Sustainable Chemistry and Pharmacy 31 (2023) 100913

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Sustainable Chemistry and Pharmacy

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

Effect of binary combination of waste gypsum and fly ash to

produce building bricks
Thandiwe Sithole *, Tebogo Mashifana, Dumisane Mahlangu, Léonel Tchadjié
University of Johannesburg, Department of Chemical Engineering, P.O. Box 17011, Doornfontein, 2088, South Africa

ARTICLE INFO ABSTRACT

Keywords: South Africa's production of wet flue gas desulfurization (WFGD) gypsum and fly ash (FA) has in-
Gypsum creased significantly owing to the country's dependence on coal power plant for electricity. These
Fly ash wastes are mainly dumped in landfills, which contributes to environmental pollution. Recycling
Beneficiation WFGD gypsum to generate value-added products may benefit the country economically and eco-
Compressive strength
logically. Given the chemical compositions of WFGD gypsum and fly ash, it is feasible to mix
Bricks
them to create a binder material. On the time when the study was done, no evidence of study had
been conducted on the binary combination of FA and WFGD gypsum produced locally to create
building materials. This study proposes a novel approach to lowering environmental pollution by
using two South African wastes, FA and WFGD gypsum, to produce sustainable building materi-
als. The mixture of WFGD gypsum and FA is intended to produce binding phases comprising et-
tringite and calcium silicate hydrate (CSH). Ettringite can be formed by hydration of alumina
(Al2O3) in fly ash with calcium sulfate (CaSO4) and calcium oxide (CaO) of WFGD gypsum, while
CSH can be generated by hydration of silica (SiO2) in fly ash under the same conditions. FA was
employed moderately to substitute WFGD gypsum in the production of FA: WFGD composite
blocks. Composite mixes were produced by substituting 0–40 wt% of WFGD gypsum with FA.
Composites bricks obtained were characterized using compression test and wet-dry cycles. Toxic-
ity characteristic leaching procedure (TCLP) were done to determine perilous elements existing
in the study sample and scanning electron microscopy (SEM) and energy dispersive spectroscopy
(EDS) for morphology analysis. X-ray diffraction (XRD) was utilized to establish the crystallinity
of the material. The strength results showed that FA used in this study was poorly reactive. As the
partial replacement of WFGD gypsum by FA increased from 0 to 40%, the strength of the compos-
ite material decreased. The pessimum effect of FA is mainly related to the low pH of the binary
mixture and low pozzolanicity of FA used. Incorporation of 20 wt% FA and curing temperature of
40 °C seemed to be suitable for the preparation of WFGD:FA composite bricks. The composite
bricks' highest UCS of 2 MPa exceeded the minimum strength for Class III mortar as per SANS
10145. Therefore, WFGD:FA composite bricks may be used as building materials.

1. Introduction
The production of electricity from coal power plants is a procedure that yields a variety of secondary products, including bottom
ash, fly ash (FA), slag, and flue gas desulfurization gypsum (WFGD), which are communally referred to as residues produced during
the combustion (KoralegedaraaNadeesha et al., 2019). In 2011, South African power stations produced around 32 million tons of fly

* Corresponding author.
E-mail address: nastassias@uj.ac.za (T. Sithole).

https://doi.org/10.1016/j.scp.2022.100913
Received 29 August 2022; Received in revised form 30 October 2022; Accepted 19 November 2022
Available online 7 December 2022
2352-5541/© 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
T. Sithole et al. Sustainable Chemistry and Pharmacy 31 (2023) 100913

ash, of which less than 10% was used by the cement industry (Eskom SOC LTD, 2020). China is expected to generate around 108 tons
of WFGD gypsum annually by 2020 (Liu et al., 2021). The expansion of the human population and industry has led to higher electric-
ity generation resulting in the production of great quantities of coal combustion residues (CCR), which are mainly dumped in land-
fills. Therefore, for industrial by-products' proper and affordable disposal is crucial aimed at the sustainable growth of industries and
environmental protection (Garg and Jain, 2010).
Waste materials are often used to produce building materials in the literature due to cost reductions, energy savings, and possibly
better products (Tchadjié et al., 2016; Sithole and Mashifana, 2020). There is a growing awareness in composite which has polymeric
constituents due to raw materials' synergetic effects, which is beneficial for composite's properties (Duan et al., 2018). Composite ce-
mentitious materials are usually produced by selecting raw ingredients with complementary chemical compositions. For example,
Kampala et al. (2014) studied the physical, mechanical and durability characteristics of calcium carbide (CC) and FA stabilized silty
clay. The results showed that CC and FA stabilization significantly increased the strength and the robustness of the stabilized silty
clay. The optimum dosage of CC and FA were around 7% and 20%, respectively. However, the high FA dosage resulted in a decrease
in strength. Tan et al. (Tan and Pu, 1998) developed a composite cement using a finely ground FA/blast furnace slag (GGBS) blended
system. They found that adding 20 wt% FA or GGBS to concrete significantly improved the early compressive strength. Similarly,
Park et al. (2016) revealed that cementless building blocks could be produced through the optimal combination of powder sludge
waste and GGBS. Sludge waste was utilized to supply silica (SiO2) and alumina (Al2O3), while GGBS served as a cause of responsive
calcium oxide (CaO). The was evidence of calcium silicate hydrate (C–S–H) and ettringite formation during the binder phase as a hy-
dration product which had positive impact on the strength development.
South Africa's production of WFGD gypsum and FA has increased significantly owing to the country's dependence on coal power
plant for electricity. The production of this material is actually a secondary product of the removal of sulfur dioxide (SO2) discharges
from thermal power plant using a wet or dry alkaline sorbent (KoralegedaraaNadeesha et al., 2019). The wet process is one of the
most frequently used WFGD techniques (Córdoba, 2015). WFGD gypsum consists mainly of sulfate dihydrate (CaSO4.2H2O) which is
used for various applications (Córdoba, 2015; Lei et al., 2017; Ma et al., 2020). Moreover, FA is a good source of reactive aluminosili-
cate minerals that have been widely employed as a cement extender in ordinary Portland cement (OPC) due to its pozzolanic proper-
ties (Gupta and Chaudhary, 2020; Yang et al., 2022a). It is well known that aluminosilicate minerals' chemical and mineralogical
composition affects their reactivity (Duan et al., 2018), (Tchadjie and Ekolu, 2018). Therefore, considering WFGD gypsum and fly
ash's chemical composition, they could be combined to develop a binder material. Telesca et al. (2013) showed that FA and WFGD
gypsum have the potential to be used to manufacture prefabricated building materials. Two ternary systems containing 25 wt% FA,
35 wt% calcium hydroxide, and 40 wt% natural or WFGD gypsum were examined. The composite mixtures were treated hydrother-
mally within the time and temperature ranges of 2 h–7 days and 55–85 °C, respectively. It was found that both reacting systems pro-
duced ettringite and C–S–H at optimal levels at curing temperature of 70 °C. Due to the difference in mineralogy between natural and
WFGD gypsum, the hydration behavior of the mixtures varied. Similarly, Yu et al. (2016) demonstrated that WFGD and river sand
may be combined without the use of hydraulic cement to produce non-fired bricks. The optimal combination for producing unfired
bricks was 75 wt% WFGD, 25 wt% river sand, and 20 wt% water based on the total weight of the two solids. The 7-day compressive
strength of the unfired brick as-prepared achieved up to 34 MPa. The good strength development was the result of the compact
macrostructure of the press-formed brick specimen and the interlocking microstructure of dihydrate gypsum crystals. Recently, Yang
et al. (2022b) investigated the activation of low reactive FA using calcium hydroxide (CH) associate with wet-milling. FA pastes of
varying particle sizes were prepared and activated with CH in concentrations of 4%, 11%, and 19%. The results demonstrated that al-
though the absolute value of compressive strength increased as the CH content increased, its value increased more rapidly when the
CH level was low. C–S–H was the primary factor affecting the development of strength. WFGD gypsum techniques is a relatively new
employed in South Africa. On the time when the study was done, no evidence of study had been conducted on the binary combination
of FA and WFGD gypsum produced locally to create building materials.
This study investigated the feasibility of using FA to stabilize wet flue gas desulfurization (WFGD) gypsum. FA was employed to
partly substitute WFGD gypsum in the manufacturing of FA:WFGD composite blocks. FA was used as an additional source of SiO2 and
Al2O3. During hydration of the WFGD:FA composite mixture, Ca2+ and SO42− ions from WFGD gypsum are expected to react with
Al2O3 and SiO2 from FA to produce binding phases for instance CSH and ettringite. Composite mixes were produced by substituting
0–40 wt% of WFGD gypsum with FA. Composites bricks obtained were characterized using compression test and wet-dry cycles. Toxi-
city characteristic leaching procedure (TCLP) were done to determine perilous elements existing in the study sample and scanning
electron microscopy (SEM) and energy dispersive spectroscopy (EDS) for morphology analysis. X-ray diffraction (XRD) was utilized to
establish the crystallinity of the material.

2. Experimental procedures
2.1. Raw material
WFGD gypsum was used as the source of calcium sulfate (CaSO4), while fly ash (FA) was an additional source of SiO2 and Al2O3.
The two components were collected from a South African coal power station. The power station is expected to generate 3.65 Mt of FA
and 1.6 Mt of WFGD gypsum annually, respectively. The materials were dehydrated for 24 h at 105 °C before being crushed and ho-
mogeneously combined using an Eriez Magnetic Rotary Riffler. Composite mixes were produced by substituting 20–40 wt% of WFGD
gypsum with FA.

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2.2. pH and density

The pH was measured using a Hanna Instruments HI 98130 pH meter. 100 mL of deionized water was used to mix 30 g of the
blended WFGD gypsum with FA composition and agitated uninterruptedly for 15 min immediately after measurement had been com-
pleted. A gas pycnometer (AccuPyc 1330, Micromeritics) was utilized to establish the relative density of raw materials. For each as-
sessment, three measurements were taken.

2.3. Geotechnical properties

2.3.1. Sieve analysis
For sieve analysis, dry material of 700 g was employed. The sample was crushed to separate the particles. A pile of sieves was pre-
pared with the following mesh sizes: 4.75, 2.50, 1.18, 0.60, 0.50, 0.125, 0.300, 0.150, and 0.075 mm. After shaking the pile of sieves
with a screen shaker for 10 min, the excess material that remained on respective screen was weighed. After washing the material from
the 0.075 mm sieve, the residual sample was determined. This test was conducted as specified in ASTM D6913/D6913 M (D6913/
D6913M 17, 2017).

2.3.2. Compaction test

ASTM D698 was used as a guide to establish the maximum dry density (MDD) and optimum moisture content (OMC) of the com-
posites (Tchadjie and Ekolu, 2018). Three equal masses samples of 2 kg of oven-dried material were prepared and split respectively.
Individual sample was hydrated to get a water content ratio. The combined sample brick was then deposited in three layers in a 1-L
mould, with each layer compacted consistently 25 times with a 2.5 kg proctor hammer. Subsequently a specimen was pressed out
from the mould and evaluated to measure its bulk density.

2.4. Mix proportions and preparation of bricks

In preparing for the building bloc/brick specimens, dry material samples of WFGD and FA were blended for two (2) minutes by
making use of a laboratory blender. Water was then used to further mix the sample. The volume of water used was determined using
the MDD and OMC values for each composite mixture. After mixing, the mixture was transferred inside a 50 mm square block moulds
and was subjected to compaction as detailed in ASTM C109 (ASTM C 109 -07, 2007). Table 1 gives the mixture proportion of the com-
posites prepared in the study. The cube specimens were initially preserved at elevated temperatures of 40 °C, 80 °C and 100 °C respec-
tively for a period of 96 h. Subsequently, the blocks were permitted to cool down, and the maximum unconfined compressive strength
(UCS) was determined. The mix design giving the optimal strength development was further investigated at ambient curing tempera-
ture, and the UCS established after 7, 14, 28, 54, and 90 days, correspondingly. To ensure the reproducibility of results, three speci-
mens were tested for each mixture.
Selected samples were tested through wet and dry cycles to determine the durability of the composite bricks obtained as per ASTM
D559-2003. Wet and dry cycle trials was performed by immersing the block sample inside water for a duration of 24 h and thereafter
oven dried it for another 24 h at 60 °C. The same procedure ware done 10 times, while determining the compressive strength of the
block sample every time when the process was repeated.

2.5. TCLP
TCLP was utilized to establish the environmental impact of the composite bricks. Sodium hydroxide and acetic acid at 20:1 liquid-
solid ratio and pH 4.93 ± 0.05 was used to extract the crushed material (Yu et al., 2016). The process extraction was carried out us-
ing a thermostatic shaker, and shaking was done for 24 h at 25±2 °C. To determine the content of heavy metal in the filtrate, atomic
absorption spectroscopy (AAS) was utilized.

2.6. Analytical techniques

Mineralogical study was executed by using SHINGAKU diffractometer with the parameters set to 40 kV and 40 milliamp current
using visible-radiation CuK energy with a wavelength of 0,154,056 1 × 10⁻⁹ m. A dispersive X-ray (XRF) spectrometer equipped was
utilized to establish the chemical composition of the sample. The scan was at the rate of 0.017o/s over the 2θ array of 4-100o. A Shi-
madzu's FTIR 8400 spectrometer was used for the analysis. Potassium bromide (KBr) pellet method was utilized to analyse the sam-
ples. Optical-instrument examinations were carried out by making use of a Scanning electron microscope (SEM) joined EDS detector.

Table 1
Mix proportions of WFGD gypsum/Fly ash brick composites.

Sample ID WFGD gypsum (wt%) Fly ash (wt%) Water (wt%)

WFGD 100 0 18.5

80WFGD:20FA 80 20 18.1
70WFGD:30FA 70 30 16.4
60WFGD:40FA 60 40 15.8

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3. Results and discussion

3.1. Physico-chemical properties of the raw materials
3.1.1. pH and relative density
Fig. 1 illustrate density and pH values of raw material WFGD gypsum, FA and the resulting WFGD: FA composites. It was deter-
mined that the density of WFGD gypsum was 2.43 g/cm3 and 2.3 g/cm3 for FA. The replacement of WFGD gypsum by FA had a negli-
gible effect on the density of the composites. This observation is reasonable because the density values for both materials are almost
identical. The pH of WFGD gypsum and FA was 7.2 and 10.8, respectively. Fig. 1 illustrate that cumulative content of FA from 20 to
40 wt% resulted to an increase in the pH of the composites from 7.8 to 8.8. It is worth noting that the basic pH obtained in the com-
posite materials is advantageous to strength development as it could favor a faster dissipation of reactive Silicon dioxide (SiO2) and
Aluminium oxide (Al2O3)from raw materials, leading to higher CSH and ettringite content in the binding process (Little, 1998), (Jafer
et al., 2018), (Zhu et al., 2017). These outcomes are comparable to those described in the literature for pH and relative density of sim-
ilar materials (Falayi et al., 2016), (Raghavendra et al., 2002).

3.1.2. Chemical and mineralogical composition

Chemical composition of WFGD gypsum and FA are shown of Table 2. The most abundant oxides of the WFGD gypsum were cal-
cium oxide (50.51%) and sulfur trioxide (44.55%), while FA consisted mainly of silicon dioxide (44.98%), aluminium oxide
(20.34%), iron oxide (14.6%) and calcium oxide (5.13%). FA was categorized as Class F due to 79.92% total amount of Al2O3, SiO2,
and Fe2O3 present in it (ASTM C618 -05, 2005).
Fig. 2 displays the morphology pattern (XRD) of WFGD gypsum and FA. Evidence of primary Mullite, Quartz, and Hematite
crystalline phases were observed on the FA sample. Whereas WFGD gypsum mainly consisted of Gypsum, Calcium di-aluminate
and Coesite. Ca-rich minerals were not detected in the FA sample, suggesting that such phases are contained in the amorphous
phase. Note that FA comprises crystal-like and ambiguous phases with a specific reactivity in alkaline conditions (Chancey et al.,
2010). The presence of amorphous phase in the FA sample is illustrated by the small bump between 10 and 40° (2θ) as indicated
on Fig. 2 (Li et al., 2015).

Fig. 1. Density and pH of FA, WFGD gypsum and the resulting WFGD: FA composites.

Table 2
Chemical compositions of the WFGD gypsum and FA.

Oxides (wt%) WFGD Gypsum Fly ash

F 0.25 –
MgO 0.71 1.60
Al2O3 0.71 20.34
SiO2 1.48 44.98
P2O5 0.01 0.41
SO3 44.55 1.68
Fe2O3 0.60 14.60
CaO 50.51 5.13
TiO2 0.12 1.72
MnO 0.41 0.24
SiO2 + Al2 O3 + Fe2O3 2.79 79.92

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Fig. 2. XRD patterns of WFGD gypsum and fly ash.

3.1.3. SEM
The microstructure analysis (SEM) of raw WFGD gypsum and FA are illustrated in Fig. 3. WFGD gypsum consisted of coarse parti-
cles with prismatic and laminar shape. FA is composed of particles of varying sizes and shapes. The regular shape is mainly composed
of cenospheres and plerospheres, while the irregular shaped particles are related to crystalline minerals and unburnt carbon (Nath
and Kumar, 2019).

3.1.4. Particle size distribution

The particle size dispersal of FA and WFGD gypsum are demonstrated in Fig. 4. It is worth noting that utmost particle of FA and
WFGD gypsum were between 0.1 and 1000 μm with mean diameters (d50) of 50.4 and 30.7 μm, respectively. Note that finer particles
have a higher reactivity and packing effect, which may promote the development of strength (Kroehong et al., 2011), (Ding and
Zhang, 2014). The higher the particle size, the lesser the chances that FA and WFGD solid particles would interacts with its surround-
ings. However, the lesser the particle size, the surface area per unit volume increases. Thus, the higher the specific surface area, good
material size dispersal and good mix of pozzolanic oxides enhances the UCS (Kroehong et al., 2011), (Ding and Zhang, 2014).

3.1.5. Maximum dry density (MDD) and optimum moisture content (OMC)
Table 3 shows the MDD and OMC results of WFGD gypsum, FA and resulting WFGD:FA composites. The results displayed
that MDD of WFGD gypsum was 1425 kg/m3 and OMC was 18.5%,. The incorporation of FA to WFGD gypsum decreased both
the MDD and OMC of the resulting composite materials. The reduction of MDD and OMC with addition of FA is due to an in-
crease in the particle packing effect (Ding and Zhang, 2014). In fact, the sphere-shaped fine FA particles may contribute to infill
the voids and reduce the compacted materials' porosity (Ogundiran and Kumar, 2016). This led to better compaction and ab-
sorption of less water.

Fig. 3. SEM microstructure analysis of FA (a) and WFGD gypsum (b).

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Fig. 4. Particle size distribution of FA and WFGD gypsum.

Table 3
MDD and OMC of FGDG and resulting WFGD:FA composites.

Sample ID WFGD gypsum (wt%) FA (wt%) MDD (kg/m3) OMC (wt%)

WFGD 100 0 1425 18.5

80WFGD:20FA 80 20 1396 18.1
70WFGD:30FA 70 30 1307 16.4
60WFGD:40FA 60 40 1263 15.8

3.2. Characterization of composites bricks

3.2.1. The impact of curing temperature on UCS
Fig. 5. Gives UCS outcomes of WFGD:FA composite bricks cured at various curing temperature. Heat treatment was employed to
speed up the hardening process in order to select the optimal mixture of WFGD and FA. It can be seen that 0 to 40 wt% partial re-
placement of WFGD gypsum by FA resulted in strength reduction of the composite sample. Additionally, cumulating the curative
temperature adversely affected the UCS of the corresponding mixture. For example, the strength of the 80WFGD:20FA composite
decreased by 20% while the cumulating curing temperature increased from 40°C to 100 °C. The control mixture exhibited the high-
est UCS of 2.3 MPa. In fact, Ca2+ and SO42− ions generated from WFGD gypsum were expected to react with Al2O3 and SiO2 com-
ing from fly ash during hydration of the WFGD:FA composite mixture, resulting in the formation of binding products for example
ettringite and CSH and good strength development (Telesca et al., 2013), (Lebedev, 2015). Due to the relatively low compressive
strengths of WFGD:FA composite bricks, FA used in the study may be considered to have low pozzolanic activity and thus acted pri-
marily as filler materials (Gupta and Chaudhary, 2020). The curing temperature of 40 °C and 20 wt% level of replacement seemed
suitable for the preparation of WFGD:FA composite bricks.
The decrease in UCS is related to the low development of hydration products in the WFGD:FA blended system. It must be noted
that the pH values in all of the composite material were less than 12.5, which is the minimum pH at which a greater extent of the hy-

Fig. 5. UCS of WFGD:FA composite bricks at various curing temperature.

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dration process of FA, also known as pozzolanic reaction, is expected (Eades and Grim, 1960; Zeng et al., 2012). The pH is a signifi-
cant parameter in cementitious materials because it impacts solubility characteristics, hydration processes, and the durability of hard-
ened products (Galan et al., 2021). In fact, as the pH exceeds 12.5, the SiO2 and Al2O3 tetrahedral crosslinked network of FA is easily
destroyed, resulting in the formation of reactive Al2O3 and SiO2 species and a significant rise in the proportion of hydration products
(Bui et al., 2015), (Zeng et al., 2012). On the other hand, upon curing at high temperatures, voids and cracks are formed due to water
evaporation, which could also contribute to strength reduction (Salvador, 2016; Little et al., 2002).

3.2.2. The effect of curing time on UCS

Fig. 6 demonstrates how longstanding curing impacts the UCS of WFGD:FA composite block. Only the 80WFGD: 20FA mixture
was further investigated as it gave optimal UCS. It was determined that curing at ambient temperature would be best to lower the en-
ergy needs of curing. A longer curing duration had a beneficial impact on the strength evolution of 80WFGD:20FA composite bricks.
A decline in the UCS was observed after 56 days of ambient curing. This decrease in compressive strength could be related to the for-
mation of expanse ettringite crystals. The continual development of these crystals generates internal tensions, which can cause the
material to crack and deteriorate (An et al., 2022), (Gadalla et al., 1990). Similar strength reversal was observed for phosphogypsum-
based binder with a curing period above 28 days (Gadalla et al., 1990). It was observed that when the curing duration was extended
by up to 90 days, saw a gain of as much as 53.8% UCS increase. An ultimate strength of 2 MPa was reached after a 90-day curing
time. The longer curing led to an increase in presence of the C–S–H compound (hydrated product) and ettringite in the binder phase
(Salvador, 2016), (Little et al., 2002). A pozzolanic reaction takes place gradually whenever Ca(OH)2 and H20 present during the re-
action (An et al., 2022), (Ma et al., 2020). Moreover, Hemalatha et al. (Gadalla et al., 1990) stated that fly ash (Class F) exhibited a
slow pozzolanic reaction and that their contribution to strength development mainly occurred at a later age. The composite bricks'
highest UCS of 2 MPa exceeds the minimum requirements as defined by SANS 10145 for Class III mortar WFGD:FA of 1.5 MPa for
composite bricks that may be employed as building materials. (Xu and Deventer JSJ Van, 2000).

3.2.2.1. Mineralogy. Fig. 7 gives XRD patterns of WFGD gypsum and fly ash and 80WFGD:20FA composite. The spectrum of the
80WFGD:20FA composite showed that after the hydration reaction, the peak intensity of gypsum in the raw materials decreased.
This indicates that this mineral was partially consumed during the hydration process. However, most of the pre-existing minerals
appeared to be chemically inert and behave mainly as filler material. Minerals, such as quartz, Coesite, and mullite, are often
weakly reactive under alkaline conditions. (Xu and Deventer JSJ Van, 2000), (Kumar et al., 2017). Moreover, no new crystalline
phases were identified in the XRD spectra of the 80WFGD:20FA composite. The latter observation suggests that the hydrated prod-
ucts were present in a negligible amount. These results agree with the low strength development observed in the WFGD:FA blended
system.

3.2.3. SEM/EDS analysis

Fig. 8 gives the SEM micrograph and EDS spectrum of 80WFGD:20FA composite. The material displayed a compact microstruc-
ture indicating that WFGD gypsum and FA particles were finely intermixed. It was identified that the spherical particles in the binder
phase were unreacted FA, indicating that these phases were hardly dissolved during hydration. The EDS spectrum of the
80WFGD:20FA composite showed that the predominant elements in the binder matrix were Al, Si, Ca, K, and S.

3.2.4. Durability
3.2.4.1. TCLP. Table 4 gives the leaching results of WFGD gypsum and 80WFGD:20FA composite bricks. The presence of Fe, Cu,
Mn, Cr, and Mg heavy materials proportion was observed to be higher in the composite material in comparison with control mix-

Fig. 6. UCS of 80WFGD:20FA composite bricks at various curing time.

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Fig. 7. XRD analysis of WFGD gypsum, FA and 80WFGD:20FA composite (G = Gypsum, CD= Calcium di aluminate, C= Coesite, Y= Yitrium, Q = Quartz, H=
Hematite, M = Mullite).

Fig. 8. SEM micrograph (a) and EDS spectrum (b) of 80WFGD:20FA composite.

Table 4
TCLP of composite bricks.

Element (% m )
m
WFGD 80WFGD:20FA

Fe 2.8 5.3
Cu 1.56 1.98
Mg 1.50 1.1
Mn 0.47 1.1
P 0.19 0.23
Al 0.08 0.03
Cr 0.01 0.15

ture. The quantity of each element found in the leachate are under the minimum leachable concentration limits for Cd, Mn, Pb, Fe,
Al, Cu, and Mg in drinking water, as per SAN 241. (SANS 241-1 -2015, 2015).

3.2.4.2. Wet-dry cycles. Fig. 9 gives the influence of wet-dry cycles on the UCS of WFGD gypsum and 20FA:80WFGD composite
preserved for up to a period of 90 days. The compressive strength reduced progressively with the number of cycles for all the sam-
ples. However, the strength loss of 20FA:80WFGD composite is higher than that of the WFGD specimen. The minor increase in
strength between the 3rd and 5th cycles may be attributed to the rehydration of gypsum that had been dehydrated during the pre-
ceding cycles (Zhou et al., 2014). Similarly, Ahmed et al. (Ahmed and Ugai, 2011) reported that stabilized soil-gypsum-cement
could gain additional strength during wet-dry cycles. After the 5th cycles, both specimens had a minimum strength of 1.5 MPa,

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Fig. 9. Variation of UCS with wet-dry cycles.

which is the minimum required strength range for Class III mortar, as per SANS 10145 (SANS 10145 -18, 2018). All of the speci-
mens were water resistant for up to 7 cycles. The 20FA:80WFGD collapsed in water after 10 cycles, but the control sample main-
tained a UCS of 0.6 MPa. The latter observation confirms the low formation of hydration products in the WFGD:FA blended sys-
tem and that FA used in this study was poorly reactive.

4. Conclusion
The potential of using FA to stabilize WFGD gypsum was studied. FA was employed to partly substitute WFGD gypsum in the mak-
ing of FA:WFGD composite building blocks. Curing at high temperatures was used to accelerate hardening, and the durability proper-
ties of the optimal composite mixture were also examined. The succeeding inferences can be made:
1. Partially substituting WFGD gypsum with FA saw a decreased in both the MDD and OMC of the resulting composite materials.
2. Increasing the FA content from 20 to 40 wt% had a insignificant impact on the density of the composite material and increased
its pH from 7.8 to 8.8.
3. The strength results showed that from 0 to 40 wt% partial replacement of WFGD gypsum by FA led to the strength reduction of
the composite material. However, using a curing temperature of 40 °C at a 20 wt% level of replacement seemed to be suitable
for the preparation of WFGD:FA composite bricks.
4. Subsequent 90 days duration of curing at ambient temperature, the UCS archived in the 80WFGD:20FA composite was
comparable to that of the control mixture. FA used in this study was poorly reactive but extending curing duration by up to 90
days at ambient temperature saw a gain of as much as 53.8% UCS of the 80WFGD:20FA composite.
5. With the increased number of wet-dry cycles, UCS reduced gradually for all the specimens. However, the strength loss of the
composite 20FA:80WFGD is more than that of the WFGD specimen. After the 5th cycles, both specimens had minimum strength of
1.5 MPa, which meets the minimum strength requirement for Class III mortar, as per SANS 10145.
6. Given the relatively low performance of the composite material produced, it is recommended that the reactivity of FA and
WFGD be altered before use by methods such as mechanical, thermal, physical separation and chemical activation.

CRediT authorship contribution statement

Thandiwe Sithole: Supervision, Conceptualization, Data curation, Writing – original draft, and revision. Tebogo Mashifana:
Supervision, Conceptualization, Data curation, Writing – original draft, and revision. Dumisane Mahlangu: Methodology, Investi-
gation, Data curation. Léonel Tchadjié: Validation, revision, Writing – review & editing.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to
influence the work reported in this paper.

Data availability
No data was used for the research described in the article.

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T. Sithole et al. Sustainable Chemistry and Pharmacy 31 (2023) 100913

Acknowledgements
The authors would like to thank the University of Johannesburg (URC) grant number:2022URC00378 and the National Research
Foundation of South Africa for the financial support, Grant Unique Numbers: BAAP200512521382 and 121885

References
Ahmed, A., Ugai, K., 2011. Environmental effects on durability of soil stabilized with recycled gypsum. Cold Reg. Sci. Technol. 66, 84–92. https://doi.org/10.1016/
j.coldregions.2010.12.004.
An, Q., Pan, H., Zhao, Q., et al., 2022. Strength development and microstructure of recycled gypsum-soda residue-GGBS based geopolymer. Construct. Build. Mater.
331, 127312. https://doi.org/10.1016/j.conbuildmat.2022.127312.
Astm C 109 -07, 2007. Compressive strength of hydraulic cement mortars (using 2-in . or [ 50-mm ] cube specimens). Am Soc Test Mater 1–9.
ASTM C618 -05, 2005. Standard specification for coal fly ash and raw or calcined natural pozzolan for use in concrete. Am Soc Test Mater 1–3.
Bui, P.T., Ogawa, Y., Nakarai, K., Kawai, K., 2015. A study on pozzolanic reaction of fly ash cement paste activated by an injection of alkali solution. Construct. Build.
Mater. 94, 28–34. https://doi.org/10.1016/j.conbuildmat.2015.06.046.
Chancey, R.T., Stutzman, P., Juenger, M.C.G., Fowler, D.W., 2010. Comprehensive phase characterization of crystalline and amorphous phases of a Class F fl y ash.
Cement Concr. Res. 40, 146–156. https://doi.org/10.1016/j.cemconres.2009.08.029.
Córdoba, P., 2015. Status of Flue Gas Desulphurisation (FGD) systems from coal-fired power plants: overview of the physic-chemical control processes of wet limestone
FGDs. Fuel 144, 274–286. https://doi.org/10.1016/j.fuel.2014.12.065.
D6913/D6913M 17, 2017. Standard test methods for particle-size distribution (gradation) of soils using sieve analysis. Am Soc Test Mater 1–35. https://doi.org/
10.1520/D6913.
Ding, X., Zhang, L., 2014. A new contact model to improve the simulated ratio of unconfined compressive strength to tensile strength in bonded particle models. Int. J.
Rock Mech. Min. Sci. 69, 111–119. https://doi.org/10.1016/j.ijrmms.2014.03.008.
Duan, S., Liao, H., Cheng, F., et al., 2018. Investigation into the synergistic effects in hydrated gelling systems containing fly ash, desulfurization gypsum and steel slag.
Construct. Build. Mater. 187, 1113–1120. https://doi.org/10.1016/j.conbuildmat.2018.07.241.
Eades, J.L., Grim, R.E., 1960. A quick test to determine lime requirements for lime stabilization. Highw. Res. Rec. 5, 61–72.
Eskom SOC LTD, 2020. Restoring Trust.
Falayi, T., Okonta, F.N., Ntuli, F., 2016. The geotechnical and microstructural properties of desilicated fly ash lime stabilised expansive soil. Mater. Struct. 49,
4881–4891. https://doi.org/10.1617/s11527-016-0831-7.
Gadalla, A.M., Saylak, D., Lindner, A.I., 1990. Comparison of strength development in waste industrial gypsum produced by the hemihydrate and dihydrate processes.
J. Am. Ceram. Soc. 73, 2255–2260. https://doi.org/10.1111/j.1151-2916.1990.tb07585.x.
Galan, I., Müller, B., Briendl, L.G., et al., 2021. Continuous optical in-situ pH monitoring during early hydration of cementitious materials. Cement Concr. Res. 150,
106584. https://doi.org/10.1016/j.cemconres.2021.106584.
Garg, M., Jain, N., 2010. Waste gypsum from intermediate dye industries for production of building materials. Construct. Build. Mater. 24, 1632–1637. https://doi.org/
10.1016/j.conbuildmat.2010.02.029.
Gupta, S., Chaudhary, S., 2020. Use of fly ash for the development of sustainable construction materials. In: New Materials in Civil Engineering. INC, pp. 677–689.
Jafer, H., Atherton, W., Sadique, M., et al., 2018. Stabilisation of soft soil using binary blending of high calcium fly ash and palm oil fuel ash. Appl. Clay Sci. 152,
323–332. https://doi.org/10.1016/j.clay.2017.11.030.
Kampala, A., Horpibulsuk, S., Prongmanee, N., Chinkulkijniwat, A., 2014. Influence of wet-dry cycles on compressive strength of calcium carbide residue – fly ash
stabilized clay. J. Mater. Civ. Eng. 26, 633–643. https://doi.org/10.1061/(ASCE)MT.1943-5533.0000853.
Koralegedaraa Nadeesha, H., Pintob, P.X., Dionysiouc, D.D., Al- Abed, S.R., 2019. Recent advances in flue gas desulfurization gypsum processes and applications – a
review. J. Environ. Manag. 251, 109572. https://doi.org/10.1016/j.jenvman.2019.109572.Recent.
Kroehong, W., Sinsiri, T., Jaturapitakkul, C., Chindaprasirt, P., 2011. Effect of palm oil fuel ash fineness on the microstructure of blended cement paste. Construct. Build.
Mater. 25, 4095–4104. https://doi.org/10.1016/j.conbuildmat.2011.04.062.
Kumar, S., Mucsi, G., Kristály, F., Pekker, P., 2017. Mechanical activation of fly ash and its influence on micro and nano-structural behaviour of resulting geopolymers.
Adv. Powder Technol. 28. https://doi.org/10.1016/j.apt.2016.11.027.
Lebedev, A.L., 2015. Kinetics of gypsum dissolution in water. Geochem. Int. 53, 811–824. https://doi.org/10.1134/S0016702915070058.
Lei, D.-Y., Guo, L.-P., Sun, W., et al., 2017. Study on properties of untreated FGD gypsum-based high-strength building materials. Construct. Build. Mater. 153, 765–773.
https://doi.org/10.1016/j.conbuildmat.2017.07.166.
microstructure and compressive behavior of fly ash/phosphate geopolymer hollow sphere structuresLi, R., Wu, G., Jiang, L., Sun, D., 2015. Interface microstructure and
compressive behavior of fly ash/phosphate geopolymer hollow sphere structures. Mater. Des. 65, 585–590. https://doi.org/10.1016/j.matdes.2014.09.063.
Little, D.N., 1998. Evaluation of Structural Properties of Lime Stabilized Soils and Aggregates. National Lime Association Arlington, VA.
Little, T.A., Holcombe, R.J., Ilg, B.R., 2002. Kinematics of oblique collision and ramping inferred from microstructures and strain in middle crustal rocks, central
Southern Alps, New Zealand. J. Struct. Geol. 24, 219–239.
Liu, S., Liu, W., Jiao, F., et al., 2021. Production and resource utilization of flue gas desulfurized gypsum in China - a review. Environ. Pollut. 288, 117799. https://
doi.org/10.1016/j.envpol.2021.117799.
Ma, Y., Nie, Q., Xiao, R., et al., 2020. Experimental investigation of utilizing waste flue gas desulfurized gypsum as backfill materials. Construct. Build. Mater. 245,
118393. https://doi.org/10.1016/j.conbuildmat.2020.118393.
Nath, S.K., Kumar, S., 2019. Role of alkali concentration on reaction kinetics of fl y ash geopolymerization. J. Non-Cryst. Solids 505, 241–251. https://doi.org/10.1016/
j.jnoncrysol.2018.11.007.
Ogundiran, M., Kumar, S., 2016. Synthesis of fly ash-calcined clay geopolymers : reactivity, mechanical strength, structural and microstructural characteristics.
Construct. Build. Mater. 125, 450–457. https://doi.org/10.1016/j.conbuildmat.2016.08.076.
Park, H., Jeong, Y., Jun, Y., Oh, J.E., 2016. Production of price-competitive bricks using a high volume of stone powder sludge waste and blast furnace slag through
cementless CaO activation. Construct. Build. Mater. 122, 343–353. https://doi.org/10.1016/j.conbuildmat.2016.06.088.
Raghavendra, S.C., Raibagkar, R.L., Kulkarni, A.B., 2002. Dielectric properties of fly ash. Bull. Mater. Sci. 25, 37–39.
Salvador, R.P., 2016. Accelerated Cementitious Matrices: Hydration, Microstructure and Mechanical Strength.
SANS 10145 -18, 2018. Concrete masonry construction. South African Bur Stand 1–33.
SANS 241-1 -2015, 2015. Drinking water Part 1 : microbiological , physical , aesthetic. South African Bur Stand 1–17.
Sithole, N.T., Mashifana, T., 2020. Geosynthesis of building and construction materials through alkaline activation of granulated blast furnace slag. Construct. Build.
Mater. 264, 120712. https://doi.org/10.1016/j.conbuildmat.2020.120712.
Tan, K., Pu, X., 1998. Strengthening effects of finely ground fly ash, granulated blast furnace slag, and their combination. Cement Concr. Res. 28, 3–8.
Tchadjie, L.N., Ekolu, S.O., 2018. Enhancing the reactivity of aluminosilicate materials toward geopolymer synthesis. J. Mater. Sci. 53, 4709–4733. https://doi.org/
10.1007/s10853-017-1907-7.
Tchadjié, L.N., Djobo, J.N.Y., Ranjbar, N., et al., 2016. Potential of using granite waste as raw material for geopolymer synthesis. Ceram. Int. 42, 3046–3055. https://
doi.org/10.1016/j.ceramint.2015.10.091.
Telesca, A., Marroccoli, M., Calabrese, D., et al., 2013. Flue gas desulfurization gypsum and coal fly ash as basic components of prefabricated building materials. Waste
Manag. 33, 628–633. https://doi.org/10.1016/j.wasman.2012.10.022.
Xu, H., Deventer Jsj Van, 2000. The geopolymerisation of alumino-silicate minerals. Int. J. Miner. Process. 59, 247–266. https://doi.org/10.1016/S0301-7516(99)
00074-5.

10
T. Sithole et al. Sustainable Chemistry and Pharmacy 31 (2023) 100913

Yang, J., Zhang, Q., He, X., et al., 2022a. Low-carbon wet-ground fly ash geopolymer activated by single calcium carbide slag. Construct. Build. Mater. 353, 129084.
https://doi.org/10.1016/j.conbuildmat.2022.129084.
Yang, J., Tang, Y., He, X., et al., 2022b. An efficient approach for sustainable fly ash geopolymer by coupled activation of wet-milling mechanical force and calcium
hydroxide. J. Clean. Prod. 372, 133771. https://doi.org/10.1016/j.jclepro.2022.133771.
Yu, D., Zhou, J., Shu, Z., Wang, Y., 2016. High-strength, cement-free concrete of flue gas desulfurization gypsum-based non-fired brick. ACI Mater. J. 113, 745–752.
https://doi.org/10.14359/51689239.
Zeng, Q., Li, K., Fen-Chong, T., Dangla, P., 2012. Determination of cement hydration and pozzolanic reaction extents for fly-ash cement pastes. Construct. Build. Mater.
27, 560–569. https://doi.org/10.1016/j.conbuildmat.2011.07.007.
Zhou, J., Yu, D., Shu, Z., et al., 2014. A novel Two-step Hydration Process of preparing cement-free non-fired bricks from waste phosphogypsum. Construct. Build.
Mater. 73, 222–228. https://doi.org/10.1016/j.conbuildmat.2014.09.075.
Zhu, F., Hou, J., Xue, S., et al., 2017. Vermicompost and gypsum amendments improve aggregate formation in bauxite residue. Land Degrad. Dev. 28, 2109–2120.

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