Developments in the Built Environment 14 (2023) 100153

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Developments in the Built Environment

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Thermal behaviour, microstructural changes and mechanical properties of

alkali-activated volcanic scoria-fired waste clay brick blends
Cyriaque Rodrigue Kaze a, b, *, Lynn Myllyam Beleuk à Moungam b,
Jordan Valdès Sontia Metekong b, Thamer Salman Alomayri c, Abdolhossein Naghizadeh d,
Leonel Tchadjie d
a
Department of Minerals Engineering, School of Chemical Engineering and Mineral Industries (EGCIM), University of Ngaoundéré, P.O. Box 454, Ngaoundéré Cameroon,
Cameroon
b
Laboratory of Materials, Local Materials Promotion Authority, MINRESI/MIPROMALO, P.O. Box 2396, Yaoundé, Cameroon
c
Department of Physics, Faculty of Applied Science, Umm Al-Qura University, P.O. Box 715, Makkah, 21955, Saudi Arabia
d
Department of Engineering Sciences, University of the Free State, South Africa

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

Keywords: The present work aims at producing volcanic scoria (Zg) based geopolymer containing high volume of waste fired
Volcanic scoria clay brick (WB). The objective was producing Zg-based geopolymer incorporating WB powders up to 50 wt% and
Waste clay fired brick then investigated a potential thermal stability. All formulated samples were prepared with sodium silicate made
NaOH
from rice husk ash and 6 M of an aqueous NaOH solution. The first series of consolidated geopolymer samples
Rice husk ash
Geopolymer
were cured at 25 ◦ C, while the second ones were exposed to high temperatures of 400, 600 and 800 ◦ C. The
Thermal behaviour specimens were subjected to mechanical performance, physicochemical and microstructural properties evalua­
Mechanical properties tion. The results indicated that incorporating the WB positively influenced the physicochemical performances of
Microstructure geopolymers. Sample prepared with 10 wt% of WB gave highest mechanical property (33 MPa) at 600 ◦ C. The
use of WB favoured the densification and strength development of end products in the range of 25–600 ◦ C.

1. Introduction process of Zg – based geopolymer biner is the main advantage in terms of

Alkali-activated materials are obtained from a mixture of an alumi­
nosilicate material or iron silicate materials (such as fayalite slag from
non-ferrous metallurgical processes) with an alkaline activator at rela­
tively low temperatures below 100 ◦ C (Rahier et al., 1996, 2007;
Davidovits, 1991; Adediran et al., 2021, 2022, 2023). The synthesized
alkali-activated materials develop high strength, good durability in
extreme conditions (acid or salt) and better thermal stability or fire
resistance than ordinary Portland in similar conditions (Tome et al.,
2021; Djobo et al., 2017; Firdous et al., 2018; Boum et al., 2020; Kaze
et al., 2022; Naghizadeh and Ekolu, 2022). Volcanic scoria (Zg) is a
sub-product of magma’s cooling after a volcanic eruption. Zg has a
honeycomb structure, considered a natural amorphous aluminosilicate
material due to its relative reactivity even without thermal activation, as
observed for clayey materials (Djobo et al., 2017; Firdous et al., 2018;
Brown et al., 2012). The absence of heat treatment in the production
energy efficiency and environmental impact, as reported by Leonelli
et al. (2007). Furthermore, Zg is widely distributed worldwide and can
be mined at a low cost (Leonelli et al., 2007). Based on these enormous
advantages, Zg was used as the solid precursor for geopolymer binder,
mortars and concretes with high mechanical performance and thermal
stability (Djobo et al., 2017; Firdous et al., 2018; Lemougna et al., 2018;
Robayo-Salazar and Mejía de Gutiérrez, 2018; Alraddadi and Assaedi,
2020; Alraddadi et al., 2020). Previous studies showed that using sec­
ondary materials such as metakaolin, slag, biomass ashes, laterite etc.
blended with Zg in the production of geopolymer binders was beneficial
for developing strong matrix and performance (Tome et al., 2021;
Lemougna et al., 2020a; Beleuk à Moungam et al., 2021; Sontia Mete­
kong et al., 2021; Tchakoute Kouamo et al., 2012; Baenla et al., 2019). In
the aforementioned studies, Zg was replaced with secondary materials at
different dosages, while the synthesized composite materials were cured
at low temperature. Limited studies were conducted on Zg-based

* Corresponding author. Department of Minerals Engineering, School of Chemical Engineering and Mineral Industries (EGCIM), University of Ngaoundéré, P.O. Box
454, Ngaoundéré Cameroon, Cameroon.
E-mail address: kazerodrigue@gmail.com (C.R. Kaze).

https://doi.org/10.1016/j.dibe.2023.100153
Received 6 December 2022; Received in revised form 4 March 2023; Accepted 23 March 2023
Available online 28 March 2023
2666-1659/© 2023 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
C.R. Kaze et al. Developments in the Built Environment 14 (2023) 100153

geopolymers subjected to high temperatures. For instance, Lemougna Table 1

et al. (2011) replaced volcanic ash with sand up to 40 wt% and the Mix proportions and heat-treatment temperatures of geopolymer pastes.
synthesized products were heated between 25 and 1000 ◦ C. It was re­ Mix ID Volcanic Waste fired clay Alkaline Heating
ported that an increase in compressive strength, reaching 30 MPa at scoria (Zg) bricks (WB) solution temperature
1000 ◦ C attributable to changes in phases occurring within the matrix. ZgWB0 1000 g 0 500 g 25, 200, 400 and
Despite the reduced mechanical performance, all the geopolymer sam­ 800 ◦ C
ples were thermally stable with better characteristics compared to those ZgWB10 900 g 100 g 500 g 25, 200, 400 and
made using Portland cement under similar conditions. The production of 800 ◦ C
ZgWB20 800 g 200 g 500 g 25, 200, 400 and
commercial sodium silicate, which is a key component of geopolymer 800 ◦ C
production at high scale, presents a significant challenge due to the high ZgWB30 700 g 300 g 500 g 25, 200, 400 and
energy requirements associated with heating a mixture of quartz sand 800 ◦ C
and sodium carbonate to 1300 ◦ C. Several researchers have addressed ZgWB50 500 g 500 g 500 g 25, 200, 400 and
800 ◦ C
this issue by producing sodium silicate from soda pellets and reactive
silica obtained from rice husk ash and waste glass, which can be used as
activators for the synthesis of geopolymers with acceptable properties their thermal stability. The applied heating calcination rate and holding
for engineering applications (Tchakouté et al., 2016; Kamseu et al., time were 5 ◦ C/min and 2h, respectively for the heat treatment. The
2017). In Cameroon, as in other parts of the world, rice industries details of mixed powders and synthesized geopolymer formulations are
generate tons of rice husks that are typically disposed of by dumping into given in Table 1.
the environment, thereby causing pollution. In some cases, these husks
are used as fertilizers in agriculture or burned by the local population for 2.3. Solubility
cleaning pots. One of the objectives of this study was to valorize this
agricultural waste (rice husk ash) by using it in the production of The dissolution test methods were used to assess the reactivity of the
low-cost and low-energy silicate. powders (labelled Zg, ZgWB10, ZgWB20, ZgWB30 and ZgWB50). Each
The current study aims to evaluate the thermal stability of geo­ powder weighed three (3) grams, and 35 mL of sodium hydroxide
polymer made from widely available Zg in Cameroon blended with WB (NaOH) 8 M solution was added to the polypropylene container.
at various proportions of 0, 10, 20, 30 and 50 wt%. The synthesized Following that, the various Zg, ZgWB10, ZgWB20, ZgWB30 and
composite materials were exposed at temperatures ranging from 25 to ZgWB50 samples in the beaker were preheated for 30 min with an
800 ◦ C. The structure of synthesized geopolymer products was assessed electric heating plaque at the three curing temperatures of 20 ◦ C. A
by X-ray diffraction (XRD). While the mechanical and physical proper­ centrifuge was used to stir the mixture at 1500 rpm for 6 h at 20 C. To
ties were evaluated by means of flexural strength, water absorption, separate the residue from the remaining solution, a centrifuge was used.
porosity and bulk density. To assess the transformation of mineral A 0.50 mm paper filter was used to filter each sample. The elemental
phases during the thermal treatment, scanning electron microscope composition of the obtained filtrate after dissolution was determined for
(SEM) coupled with EDS was used. each sample using inductively coupled plasma optical emission spec­
troscopy (ICP-OES) equipment Optima 2000 DV (Perkin Elmer, Wal­
2. Experimental program tham, MA, USA). The percentage of dissolved Si, Al, and Fe in each
mixture would be determined by this analysis.
2.1. Materials
2.4. Characterization techniques
Zg used as the main solid precursor was collected from Galim, lo­
cality situated in Cameroon’s west region. While the waste fired clay The chemical compositions of both solid precursors were determined
brick was collected at MIPROMALO factory located in Yaoundé town in using XRF. For this purpose, each sample was mixed with lithium
Centre region. Both materials were oven-dried for 48 h, then crushed borated salt and then vitrified within a Pt crucible at 1050 ◦ C. Loss on
and sieved through 80 μm sieve, prior to their use in geopolymer mix­ ignition (L.O.I) was determined by heating the sample to 1050 ◦ C. All
tures. The alkaline solution was obtained by mixing 6 M of an aqueous elements are analysed on a fused bead. The WD-XRF used was a Rigaku-
NaOH solution with appropriated amount of reactive silica from rice Primus IV, equipped with a Rh tube, operated using ZXS software.
husk ash (RHA), according to previous study (Kamseu et al., 2017). RHA The mechanical performance was assessed with an Instron® 1195
powder to NaOH solution mass ratio was kept at 0.56. The silica to alkali compressive testing machine at a constant displacement rate of 0.5 mm/
silica oxide of the activator solution was fixed at SiO2/Na2O equal to 1.6 min. The flexural strength test results were the average of five
and H2O/Na2O equal to 10. measurements.
XRF analysis took place in order to obtain the compositions of the
2.2. Geopolymers mixture preparation calcined and non-calcined raw materials. Samples were milled in a same
manner as those prepared for XRD analysis. Loss on ignition (L.O.I) was
Before preparing the geopolymer products, Zg powder was hand determined by heating the sample to 950 ◦ C, after which a portion of the
mixed with waste fired clay brick at different dosages of 0, 10, 20, 30 sample is fluxed, and a bead is moulded. A 4 kW WD-XRF Rigaku-Primus
and 50 wt%. Hence, the prepared alkaline solution was mixed with each IV was used for analysis with a Rh tube.
formulation for 5 min in a laboratory mortars mixer with a constant solid SEM analysis conducted to study the methodology both raw mate­
precursor to alkaline solution mass ratio of 0.5, in order to obtain rials as well as synthesized geopolymers. A portion of the original
acceptable workability. The fresh geopolymer paste was poured into samples were placed on double sided carbon tape on a glass section and
prismatic moulds of 140 mm × 10 mm × 10 mm dimensions. The carbon coated using a Quorum Q150 sputter coater. A Jeol JSM 6610
moulded samples were compacted using an electrical vibrating table for Scanning Electron Microscope equipped with an EDS (JED-2300 EDS)
5 min, then sealed with a thin plastic bag and kept at room temperature detector, was used for analysis. The accelerating voltage of the filament
(24 ± 3 ◦ C) until mechanical tests were performed at 28 days. The paste is run at 20 kV.
samples were labelled ZgWB0, ZgWB10, ZgWB20, ZgWB30 and
ZgWB50, based on their WB proportions of 0, 10, 20, 30 and 50%,
respectively. All the formulated samples were cured for 28 days and then
subjected to high temperatures treatment at 200, 400 or 800 ◦ C to assess

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C.R. Kaze et al. Developments in the Built Environment 14 (2023) 100153

Fig. 1d. Dissolution rate of Al, Si and Fe from ZgWB0, ZgWB10, ZgWB20,
Fig. 1a. X-ray patterns of volcanic scoria (b) and waste fired clay bricks (a).
ZgWB30 and ZgWB50 samples at 20 ◦ C.

3. Results and discussion

3.1. Characterization of raw materials

Fig. 1b. Particle size distribution of volcanic scoria (Zg), waste fired clay brick
(WB) and rice husk ash (RHA).
Fig. 1c. Particle size distribution of ZgWB0, ZgWB10, ZgWB20, ZgWB30 and
ZgWB50 Samples.
Fig. 1a–b displays the XRD patterns of Zg and WB used as raw ma­
terials. It can be seen that Zg (Fig. 1a) mineralogy comprised crystalline
phases such as Augite (Ca(Mg, Fe)Si2O6, JCPDS no. 00-024-0203),
Forsterite (SiMg1.8Fe0.2O4, JCPDS no. 01-072-2461), Anorthite (CaN­
aAl2Si2O8, JCPDS no. 00-009-0465) and Nepheline
(K0.7Na2.75Ca0.15Al3.75Si4.25O16, JCPDS no. 04-012-7095). The major
crystalline phases of WB (Fig. 1a) were Quartz (SiO2, JCPDS no. 01-075-
8320), Hematite (Fe2O3, JCPDS no. 04-003-1445) and Kaolinite
(Al2Si2O5(OH)4, JCPDS no. 00-058-2006). However, the firing of the
bricks was carried out in an artisanal kiln, so the firing was not uniform,
which would justify the presence of kaolinite peaks on the diffractogram
of WB ((Fig. 1a). The absence of kaolinite peaks on the diffractograms of
the geopolymers (Figs. 3–6) implies that this mineral would have been
altered after alkaline activation and would therefore be less crystallised.
The chemical composition of Zg and WB as determined by XRF
analysis are 42.68, 11.93 and 12.69 wt% and 57.73, 23.65 and 10.73 wt
% respectively for SiO2, Al2O3 and Fe2O3 as major oxides contained in
volcanic scoria and waste fired clay bricks (Table 2). The other elements
in trace only contained in Zg were Na2O (4.01 wt%), CaO (2.59 wt%),
MnO (9.32 wt%) and MgO (11.6 wt%). While the specific surface values
are 0.96 and 10.53 m2/g, respectively for Zg and WB powders. For Zg
the average particles d10, d50 and d90 were 1.22, 11.10 and 67.40 μm,
whereas for WB, they were 4.01, 28.0 and 151.0 μm, respectively
(Fig. 1b–c). For ZgWB10, ZgWB20, ZgWB30 and ZgWB50 the average
particles d10, d50 and d90 were 1.91, 14.11 and 71.40 μm; 2.12, 17.10
and 72.21 μm; 3.52, 19.10 and 75.11 μm; 4.02, 21.10 and 79.01 μm.
The dissolution of Zg, ZgWB10, ZgWB20, ZgWB30 and ZgWB50
powders in 8 M of NaOH solution is reported in Fig. 1d. In general it is
noticed that incorporating the waste fired clay powders (WB) improved
the reactivity of Zg. This is demonstrated by low solubility of Al, Si and
Fe recorded on Zg compared to ZgWB10, ZgWB20, ZgWB30 and
ZgWB50 powders. The recorded values are 3, 8 and 10 wt% respectively
for Fe, Al and Si from Zg. For samples containing 10, 20, 30 and 50% of
WB powders, the solubility of Fe, Al and Si are 5, 12 and 18 wt%; 6, 19,
and 27 wt%; 7, 26 and 31 wt%; 7, 35 and 42 wt%, respectively for
ZgWB10, ZgWB20, ZgWB30 and ZgWB50 samples. The emergence of
the amorphous phase may have favoured the dissolution by releasing
more Si, Al, and Fe as a result of the increase in dissolved Si, Al, and Fe
elements in the mixture. Increased reactivity during the

3
C.R. Kaze et al.
Fig. 2. Appearance of geopolymer products heated at (a) 25, (b) 400 and
(c) 800 ◦ C.
geopolymerization process is known to favor higher dissolution, which
leads to superior strength development.
3.2. Geopolymer materials
3.2.1. Visual aspect of geopolymer specimens
The photographs of unheated and heated synthesized geopolymer
products are represented in Fig. 2. For the unheated sample (Fig. 2a) the
colour is dark and became dark brown with the incorporation of WB
powder. The reddish colour of geopolymer is due to iron minerals like
hematite that have influenced the colour of geopolymer products. This
change colour upon heating in all geopolymer samples could be attrib­
utable to the transition state of iron atom (Fe3+ to Fe2+ vice versa)
(Nazari et al., 2017; Bernal et al., 2014). When the calcination reached
800 ◦ C all samples exhibit light grey colour and micro fissures on their
surface (Fig. 2c). The micro fissures imply the degradation of amorphous
phase with increased temperature into crystalline phase attributable to
the possible beginning of sintering. In addition, these naked micro fis­
sures appearing on the surface of samples containing WB powders could
be attributed to the release of water out geopolymer matrix weakening
the structure and explaining the decrease in mechanical properties.
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Developments in the Built Environment 14 (2023) 100153
Fig. 3. Geopolymer samples prepared at ambient temperature: (a) ZgWB0, (b)
ZgWB10 and (b) ZgWB50.
Fig. 4. Geopolymer samples calcined at 400 ◦ C: (a) ZgWB0, (b) ZgWB10 and
(b) ZgWB50.
3.2.2. Phase evolution
Figs. 3–6 show the XRD patterns of selected geopolymer samples
treated at different temperatures. It can be seen that no new crystalline
phases were formed after geopolymerization, as evidenced by the
absence of new peaks in specimens cured at room temperature
(Fig. 3a–c). It is well known that the structure of the major binding
matrix in geopolymer is comparable to that of synthetic or natural
crystalline zeolites, although it is predominantly amorphous at ambient
curing temperatures (Rahier et al., 1996). The diffraction peaks of
Quartz present in sample ZgB50 (Fig. 3c) are due to a higher proportion
of waste clay bricks in that binder mixture compared to samples ZgWB0
(Fig. 3a) and ZgWB10 (Fig. 3b).
Geopolymer samples heated at high temperatures of 400 ◦ C
(Fig. 4a–c) and 600 ◦ C (Fig. 5a–c) showed new peaks at 19 and 29⁰ (2-
theta), associated with the formation of Pigeonite ((Fe0.253Mg0.747)
(Fe0.755Mg0.124Ca0.12)Si2O6, JCPDS no. 01-078-5152). The weak
diffraction peak of Antigorite (Mg24Si17(OH)31O42.5, JCPDS no. 01-089-
7423) at 12.4⁰ (2-theta) was observed in the sample ZgWB50 (Fig. 5c)
after calcination at 600 ◦ C, suggesting that WB (Fig. 1a) contained a
C.R. Kaze et al. Developments in the Built Environment 14 (2023) 100153

the geopolymer matrix during thermal treatment at high temperatures

usually reduces the amount of amorphous phase and causes volume
change, resulting in a degradation of mechanical properties [()].

3.2.3. Mechanical properties

Fig. 5. Geopolymer samples calcined at 600 ◦ C: (a) ZgWB0, (b) ZgWB10 and
(b) ZgWB50.
Fig. 7 highlights the flexural strength of unexposed (25 ◦ C) and
heated samples containing 0, 10, 20, 30 and 50 wt% of WB. Overall, it
was noticed that the increased WB content up to 50 wt% improved the
flexural strength from 4.56 to 13.0 MPa and 15.0–23.02 MPa for samples
cured at 25 ◦ C and 400 ◦ C, respectively. Thus, incorporating WB powder
was beneficial and favourable in reinforcement of geopolymer matrices
heated up to 400 ◦ C. This densification could be related to synergetic
effect of Zg/WB ensuring better equilibrium between components.
However, all the samples heated at 600 ◦ C exhibits a slight increase from
21 to 34 MPa, respectively for samples ZgWB0 and ZgWB10, followed by
a decrease from 34 to 17 MPa from samples containing 20, 30 and 50 wt
%. Such improvement could be attributed to beginning of sintering
related to the physico chemical transformation occurring within the
geopolymer matrix. The decreased performance in samples ZgWB20,
ZgWB30 and ZgWB50 heated at 600 ◦ C could be either attributed to
intrinsic properties of solid precursor or interfacial zone and surface of
Zg-WB particles within the powders which are less stable when heating
at high temperature (Lemougna et al., 2020b). Nevertheless, further
studies need to be conducted to assess this change. However, after
exposure at 800 ◦ C, it observed a drastically decrease in flexural strength
in all the formulated geopolymer samples containing WB powder.
Nevertheless, the recorded mechanical strength values in all geo­
polymer composites are higher than that of the specimens cured at
25 ◦ C. This reduction in mechanical performance is in agreement with
the appearance of fissures observed on these samples as seen in Fig. 2c.
Similar observation was reported in literature where the authors
investigated the thermal stability of geopolymer using metakaolin and
fly ash (Kamseu et al., 2012; Rashad and Ouda, 2019; Nobouassia Bewa
et al., 2018; Nikolov and Karamanov, 2022). These studies associated
the formation of micro fissures after exposure to high temperatures
caused by the alteration or degradation of geopolymer network

Fig. 6. Geopolymer samples calcined at 800 ◦ C: (a) ZgWB0, (b) ZgWB10 and
(b) ZgWB50.

mixture of Antigorite and Kaolinite. In fact, Antigorite and kaolinite are

clays minerals of the kaolin-serpentine group with a similar crystalline
structure classified as 1:1 type (Davidovits, 1991). Furthermore, when
the calcination temperature was increased to 800 ◦ C, the XRD patterns
of ZgWB0 (Fig. 6a) and ZgWB50 (Fig. 6b) revealed the presence of the
reflection peaks of Leucite (KAlSi2O6, JCPDS no. 01-076-8733) with the
intensity of the peaks decreasing as the proportion of WB in the mixture
increased.
Similarly, the formation of a substantial amount of Leucite was
previously reported in metakaolin-based geopolymer paste during
thermal treatment at 800 ◦ C and was correlated with enhanced re­
Fig. 7. Flexural strength of geopolymers heated at 25, 200, 400 and 800 ◦ C.
fractory properties [()]. It is important to note that the crystallization of

Table 2
Chemical composition of raw materials (L.O.I = loss on ignition).
Samples SiO2 Al2O3 K2O Na2O Fe2O3 P2O5 TiO2 CaO MnO MgO L.O.I

Waste fired clay brick (WB) 57.73 23.65 0.10 – 10.73 0.16 1.65 0.12 0.02 – 4.59
Volcanic scoria (Zg) 42.68 11.93 1.60 4.01 12.69 0.61 2.59 9.32 0.19 11.6 − 0.10
Rice husk ash (RHA) 88.01 0.53 2.01 – – 1.05 – 0.55 – – 5.40

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C.R. Kaze et al. Developments in the Built Environment 14 (2023) 100153

Fig. 8. Scanning electron microscopy features of geopolymer made using volcanic ash (Zg) alone as the raw material: a – without exposure to elevated temperature,
b – exposed to 400 ◦ C, c – exposed to 800 ◦ C.

Fig. 9. Elemental analysis of geopolymers made using 100% volcanic ash (Zg) as the raw material exposed to a - 400 ◦ C and b - 800 ◦ C.

responsible to better cohesion and densified structure (Bakharev, 2006;
Elimbi et al., 2014; Kuenzel et al., 2012). Thus, heating the consolidated
geopolymers at high temperature can lead to release of “hydroxyl water”
from geopolymer network upon firing inducing the progressive modi­
fication within the geopolymer structure resulting in less compact and
densified structure (Kamseu et al., 2012; White et al., 2010; Tiffo et al.,
2020; Duxson et al., 2007; Assaedi et al., 2016).
3.2.4. Microstructure
Fig. 8 shows the SEM features of geopolymers made using 100% Zg
as the raw material. It can be seen that as-prepared pastes containing
100% Zg as raw material (Fig. 8a) show a relatively denser binder matrix

6
C.R. Kaze et al.
Fig. 10. Scanning electron microscopy features of geopolymers made using 50% volcanic ash (Zg) and 50% brick waste (WB) as the raw material: a, b – without
exposure to elevated temperature, b, c – exposed to 400 ◦ C, d, e – exposed to 800 ◦ C.
compared to those that were exposed to elevated temperatures at 400 ◦ C
(Fig. 8b) or 800 ◦ C (Fig. 1c). Exposure of 100% Zg geopolymers to an
elevated temperature at 400 ◦ C (Fig. 8b) led to extensive cracking
throughout the binder matrix. An increase in heat–treatment tempera­
ture from 400 C to 800 ◦ C resulted in severe cracking and disintegration
in the binder (Fig. 1c). Similar observations were reported in other
studies (Vickers et al., 2014; Naghizadeh et al., 2020). The observed
damage in geopolymer pastes due to their exposure to elevated tem­
perature can be attributed to dehydration of the hardened binder
network during the heat-treatment process. Other mechanisms, such as
the polymorphic transition of quartz, partial oxidation of the amorphous
iron etc., may also contribute to the adverse strength loss of geopolymer
binders exposed to elevated temperature (Temuujin et al., 2011)
{Alraddadi, 2022 #2; Tayeh et al., 2022 #1}. Fig. 9a and b give the
elemental analysis of the 100% Zg geopolymer paste exposed to 400 ◦ C
and 800 ◦ C, respectively. It can be seen that the binders give typical
geopolymer chemical compositions containing Si, Al, and O along with
K, Na and Ca elements. Variation in the heat–treatment temperature did
not result in any significant change in the composition of the binders.
Figs. 10a–3f show the SEM features of geopolymer pastes that were
prepared using 50% Zg + 50% WB as the raw materials. It can be seen
that the as-prepared Zg/WB geopolymer pastes (Fig. 10a and b) contain
WB particles with darker colours and relatively rounded shapes, along
with Zg particles with the lighter colour, relatively angular shapes, and
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Developments in the Built Environment 14 (2023) 100153
smoother edges. In the case of Zg/WB geopolymer pastes subjected to
heat treatment at 400 ◦ C (Fig. 10c and d), some WB particles have
transformed to glassy morphology. In contrast, there is no similar
transformation in unreacted Zg particles. An increase in the heat-
treatment temperature up to 800 ◦ C promoted the formation of glassy
phases within the binder (Fig. 10e and f).
Furthermore, Zg/WB samples exposed to elevated temperatures
(Fig. 3c and e) have a relatively denser binder network with very little
micro-cracking compared to those prepared using only Zg and exposed
to high temperatures (Fig. 8b and c), regardless of the heat-treatment
temperatures. The observed improvement in the physical properties of
geopolymer paste upon their exposure to elevated temperature can be
attributed to the transformation of unreacted WB particles. Where
unreacted WB particles transformed to a gel-like substance during the
heat treatment, filling the gaps and cracks caused by dehydration of
geopolymer binder. As a result, the formation of a denser binder network
of heat-treated Zg/WB geopolymers (Fig. 10c and e) led to improved
mechanical performance than the heat-treated Zg geopolymers (Fig. 8b
and c). These observations are consistent with the compressive strength
results presented in the foregone.
Fig. 11a and b shows the elemental analysis of transformed WB
particles in the Zg/WB geopolymer paste exposed to 400 ◦ C and 800 ◦ C,
respectively. It can be seen that the glassy phase formed through the
transformation of WB particles has similar compositions to those of
C.R. Kaze et al.
Fig. 11. Elemental analysis of geopolymer made using 50% volcanic ash (Zg) and 50% brick waste (WB) as the raw material exposed to a - 400 ◦ C and b - 800 ◦ C.
Fig. 12a. Water absorption of unheated (25 ◦ C) and heated (400, 600 and
800 ◦ C) geopolymers containing 0, 10, 20, 30 and 50 wt% of WB.
geopolymer gel. However, quantitative elemental analysis shows that
formed glassy phases in geopolymer binder have relatively higher Si/Al
ratios ranging from 2.7 to 3.22, while this ratio in geopolymer gel was
between 1.72 and 2.07 (data collected from EDS analysis).
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Developments in the Built Environment 14 (2023) 100153
3.2.5. Physical properties
Fig. 12a presents the results of water absorption recorded on un­
heated and heated samples immersed in water for 24 h. From Fig. 12 it is
observed that incorporating WB up to 50 wt% reduced the water ab­
sorption of geopolymer samples heated between 25 and 400 ◦ C. The
corresponding values decreased from 12.50 to 8.30% and 10.12 to 8.31,
respectively. Such reduction on samples heated at 400 ◦ C is likely
related to the chemical transformations occurring upon heating that
reinforced and densified the geopolymer matrix resulting in few open
accessible voids. Whereas, for the samples cured at 25 ◦ C incorporating
the WB powders increased the reactive phase content releasing more Si-
and Al-oligomers in alkaline medium favourable for the high poly­
condensation and extended the geopolymer network justifying the
strength development. Such increase in mechanical strength is a logical
consequence of densified structure with enough produced geopolymer
binder ensuring better cohesion alongside the matrix with less open
voids (Kljajević et al., 2017; Wang et al., 2015). Heating the geo­
polymers from 600 to 800 ◦ C, led to increase in water absorption values
from 8.30 to 11.30% and 11.10–15.70%, respectively. The recorded
reduction in water absorption is related to denaturation of geopolymer
binder upon heating that weakened the structure and lead appearing the
open voids favourable for the retention of water once samples are
immersed in water for the measurements. Similar observation was
previously reported in the literature when the consolidated geopolymers
were heated at high temperatures up to 1000 ◦ C (White et al., 2010;
Tiffo et al., 2020; Naghizadeh et al., 2020; Walkley et al., 2018; Chen­
g-Yong et al., 2017; Khater and Gharieb, 2022). The mentioned studies
have reported that heat-treatment of geopolymer products at high
C.R. Kaze et al.
Fig. 12b. Porosity of unheated (25 ◦ C) and heated (400, 600 and 800 ◦ C)
geopolymers containing 0, 10, 20, 30 and 50 wt% of WB.
Fig. 12c. Bulk density of unheated (25 ◦ C) and heated (400, 600 and 800 ◦ C)
geopolymers containing 0, 10, 20, 30 and 50 wt% of WB.
temperatures resulted in crystallization of the disordered geopolymer
binder inducing the formation of crystalline phases such as nepheline
and sodalite.
A similar trend was recorded on porosity of geopolymer specimens
(Fig. 12b). for the geopolymer samples treated between 25 and 400 ◦ C,
the values decreased from 24 to 16% and 20.12 to 17.05%, respectively.
Such reduction is consistent with development of compact and dense
structure with less fissures and open voids within the matrix. When
heating the geopolymer specimens between 600 and 800 ◦ C, the
porosity values increased from 15 to 22% and 21–30%, respectively.
This increase in porosity and water absorption justifies the fact that
increasing the heating temperature above 400 ◦ C results in the alteration
of geopolymer network followed by the formation of open voids and
micro cracks within the geopolymer matrix, as confirmed by the SEM
analysis (Fig. 10). However, the low values of water absorption
(Fig. 12a) and porosity (Fig. 12b) recorded on geopolymer samples
ZgWB10 and ZgWB20 heated at 600 ◦ C are in line with the high
strengths achieved (Fig. 7). This suggests the formation of densified
structure due to the beginning of sintering allowing the chemical
transformation upon heating which appear beneficial for the strength
development.
9
Developments in the Built Environment 14 (2023) 100153
Fig. 12c gives a plot of bulk density of unexposed (25 ◦ C) and heat-
treated (at 400, 600 and 800 ◦ C) geopolymer samples labelled ZgWB0,
ZgWB10, ZgWB20, ZgWB30 and ZgWB50, respectively. The results
indicate that, the bulk density of all geopolymers showed an increase
with the rise of heating temperature up to 600 ◦ C. This might be linked
to improvement of geopolymerization process with rising in tempera­
ture to 600 ◦ C along with the incorporation of WB powders. Heating the
geopolymer samples at high temperature would have favoured the
creation of an excessive number of hydration products, which build up
in the hardening pastes’ pore system and raise bulk density (Tchakouté
et al., 2017; Nana et al., 2021). The bulk density of the samples heated at
25, 400 and 600 ◦ C, increased from 1.70 to 1.80 g cm− 3, 1.80–1.85 g
cm− 3 and 1.93–1.98 g cm− 3, respectively. The improvement in the bulk
density values of the geopolymer products containing WB is attributable
to the WB’s fine particle size, WB powder has a surface area (10.53
m2/g) that fills the pores between paste particles and the aluminosili­
cates hydrate gel, causing a more uniform and dense microstructure to
form a homogenous and denser structure thermally stable up to 600 ◦ C.
the decrease in bulk density of the samples that were heated at 800 ◦ C
from 1.93 to 1.90 g/cm− 3 is related to alteration of geopolymer matrix
resulting in open voids and micro fissures that made the samples less
heavy in comparison with those heated up to 600 ◦ C (Alraddadi and
Assaedi, 2022; Tayeh et al., 2022).
4. Conclusion
The present work evaluated the effect of waste fired clay brick (WB)
collected from MIPROMALO factory, on thermal and microstructural
properties of volcanic scoria (Zg) - based geopolymer heated up to
800 ◦ C and the following conclusions could be drawn:
• Incorporating the WB powders in Zg-geopolymers enriched the sys­
tem with more reactive phase by promoting more Al- and Si-
oligomers, resulting in high polycondensation ensuring by the
strength development.
• The inclusion of WB in Zg improved the reactive phase and me­
chanical properties in the mixture by increasing the geopolymer
binder justifying the high performance achieved on samples heated
from 25 to 400 ◦ C.
• The high flexural strength of about 33 MPa was achieved on sample
ZgWB10 made with 10 wt% of WB and exposed at 600 ◦ C, however,
the higher temperature of 800 ◦ C was found to be detrimental to the
mechanical performance in all the composite samples.
• Regardless the performance achieved the geopolymer composites
were found to be thermally stable upon heating, suggesting their
suitability for use as low-grade refractories and in potential building
applications. But there is a need to complete the investigation with
thermal properties (TG/DTA and dilatometry).
Cyriaque Rodrigue Kaze conceptualization, Investigation, data
Formal analysis, writing—original draft, writing—review and editing.
Lynn Myllyam Beleuk à Moungam:, writing—review and editing. Sontia
Metekong valdez Jordan:, writing—review and editing. Thamer Salman
Alomayri: writing—review and editing. Abdolhossein Naghizadeh:
Investigation, data Formal analysis, writing—original draft, wri­
ting—review and editing. Leonel Tchadjie: investigation, data Formal
analysis, writing—original draft, writing—review and editing.
Funding
Not applicable.
Ethics approval and consent to participate
Not applicable.
C.R. Kaze et al.
Consent for publication
Not applicable.
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
The authors do not have permission to share data.
Acknowledgements
The authors extend their appreciation to the Department of Engi­
neering Sciences, University of the Free State, South Africa, for running
all the analysis in this project.
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