
10.68%–12.95% in 100% RCA mixes. This clearly indicates
densification of its pore structure due to the presence of GO
in the GC mixes. Besides, all GC mixes depicted low electrical
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resistivity values due to alkalis present in the pore solution. But
the resistivity increased with curing age, which could be attrib-
uted to increase in geopolymerization reaction that leads to the
formation of a dense microstructure and disconnected pore
structure.
• SEM micrographs of all mixes depicted somewhat similar mi-
crostructures. The most distinguishing difference was increases
in the number of pores in mixes with WFS and RCA, besides the
presence of porous RCA with adhered mortar in RCA mixes.
XRD diffractograms of the GCs also depicted the appearance
of additional peaks of microcline and calcite, which could be
the reason for additional strength gain in GO mixes.
• FT-IR spectrum analysis confirmed the coexistence of C-S-H
gel along with N-A-S-H gel in the GC mixes. The magnitude
of these bands increased with GO addition, which indicates
that GO enhanced the geopolymerization reaction. Besides, the
peaks depicting atmospheric carbonation (calcite formation)
decreased with WFS addition but increased to some extent with
addition of GO. The calcite formation helps to some extent in
decreasing the porosity by filling up the pores of concrete.
Data Availability Statement
All data, models, and code generated or used during the study
appear in the published article.
Acknowledgments
The authors would like to greatly acknowledge the valuable support
of Material Testing Laboratory’s staff, Civil Engineering Depart-
ment, as well faculties and staff of Department of Material Science
and Engineering and Department of Physics and Photonic Science,
National Institute of Technology, Hamirpur, India, for carrying
out testing of concrete work reported in this study. The Ministry
of Human Resources and Development, India, is also gratefully
acknowledged for providing financial support to one of the authors.
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