Construction and Building Materials 309 (2021) 124974

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Construction and Building Materials

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

Delithiated 𝛽−spodumene as a geopolymer precursor

A. Karrech a ,∗, M. Dong a , J. Skut b , M. Elchalakani a , M. Shahin c
a
School of Engineering, Department of Civil, Environmental and Mining Engineering, University of Western Australia, 35 Stirling Hwy, Crawley WA 6009, Western
Australia, Australia
b
Covalent Lithium Pty. Ltd., L18, 109 St Georges Tce Perth WA 6000, PO Box Z5200 St Georges Tce Perth WA 6831, Australia
c
Department of Civil Engineering, Curtin University, Kent Street, Bentley, Perth, 6102, Western Australia, Australia

ARTICLE INFO ABSTRACT

Keywords: There is an increasing demand for lithium, which is perceived as the key element of the green revolution. This
Pozzolan green image remains incomplete without the circular economic uptake of delithiated 𝛽−spodumene (D𝛽S).
Lithium In a recent contribution, the authors proved that D𝛽S has remarkable pozzolanic properties (Karrech et al.,
Waste management
2019). This paper sheds more light on the early-age and long-term behaviour of D𝛽S derived geopolymer by
Recycling
using advanced characterisation tools based on microscopy and spectroscopy along with standard material
By-products
Circular economy
testing. Important new results have been obtained using this campaign; while D𝛽S proved to be an acceptable
geopolymer precursor, flowability and penetration resistance tests proved that it improves workability and
increases initial setting times. The long-term testing proved that embedding D𝛽S produces lower shrinkage,
which indicative of good durability.

1. Introduction
The demand for portable electronic devices that use lithium-ion bat-
teries (LIB) has contributed to increasing the production of lithium sig-
nificantly [1]. Current statistics indicate that batteries consume about
65% of the total production (see Table 1). According to the latest USGS
report [2], Australia is still the largest producer of lithium (54.19% of
the global total), despite the decrease in production recorded in 2019.
The country’s resources occur essentially in hard rock pegmatites that
contain Li-bearing minerals including spodumene. The chemical for-
mula of spodumene is Li2 O ⋅ Al2 O3 ⋅ 4 SiO2 , which indicates about 8%
lithium oxide and 92% or aluminosilicates by mass in ideal scenarios.
In reality, lithium ore is always associated with gangue and the actual
grades are significantly lower than the ideal figure. Spodumene can
be processed in various ways [1] and in Australia, processing plants
typically produce lithium hydroxide along with D𝛽S (essentially alu-
minosilicates and gypsum/limestone) and sodium sulphate (ignored in
this study). Given that Western Australia is expected to produce about
153.0 ktpa (thousand tonnes per annum) of lithium hydroxide, the state
would generate about 1.6 Mt per annum of D𝛽S and other secondary
refinery outputs. According to the latest National Waste Report (2018),
Australia generated 67 million tonnes (Mt) of wastes including 28.8
mineral processing residues, 12.3 Mt of ash from electricity generation
and 1.8 Mt of mining wastes (mainly tailings dams). Western Australia
(WA) generated about 5.18 Mt, which corresponds to the highest waste
production per capita in the country. This means that D𝛽S is expected to
increase the state’s share by 30%, which needs to be managed correctly.
The government is expected to administer this increase through legisla-
tions and policies that regulate the waste management. WA’s strategy
uses a hierarchy that ranks the management procedures according to
their environmental desirability (i.e. avoidance, reuse, recovery, treat-
ment, and disposal). Anticipating these circumstances, we investigate
the potential of D𝛽S as a key precursor for geopolymer, targeting one
of the highest procedures in the management hierarchy.
Recently, Karrech Ha discovered that D𝛽S has relevant pozzolanic
properties. The team synthesised ten mixes and investigated the perfor-
mance of D𝛽S originating from Greenbushes and processed by Tianqi
Lithium Australia Pty. Ltd., fly ash, ground granulated blast-furnace
slag (GGBS), kaolin and metakaolin. The study indicated that the pres-
ence of D𝛽S in geopolymer mixes significantly improved the efficiency
of other binder materials. D𝛽S seemed to reduce micro-cracking by
filling interstitial gaps between sand grains. Our analysis indicated that
this product could effectively retard the setting of geopolymer mixtures.
A mix binder containing 50% D𝛽S and 50% GGBS produced a 28 day
compressive strength of 84.8 MPa. The current study will investigate
similar aspects using D𝛽S originating from Mt Holland and processed by
Covalent Lithium Pty Ltd. The purpose of this exercise is not to provide
a superlative comparison between the delithiated materials of Covalent
and Tianqi (referred to as D𝛽S-C and D𝛽S-T, respectively), but rather
to provide a ‘‘portrait’’ of a typical Western Australian D𝛽S that could
be commercialised in the future.

∗ Corresponding author.
E-mail address: ali.karrech@uwa.edu.au (A. Karrech).

https://doi.org/10.1016/j.conbuildmat.2021.124974
Received 8 June 2021; Received in revised form 3 September 2021; Accepted 16 September 2021
Available online 7 October 2021
0950-0618/© 2021 Elsevier Ltd. All rights reserved.
A. Karrech et al.
Table 1
Use of lithium products in the United States (in percentage), according to the United States Geological Survey report [2].
Year 2011 2012
Batteries 23 27
Ceramics and glass 31 29
Lubricating greases 9 12
Continuous casting mould powders 4 5
Air treatment 6 4
Polymers 4 3
Others 23 20
2. Geopolymer
The term geopolymer was coined by Davidovits [3] to describe the
networks of mineral molecules linked with covalent bounds that form
when raw materials of geological origin (aluminosilicates) react with
alkaline solutions. He [4] indicated that the main geopolymerisation
steps are alkalination (formation of tetravalent Al in the side group
sialate), depolymerisation (attachment of OH to the silicon atom), and
condensation (formation of 3D structure polymers). The resultant paste
cures into a ceramic-like polymer at relatively low temperature (gener-
ally below 100 ◦ C), which justifies its use as a binder for construction.
Geopolymer is often considered a category of Alkali-Activated Materials
(AAM), which has been researched since the early forties [5]. How-
ever, it is believed that the term ‘‘alkali-activated’’ can be misleading
because it can be confused with ‘‘alkali-aggregate reaction (AAR)’’ that
is unacceptable in concrete. Theoretically, any precursor amenable to
alkali activation and containing silica and alumina can form AAM,
but precursors that are exclusively made of silica and alumina such
that the calcium content is low form zeolite-like network structures,
or geopolymer [6]. According to Duxson [7], alternative names such
as inorganic polymer concrete or geocement are often used by some
researchers.
Geopolymer is arguably an ancient construction material that can
be encountered in monuments such as the Egyptian pyramids and the
South American Tiwanaku ruins [8,9], yet its potential for modern
construction is still being explored. Promising applications have been
identified given the unique physical properties of geopolymer related to
its high thermal insulance, fire resistance, strength, and durability [7].
For example, it has been used in buildings for protective coating [10],
fireproofing [11], and thermal insulation [12]. It has also been used
in various industries as alkali bonded ceramic [13] or inorganic ad-
hesive [14]. Geopolymer has the potential to replace plastics that
proved to be detrimental to the environment given their impact on
living species, soil and water. Replacing conventional concrete with
geopolymer reduces greenhouse gas emissions and consumes large
volumes of industrial wastes [3], which indicates that it is a sustainable
construction material.
Low-calcium fly ashes and metakaolins are popular geopolymer
precursors [15]. Fly ash (FA) is an industrial waste generated by coal
fired power plants. It contains a large amount of active aluminosil-
icate and can be obtained for a low cost, or even for free in some
regions in the world. Other geopolymer precursors that have been
considered previously including metakaolin [3], GGBS [16], municipal
solid waste [17], fayalite slag [18], red mud [19], rice hull and husk
ashes [20], silica fume [21], and geothermal silica [22]. Since D𝛽S
shares many physical and chemical properties with FA, the authors
identified it as a potential geopolymer precursor [23]. Traditionally,
geopolymer concrete develops strength very slowly at early stage due
to the lack of calcium content. Heat curing the composite in an oven
at 60◦ –120◦ for an extended period often reaching 24 h is also com-
mon. This method is suitable for producing precast concrete structures,
which applicability depends on size, cost and proximity to designated
location. Early findings suggested that geopolymer generally has com-
parable properties to ordinary Portland cement (OPC) concrete [24],
but more recent progress reported by Wagners Global Services and
AECOM indicate that the ‘‘low shrinkage and heat of hydration as well
Construction and Building Materials 309 (2021) 124974
2013 2014 2015 2016 2017 2018 2019 2020
22 35 31 35 30 46 56 65
30 29 35 32 39 27 23 18
11 9 8 9 8 7 6 5
4 6 6 5 5 4 3 3
4 5 5 5 3 2 2 1
3 5 5 4 5 5 4 3
26 11 10 10 10 9 6 5
as the high tensile strength mean that the material may have technical
advantages over traditional concrete’’ and discussed various projects
where geopolymer has been instrumental [5]. Recently, high strength
fly ash based geopolymer mortar has been produced by Khan [25] at
ambient conditions with the addition of slag. This allowed geopolymer
to cure at room temperature, with sufficient early-age strength to be de-
moulded without damage. However, the use of calcium-rich slag could
fundamentally alter the chemistry of construction materials, as it may
introduce the same problem that ordinary cement composite faces, for
example, the decalcification reaction. Therefore, there is a school of
thoughts suggesting that geopolymer should have some calcium content
to assist in its curing and strength development [26]. It was also found
that calcium gels would not affect the formation of geopolymeric gels
and could coexist with them [27].
Another main constituent that distinguishes geopolymer products
from cement based products is the activator. Traditional activators
are caustic solutions that are commonly available and highly reactive
(including in terms of rate). Qiu et al. [28] investigated the flexural
strength of geopolymer synthesised with alkaline hydroxide solutions
such as NaOH, KOH and Ca(OH)2 with Na2 SiO3 . The activator contain-
ing 10 mol/L NaOH performed best, with the 28 day flexural strength
being 47.1% higher than 10 mol/L KOH and 196.4% higher than the
low concentration (3 mol/L) Ca(OH)2 . Lloyd and Rangan [24] stated
that the combination of NaOH or KOH with Na2 SiO3 or K2 SiO3 was
more effective for activating fly ash geopolymer than using hydroxides
alone. Al-Bakri [29] suggested an activator mixture containing 12 M
NaOH and Na2 SiO3 with a Na2 SiO3 /NaOH ratio of 2.5 as an optimal
solution. A mixture of Na2 SiO3 and NaOH with a ratio by weight of
2.5 was also adopted by [30], which proved to be effective. For mixes
with slag, it has been determined that silicate based activators show the
best performance. It was found that the sodium silicate modulus (Ms =
SiO2 /Na2 O) should be within 1–1.5 [31]. However, the most common
commercially available sodium silicate solutions have Ms values of 2–
3.2, which is higher than the desired values. One of the purposes of
sodium hydroxides is to break the polymer silicate chains and reduce
the Ms to an optimal ratio. Therefore, depending on the combination
of materials used, an optimal Ms could be determined to maximise the
activator efficiency. Recent developments in terms of activators have
been the use of solid activators [32,33]. Solid activators have some
advantages over activator solutions. Firstly, they are safer to handle
when they remain undissolved. Secondly, many types of solid sodium
silicates (sodium metasilicate) have Ms moduli close to 1, which means
that no other preparation is required for geopolymer with slag. Thirdly,
the just-add-water mixing procedure is more in line with the ordinary
cement mixing, thus more convenient and less error-prone. However,
the major drawback is their low solubility in water; not all the solid
particles would dissolve during mixing [34]. This may not be desirable
but can be used to control the rate of reaction. Further studies are
required to corroborate this observation.
Water content plays an important role in the compressive strength of
geopolymer composites. Lloyd and Rangan [24] discovered the inverse
relationship between water-to-geopolymer-solids ratio and compressive
strength. With a water-to-geopolymer-solids ratio ranging from 0.16
to 0.24, the design compressive strength was expected to be dropping
from 60 MPa to 30 MPa while workability improved. Attempts have
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A. Karrech et al. Construction and Building Materials 309 (2021) 124974

been made to improve the workability of geopolymer without sacrific-

ing strength. Superplasticisers can be incorporated to retard the setting
time of geopolymer and improve its workability [33,35]. Naphthalene-
based superplasticiser performs similarly for both Class-F and Class-C
fly ash, but it is slightly more effective than polycarboxylate-based su-
perplasticiser in Class F geopolymer as demonstrated by [36]. Carabba
et al. [37] confirmed the importance of superplasticisers and indicated
that optimum results where obtained at around 1% of solid precursor
by weight. Laskar and Bhattacharjee [38] discovered that superplas-
ticiser dosage has adverse effects on the rheology when the molar
concentration of NaOH exceeds 4%. However, despite the benefits of
better workability and reduced water usage, the inclusion of superplas-
ticisers can have detrimental effects on the composite strength [39].
This is mainly attributed to the complex chemistry of geopolymer: the
highly alkaline condition during mixing is hostile to many types of
superplasticisers. For example, the polymer chains in polycarboxylate-
based superplasticiser can disintegrate in highly alkaline solutions. The
required amount of superplasticiser can be tenfold higher in geopoly- Fig. 1. Particle size distribution of sand , D𝛽S-C , D𝛽S-T , class F fly
mer than in OPC [40]. Attention has been shifted to developing unique ash , and GGBS .
superplasticiser specifically for geopolymer, with limited impact so
far. Different methods to control curing are also being explored, for
example, by taking advantage of the low solubility of metasilicate 3. Characterisation of D𝜷S
solids.
Other recent developments in the realm of geopolymer include This research work focuses on the effect of D𝛽S on the plastic and
the use of fibres to increase strength, toughness and alter the failure hardened behaviour of geopolymer compared to known binder combi-
modes. Ranjbar et al. [41] used polypropylene fibres in geopolymer nations. Apart from D𝛽S, the proposed mixes embed activators (NaOH
and reported that they reduce workability and compressive strength. and Na2 SiO3 ) and additional binders (GGBS and FA). Sodium hydroxide
However, these authors observed that the presence of polypropylene (NaOH) was purchased from Redox and water glass (Na2 SiO3 ) was
fibres improves toughness and flexural strength. In terms of shrinkage, obtained from Coogee Chemicals (both companies are located in Perth,
it was noted that 3% of polypropylene fibres gives optimal perfor- Western Australia). GGBS is used to ensure that mixes can be cured at
mance. A similar experiment carried out at higher temperature (80 room temperature and can reach acceptable strength within 28 days for
to 90 ◦ C) by [42] showed that adding polypropylene fibres improves practical applications. It was acquired from BGC Concrete in Western
ductility. Interestingly, Reed’s team revealed an increase in compressive Australia. FA is Class F, which is a popular geopolymer precursor that is
strength with fibre content for low strength mixes, which may be less costly than metakaolin. It was collected from the Gladstone coal-
attributed to the effect of temperature. In a comparison carried out by fired power plant in Queensland, where it experienced a combustion
Shaikh [43] in terms of flexural strength, steel fibres were found to out- temperature of about 540 ◦ C in the coal boiler. As its name suggests,
perform polyvinyl alcohol fibres. Steel fibres also develop higher bond D𝛽S is obtained from lithium refining plants [1,23].
strength in geopolymers than in OPC, which results in higher deflection,
toughness and ductility at peak load. Ranjbar et al. [44] performed 3.1. Grain size distribution
experiments with copper coated micro steel fibres of 22 mm in length
Fig. 1 shows the particle size distributions of the geopolymer pre-
and 0.2 mm in diameter and showed that those fibres improve both
cursors used in this study, including D𝛽S-T that is presented here as
flexural strength and toughness. The tested specimens failed in a ductile
a reference material, and sand. The sand used in this case has a d50
compressive manner and no improvement in compressive strength was
(diameter at 50% passing) of 300 μm. The binders, by descending order
observed. Ranjbar et al. [45] also tested the inclusion of carbon fibre in
of fineness based on d50 are D𝛽S-T, D𝛽S-C, GGBS, and fly ash. Fig. 2 is a
the geopolymer. Their results indicate that 1% of graphene nanoplatelet
Ferret Triangle used to visually assess the texture classes of the binders
fibres improve the flexural and compressive strength by 1.44 and 2.16
relevant to this study. The figure depicts three textural percentage
times, respectively. However, the high performance gain was based on
values in terms of clay, silt, and sand for each binder and indicates
a weak mix design, which had a compressive strength of 32 MPa and a
to what class each material belongs. As can be seen, D𝛽S-C and D𝛽S-T
flexural strength of 2.8 MPa. The same results may not be reproducible
both belong to the class ‘‘silt loam’’ with a textural distribution of (clay:
for ultra-high strength geopolymer. Organic fibres, e.g. cotton fibre 5%, silt: 40%, and sand: 55%). The figure also shows that both fly ash
and wool, were also investigated. Alzeer and MacKenzie [46] used and GGBS belong to the class ‘‘silt’’ with textural distributions of (23%,
chemically improved wool by removing lipids and fatty acids and 67%, 10%) and (12%, 80%, 7%), respectively. In this study, D𝛽S are
improving the alkali resistance and tensile strength of the fibres. The used as received, without oven drying. It is known that harsh drying
experimental data revealed that those treatments increase the flexural techniques can lead to the removal of water from hydrates, which can
strength by 40%, provide graceful failure and produce better thermal alter the microstructure. However, we measured the moisture content
stability. Alomayri et al. [30] investigated the effect of cotton fibres of D𝛽S-C, according to AS/ZNS 3583.2 [47] and obtained 2%.
on the performance of geopolymer (with and without OPC additives).
By adding cotton fibres to the mix, flexural strength increases by about 3.2. Oxide composition
65% regardless of the level of OPC replacement. The results indicated
that the addition of OPC assists in the formation of calcium-silicate- Table 2 shows the oxide composition of D𝛽S-C, subject of the
hydrate (C-S-H) gels and improves fibre-matrix bonding as well as current study as well as those of D𝛽S-T, FA and GGBS. As expected,
thermal stability. As seen from the above researches, fibres play an D𝛽S-C is rich in aluminium and silicon oxides since Al2 O3 and SiO2
important role in altering failure modes, increasing geopolymer flexural amount to 20.8% and 62%, respectively. Given the spodumene pro-
strength and improving thermal stability. cessing approach used by Covalent, the content in calcium oxide and

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A. Karrech et al. Construction and Building Materials 309 (2021) 124974

Table 2
Oxide analysis of the raw materials.
Material Al2 O3 CaO Fe2 O3 K2 O MgO MnO Na2 O P2 O5 SiO2 SO3 TiO2 Hydration Basicity
% % % % % % % % % % % modulus coefficient
D𝛽S-Covalent 20.8 4.0 1.4 0.6 0.5 0.2 0.6 0.3 62.0 3.9 0.1 0.41 0.05
D𝛽S-Tianqi 23.5 0.3 0.7 0.5 0.2 0.0 0.2 0.2 71.3 0.3 0.1 0.34 0.00
Fly ash 23.9 7.0 7.9 1.0 1.3 0.1 0.4 0.5 55.9 0.3 1.3 0.58 0.10
Slag 3.1 43.2 0.8 0.3 5.5 0.2 0.3 0.0 31.4 4.0 0.6 1.97 1.09

Fig. 3. XRD analysis of D𝛽S; A: Aluminosilicate, Q: quartz, O: Orthoclase, and G:

gypsum/bassanite.

Fig. 2. Ferret’s triangle indicating the textures of D𝛽S (represented by the symbol (◦),
Table 3
D𝛽S-C and D𝛽S-T almost coincide), fly ash (⋆), and GGBS (∗).
Mix designs.
Group A B C
SS:SH ratio 1.5 2 2.5
sulphur trioxide in D𝛽S-C are high compared to D𝛽S-T; they amount Binder 26% 26% 26%
Activator, which consists of:
to 4% and 3.9%, respectively, which suggests the presence of gypsum. 10% 10% 10%
12 M sodium hydroxide solution
An XRD analysis was conducted on D𝛽S-C, which showed that this 4% 3.3% 2.9%
Sodium silicate solution
6% 6.6% 7.1%
aluminosilicate by-product comprised leached pyroxene (62%–63%),
Sand 60% 60% 60%
quartz (18%–20%), gypsum/bassanite (7%–8%), K-feldspar (3%–4%) Water 4% 4% 4%
and other minerals (see Fig. 3). Gypsum (CaSO4 ⋅ 2 H2 O) and Bassanite
(CaSO4 ⋅ 0.5 H2 O) are calcium sulfates that from due to acid neutrali-
sation used in the delithiation process. The existence of gypsum may
4. Development and testing of spodumene-derived geopolymer
provoke the formation of ettringite, which can have an adverse effect
on durability. Fly ash has low amounts of CaO and SO3 compared to
4.1. Mix design
requirement of AS/ZNS 3582.1 [48] specifying the limits at 10% and
3%, respectively. GGBS has low alumina content compared to the limit
A total of 18 mixes were synthesised and compared in this study.
specified in AS/ZNS 3582.2 [49] as 18%. In addition, it contains 43%
The mixes were categorised into 3 groups based on their sodium silicate
CaO, which boosts the geopolymer hardening. Table 2 also contains
to hydroxide ratios (SS:SH), specifically, 1.5, 2 and 2.5. In each group,
the hydration modulus H𝑚 = (Al2 O3 + CaO + MgO)/SiO2 and the
the D𝛽S replaces 0%, 10%, 20%, 30%, 40%, and 50% of the binder.
basicity modulus K𝑏 = (CaO + MgO)/(SiO2 + Al2 O3 ) that are used to
It will be seen that higher fractions of D𝛽S exhibit low strength. The
assess the hydration activity and the basic versus acidic oxides of binder
three groups are shown in Table 3 and mixes were designated by the
materials, respectively. The modulus H𝑚 is usually applied to assess the SS:SH ratio followed by the D𝛽S replacement ratio. For example, 1.5–
activity of slag-based cements, although Wang et al. [50] indicated that 20 means a mix having SS:SH ratio 1.5 and D𝛽S replacement ratio
the correlation between those moduli and strength is not guaranteed. 20%. The binder content, the activator to binder ratio, the amount of
Chang [51] suggested that H𝑚 should exceed 1.4 to ensure adequate water and the quantity of sand were kept consistent in all mixes. The
hydration properties. With its high CaO content, GGBS has the highest geopolymer binder was made up of 80% low calcium fly ash and 20%
hydration activity among the various binders considered in this study. ground granulated blast-furnace slag (GGBS). The D𝛽S replaced both fly
From least to most active, those products can be listed as D𝛽S-T, D𝛽S- ash and GGBS proportionally by the designated amount. The activator
C, FA, and GGBS as shown in the penultimate column of Table 2. In was composed of 12 molar sodium hydroxide solution and the grade
calculating K𝑏 , some oxides of small solid concentrations are omitted H sodium silicate solution mixed at a given ratio. Additional water
(c.f. [52]). The last column of Table 2 indicates that the binders are all accounted for 4% by weight of the total mix to improve the workability
acidic (K𝑏 < 1) except for GGBS which is alkaline (K𝑏 = 1.97 > 1). Basic and prevent flash setting. The sand represented 60% of the mixture by
binders usually develop high strength, while their acidic counterparts weight.
are more difficult to activate and produce low strength [53]. Based on The 12 M sodium hydroxide solution was prepared by mixing
the hydration and basicity moduli, it can be seen that adding GGBS to sodium hydroxide pearls with water. The solution was left covered
the mix is necessary to obtain ambient curing. in ambient temperature for at least 24 h for the exothermic reaction

4
A. Karrech et al.
Fig. 4. Slump flow test of mix 2.0–10.
Fig. 5. Slump flow of the mixes within 15 min after mixing of (a) group A; (b) group B; (c) group C.
to occur and fully cool down. The hybrid activator was prepared
half an hour prior to the mixing, by combining the 12 M sodium
hydroxide, sodium silicate solution and free water. The mixture was
constantly stirred to make sure that the depolymerisation reaction of
sodium silicate was complete. The dry constituents were measured to
the desired quantities and mixed for 3 min in a planetary mixer. The
activator was then added to the dry constituents, and the wet mixing
was timed to be 30 s long before transferring the fresh mortar to the
moulds. The specimens were all demoulded one day after pouring and
placed in the ambient curing room with temperature set to 23 ± 2 ◦ C
and humidity to 95 ± 5%.
5
Construction and Building Materials 309 (2021) 124974
4.2. Behaviour of plastic geopolymer
The plastic behaviour of geopolymer was identified at the early age
using slump and penetration resistance tests. Slump tests are usually
undertaken following the Australian Standard AS 1012.3 to determine
the consistency of fresh geopolymer. In this study, the slump test
was carried out immediately after mixing, then every 2.5 min until
10 min, then the final test at 15 min after the initial test. The mortar
was transferred to the mini slump cone with a bottom diameter of
38 mm. The conducted tests showed that the mortar flows very well in
most cases, therefore the flow (spread) is measured instead of vertical
displacement, as the latter is very high and can be misleading in this
situation. Two measurements at right angles to each other were taken
in each case. Penetration resistance tests were conducted to determine
the setting time, in accordance with AS 1012.18 (AS, 2014). A circular
A. Karrech et al.
Fig. 6. Penetration resistance of (a) group A; (b) group B; (c) group C.
mould was filled with mortar and placed beneath the standard appa-
ratus. A suitable penetration needle was chosen and inserted into the
mortar by 25 mm within 10 s. The force required to push the needle
into the mortar was recorded. Depending on the state of the mortar, a
smaller needle may be selected for the subsequent tests. The subsequent
impressions should be at least 15 mm from previous holes and at least
25 mm from the side of the container. After the test, the penetration
results were converted to MPa and plotted with respect to time.
4.2.1. Slump test
A typical slump flow test is demonstrated in Fig. 4 with mix 2.0–
10. A 15-minute test period was sufficient for all studied mixes. A
substantial reduction in the slump flow with respect to time can be
seen in figure; towards the end of the test (last figure), practically no
slump could be recorded.
The changes in the flow diameter of the 18 mixes are compared in
Fig. 5. The bottom limit of the flow diameter is the bottom diameter
of the slump cone, which corresponds to the situation where no slump
flow can be observed. Fig. 5-(a) shows the slump flow of the six mixes in
group A with an SS:SH ratio of 1.5. The initial flow of the mix without
D𝛽S was the lowest among the six mixes, and reduced rapidly as time
went on. No flow was recorded at 7.5 min after pouring. With 10%
D𝛽S replacement, the flow increased substantially, and the duration it
took to reach no flow was longer. The subsequent mixes with higher
D𝛽S replacement ratios had progressively better workability. The final
mix 1.5–50 had taken twice required for mix 1.5–0 to reach 0 flow.
Fig. 5-(b) shows the slump flow of the mixes with SS:SH ratio 2.0.
D𝛽S replacement again improved the workability of the mixture, and
the most significant improvement was still with a dosage of 10% D𝛽S.
The difference among the mixes was smaller than that in group A.
Fig. 5-(c) shows the slump flow of group C mixes. The plain mix 2.5–0
(without addition of D𝛽S) had higher flow than the other plain mixes
1.5–0 and 2.0–0, discussed above. Again, a replacement of 10% D𝛽S
6
Construction and Building Materials 309 (2021) 124974
was beneficial in improving workability. The workability of the mixes
reduced slightly as the D𝛽S ratio continued to increase, similar to the
trend found in group B mixes. This could be due to the affinity of
gypsum in the D𝛽S to sodium silicate, which may increase the viscosity
of the mixture and influence flowability. As can be seen in Section 3.2,
gypsum/bassanite represent 7%–8% of the total mass of D𝛽S. The 10%
replacement ratio was shown to be the superior option for mixes with
all three SS:SH ratios. The presence of gypsum in alkaline mixes is
known to form ettringite in the form of fine-grained crystals, which
keeps the paste plastic and workable [54]. Gypsum is known to retard
the hydration process and it is usually present in cement as a retar-
dant agent to prevent flash setting during concrete manufacturing and
placing.
4.2.2. Penetration resistance
The penetration resistance test results are plotted in Fig. 6. For
group A mixes, Fig. 6-(a) indicates that the penetration resistance of the
plain geopolymer mortar 1.5–0 exhibited the highest resistance until
shortly before the end of testing. The penetration resistance plateaued
one hour after pouring with a penetration resistance reaching about
25 MPa. As the D𝛽S replacement ratio increased, the penetration re-
sistance decreased, and the duration from pouring to the initial setting
increased drastically. Mix 1.5–10, although hardened at a slower pace
than the control mix, was recorded with a higher penetration resistance
at the end of testing. The gypsum content in the D𝛽S increased the
degree of reaction and resulted in a stronger strength development
than the plain mortar. Mixes with higher D𝛽S replacement ratios had
longer initial setting time, which is beneficial for the transportation and
casting of the mortar. A similar trend could be observed for the group
B mixes, as shown in Fig. 6-(b). The penetration resistance of 2.0–10
went past that of 2.0–0 earlier than the corresponding mixes in group A,
demonstrating the effect of higher sodium silicate concentrations. The
penetration resistance of the mixes with higher D𝛽S contents appeared
A. Karrech et al. Construction and Building Materials 309 (2021) 124974

Fig. 7. Failure modes of the specimens tested at 28 days. Top row: 1.5–0 with horizontal and vertical strain gauges before and after testing showing the shear failure; bottom
row: 1.5–50 before and after testing showing the columnar failure.

Fig. 8. Compressive strengths at different ages.

consistently higher than their corresponding mixes in group A. The group C with the highest sodium silicate concentration shown in Fig. 6-
(c), the penetration resistance results were among the highest. Mixes
effect of D𝛽S in delaying the setting was still evident. For mixes in with 10%–30% D𝛽S surpassed the penetration resistance of 2.5–0 at

7
A. Karrech et al.
Fig. 9. Elastic responses of the group A mixes.
Fig. 10. Total shrinkage after 16 weeks of curing.
the end of testing. The increase in D𝛽S percentages still delayed the
setting of the mortar mixes, although the extent was comparatively less.
It could be seen that the D𝛽S had a positive effect on increasing the
setting time, and improving the strength development when the sodium
silicate content was high. Overall the results complemented the slump
flow test results quite well. A close look into Table 2 shows that the
hydration modulus of D𝛽S is small compared to FA and GGBS. This
explains the slower hydration reaction that occurs in the presence of
D𝛽S and the subsequent improvement of setting time.
4.3. Behaviour of hardened geopolymer
The hardened mechanical behaviour of geopolymer was identified
using Uniaxial Compressive Strength tests, shrinkage tests, X-ray diffrac-
tion (XRD) analysis, and Scanning electron microscopy (SEM)/energy
dispersive spectrum (EDS) analyses.
• Uniaxial Compressive Strength tests were conducted according
to the Australian Standards (AS 1012). At 3, 7, 14, 21 and 28
days after pouring, the specimens were taken out of the ambient
curing room and mounted on a universal testing machine with a
capacity of 600 kN. The loading rate was kept at 20 ± 2 MPa/min
in accordance with AS 1012.9 (AS 1012.9, 2014). For each mix
at a given age, three identical specimens were tested by loading
them axially until failure to identify their Uniaxial Compressive
Strengths (UCS). At 28 days, two strain gauges were applied on
two separate sides of the specimen (one horizontal and one verti-
cal). These strain gauges measured the expansion or contraction
of the mid-section of the specimen. The results were used in
conjunction with the loads recorded by the testing machine to
obtain the elastic moduli and Poisson’s ratios.
8
Construction and Building Materials 309 (2021) 124974
• Shrinkage measurements of the specimens were taken after 16
weeks of curing in a drying chamber. Each specimen used to mea-
sure shrinkage had 25 mm wide square cross-section and 285 mm
length. Humidity was controlled by a saturated sodium bromide
salt bath, which gave a humidity of 65 ± 5%. Temperature was
kept consistent at 23 ± 2 ◦ C. On each end, copper studs were
embedded into the mortar to facilitate its insertion into the gauge.
The length change was compared against the length of a standard
steel rod.
• XRD analysis In this study, the broken pieces after 28 day com-
pression testing were separated from the mortar and sufficiently
dried in an oven. They were then ground to a fine powder in
a mortar and pestle by hand. The powder was analysed in a 2𝜃
angle from 5 to 90◦ , at a rate of 1◦ per minute. For mix 2.0–40,
samples were taken 3 h, 24 h, 7 days and 28 days after pouring to
investigate the transition in the crystallography of the D𝛽S mixes.
• SEM and EDS analyses were used to study the microstructures
and elemental distributions in the geopolymer specimens. The
broken pieces were collected from the remaining mortar after the
28 day compression tests. They were dried and placed onto a
sample stage before coating them with a thin layer of platinum.
The handling and transportation of the samples were through
a fully sealed container to avoid carbonation after coating. The
samples were analysed in a field emission SEM machine. For
selected mixes, thin film samples were prepared by grinding the
sample embedded in hardened resin to a depth of 20–30 μm.
They were then coated with platinum for SEM and EDS analysis.
The elemental compositions were acquired at selected points and
mapped using an EDS probe at selected regions.
4.3.1. Mechanical behaviour
The two typical failure modes are demonstrated in Fig. 7. The high-
strength specimens experienced shear failure, as shown by the two
pyramids left after testing. The strain gauges remained attached until
the peak load was reached. The low-strength specimens, for mixes with
higher D𝛽S replacement ratios or those tested at early ages, showed
a columnar failure mode. Gradually, more and more vertical cracks
appeared around the sides of the specimens, resulting in a ductile and
progressive failure.
The compressive strength of the specimens at different curing ages
are shown in Fig. 8, which reveals that for group A mixes, the strength
hardening slowed down significantly after 21 days of curing in the
ambient room. As the D𝛽S content increased, the compressive strength
reduced. At 10% D𝛽S replacement, the compressive strength was 12%
lower than that of 1.5–0, after 28 days of curing. At a replacement
ratio equal to or greater than 20%, the strength reduced substantially.
The trend continued until it bottomed at 3 MPa after 28 days for mix
1.5–50. For group B mixes in Fig. 8-(b), the strength development after
21 days was slightly higher than that of group A mixes. The 28 day
strengths of 2.0–0 and 2.0–10 were almost identical to 1.5–0 and 1.5–
10, while the group B mixes with higher D𝛽S contents had higher
strengths than the corresponding mixes in group A. The higher silicate
content benefited mixes with higher gypsum contents. For example, mix
2.0–50 had almost tripled the 3 day compressive strength of 1.5–50
and almost doubled the 28 day strength of 1.5–50. Fig. 8-(c) shows the
compressive strengths of group C mixes. The high SS:SH ratio resulted
in a reduction in compressive strengths in the plain mixes, with 2.5–0
having 14% lower 28 day compressive strengths than 1.5–0 or 2.0–0.
However, the 2.5–10 had comparable strengths to 1.5–10 and 2.0–10.
Remarkably, the strengths of 2.5–10 and 2.5–0 remained comparable
throughout the 28 day period, demonstrating the benefit of using D𝛽S
in an environment with high silicate concentrations. The group C mixes
with higher D𝛽S replacement ratio were also much stronger than group
A mixes.
Fig. 9 shows the elastic responses of the specimens in group A. It
could be seen that the differences in the elastic responses with D𝛽S
A. Karrech et al.
Table 4
Elastic properties of the mixes.
1.5–0 1.5–10
Elastic modulus (GPa) 20.7 22.4
Poisson’s ratio 0.31 0.31
2.0–0 2.0–10
Elastic modulus (GPa) 23.46 26.4
Poisson’s ratio 0.26 0.3
2.5–0 2.5–10
Elastic modulus (GPa) 22.75 25.77
Poisson’s ratio 0.23 0.37
replacement ratio up to 30% were relatively small. The behaviour of
1.5–40 and 1.5–50 were distinctly different from those with a lower
D𝛽S content. Table 4 summarises the elastic moduli and Poisson’s ratios
obtained from the strain gauges attached to the 28 day specimens. It
should be noted that due to the square geometry of the specimens,
the Poisson’s ratios may differ from those obtained using cylinders.
However, comparing the different mixes is still useful as it indicates
that the variation of strain ratios with respect to D𝛽S content is con-
sistent with other mechanical properties. The elastic moduli increased
then decreased as the D𝛽S replacement ratio increased from 0%–50%.
This result is consistent with the compressive strength, which followed
a similar variation. The Poisson’s ratio also increased at first, then
decreased with the increase of D𝛽S dosage. The differences in elastic
moduli between the binder and the D𝛽S would likely cause an increased
dilation under shear. At high D𝛽S concentrations, the reduction in the
Poisson’s ratio was likely caused by the increased voids due to a lower
amount of binder, which gave the composite more place to expand
under mechanical loading.
4.3.2. Total shrinkage
Fig. 10 shows the total shrinkage (autogenous and drying shrinkage)
results after 16 weeks in the drying chamber. The differences among the
mixes with different SS:SH ratios were small. However, it was clear that
the addition of the D𝛽S reduced the total shrinkage of the mortar, most
noticeably at higher dosages. As the D𝛽S content increased, the amount
of fly ash and GGBS reduced, which in turn led to a reduction of the
total shrinkage. The aluminosilicate in the D𝛽S could also increase the
interlocking of the aggregates and reduce shrinkage. It is known that
high-MgO binders develop higher autogenous and drying shrinkage
[55,56]. In this case, D𝛽S-C has lower MgO than fly ash and slag, which
explains the observed improvement in total shrinkage.
4.3.3. XRD analysis
Fig. 11-(a) shows the XRD analysis of mix 2.0–40 after curing for
3 h, 1 day, 7 days and 28 days. It can be seen that the mortar is mostly
amorphous, apart from the quartz peaks. Additionally, the calcium-
silicate-hydrate (C-S-H) and calcium aluminosilicate hydrate (C-A-S-H)
gels can also be observed after 7 days of curing, due to the use of
GGBS. The intensity of the aluminosilicate peaks from the D𝛽S did not
vary significantly throughout the 28 days of curing. Gypsum cannot be
observed in any of the samples, even 3 h after mixing. It appears that
gypsum had been fully consumed by the activator within 3 h, which
is consistent with the penetration resistance testing results, where the
hardening rate reduced sharply after 1 h. Fig. 11-(b) shows the XRD
diffractograms corresponding to the six mixes in group A obtained 28
days after pouring. As expected, gypsum cannot be observed in the
mixes after 28 days, including for the mix 1.5–50 with 50% D𝛽S as
the binder. The aluminosilicate peaks had larger intensities in mixes
with higher D𝛽S replacement ratios.
9
Construction and Building Materials 309 (2021) 124974
1.5–20 1.5–30 1.5–40 1.5–50
23.6 19.87 10.3 3.0
0.4 0.33 0.3 0.28
2.0–20 2.0–30 2.0–40 2.0–50
24.66 23.1 16.2 3.99
0.29 0.32 0.37 0.34
2.5–20 2.5–30 2.5–40 2.5–50
28.44 97.6 6.58 4.7
0.38 0.41 0.44 0.37
4.3.4. SEM/EDS analysis
The broken pieces of the specimens recuperated upon uniaxial
testing were used to examine the texture of reaction products. Fig. 12
shows the cementitious material of three mixes with different D𝛽S
replacement ratios in group C. It could be seen that the textures of the
cementitious materials were almost identical. Due to the low fly ash and
GGBS content in 2.0–40, the degree of refinement of the binder to the
cracks and pores was low. Therefore, this mix was more susceptible to
CO2 ingress than mixes with lower D𝛽S dosage. Carbonates were seen
to form near the cracks, indicating the absorption of CO2 into the pore
fluids.
Fig. 13 shows the SEM images of the thin film specimens 2.0–0, 2.0–
30 and 2.0–40. The thin films can be used to study the cross-section
of the binder or aggregate grains, identify the distribution of aggre-
gates in the mortar, and provide a flat surface for EDS analysis. The
backscattered detector was used in the SEM imaging. Heavier elements
appear brighter and lighter elements appear darker in these images.
From this figure, it is immediately seen that the D𝛽S particles are
much finer and fill the gaps between larger sand grains. They appear
much darker than quartz sand, which is primarily made from SiO2,
perhaps due to the processing history that they have gone through
during delithiation. It can be seen that the D𝛽S particles have many
voids. This may explain the reduced compressive strength obtained at
excessive D𝛽S replacement ratios.
Fig. 14 shows the high magnification images of a D𝛽S particle.
It can be seen that the surface of the particle contains microscopic
cracks and voids, which influence its mechanical performance. This
also means that under mechanical loading, D𝛽S particle may experience
local failure and result in the dilation due to internal shear forces.
Fig. 15-(a) depicts the elemental distribution of a thin film taken
from a 2.0–30 specimen at 28 days. Sulphur was detected throughout
the scanned region, which means that a large amount of gypsum
was converted into reaction products by the activator. The obtained
distribution is uniform in the mortar matrix, which indicates an ade-
quate diffusion through the mixture. Fig. 15-(b) shows the elemental
distribution within a 2.0–40 specimen. It can be seen that the amount
of sulphur increased and the distribution remained similar. Even with
a high D𝛽S replacement ratio, which contained a large amount of
gypsum, the activator used for geopolymer synthesis could effectively
convert all gypsum into reaction products. The results are consistent
with the XRD analysis, where gypsum peaks disappeared completely at
28 days even for mixes with 50% D𝛽S replacement in the binder.
5. Conclusion
Geopolymer is gaining acceptance as a sustainable alternative to
conventional construction materials. In addition, the process of lithium
extraction from pegmatites is fairly well understood as indicated in
a literature review by [1]. However, there is a very limited work on
delithiated spodumene and its potential as a supplementary cement-
ing material. D𝛽S in geopolymer is a new concept that the authors
introduced fairly recently [23,54]. While a proof of concept has been
provided in the past, the long term and early age behaviour D𝛽S
based geopolymer have not been investigated in details. This paper is
A. Karrech et al.
Fig. 11. XRD analyses.
essentially to address this gap by characterising D𝛽S and studying the
performance of D𝛽S derived geopolymer. Based on the characterisation
work, if has been shown that D𝛽S belongs is a ‘‘silt loam’’ and the
products of Covalent and Tianqi’s products do not differ much from
this perspective. The results also revealed that D𝛽S has low basicity
and hydration moduli. As for the experimental study of D𝛽S derived
geopolymer, the following conclusions could be drawn:
10
Construction and Building Materials 309 (2021) 124974
• D𝛽S aluminosilicate particles are more porous than sand, which
affects strength at excessively high replacement ratios. How-
ever, replacement ratios up to 10% maintained a relatively high
strength; our experimental data reveal that mixes with SS:SH 2.5
had a similar strength to plain geopolymer mortar.
• The addition of D𝛽S increased the quality of slump flow. This im-
proved workability is important for the future uptake of geopoly-
mer, which is known to flash set and to exhibit low workability.
This study suggested that this improvement of workability is
due to the presence of gypsum in the raw material. The affinity
A. Karrech et al. Construction and Building Materials 309 (2021) 124974

Fig. 12. Microstructure at 28 days of (a) 2.0–0; (b) 2.0–20; (c) 2.0–40.

Fig. 13. Thin film at 28 days of (a) 2.0–0; (b) 2.0–30; (c) 2.0–40.

Fig. 14. Surface texture of the D𝛽S particles.

of gypsum to sodium silicate is known to influence early age mixes with 10% D𝛽S and a SS:SH ratio larger than 2.5 had many
viscosity and flowability. attractive engineering properties, and its utilisation could reduce
• Similarly, the addition of D𝛽S led to longer initial setting times the consumption of fly ash and GGBS.
based on the penetration resistance test results. This is a consid-
erable advantage of D𝛽S because longer initial setting times are CRediT authorship contribution statement
beneficial for the transportation and casting geopolymer mortars.
This study explained the increase in setting time by the slower
A. Karrech: Conceptualisation, Methodology, Homogenisation
hydration reaction that occurs in the presence of D𝛽S. Our data
model, Supervision, Writing – review & editing. M. Dong: Experimen-
indicated that the hydration modulus of D𝛽S is small compared
tal, Data curation, Writing – review & editing. J. Skut: Methodology,
to FA and GGBS.
Validation, Writing – review & editing. M. Elchalakani: Methodology,
• Geopolymer embedding D𝛽S exhibited lower shrinkage than their
Validation, Writing – review & editing. M. Shahin: Methodology,
plain counterparts. Lower shrinkage is significant since excessive
Validation, Writing – review & editing.
shrinkage can cause internal tensile stresses, which may lead to
cracking, internal warping, deflection, and other pathologies even
in the absence of mechanical external loading. Our data indicated Declaration of competing interest
that D𝛽S-C has lower MgO content than fly ash and slag; lower
MgO content explains the lower levels of shrinkage. The authors declare that they have no known competing finan-
• In summary, all the mixes with 10% D𝛽S also had superior cial interests or personal relationships that could have appeared to
workability than their respective control mixes. The geopolymer influence the work reported in this paper.

11
A. Karrech et al.
Fig. 15. Elemental mapping at 28 days using EDS.
References
[1] A. Karrech, M.R. Azadi, M. Elchalakani, M.A. Shahin, A.C. Seibi, A review on
methods for liberating lithium from pegmatities, Miner. Eng. 145 (2020) 106085,
[2] USGS, Mineral Commodity Summaries 2020, United States Geological Survey,
Virginia, 2020.
[3] J. Davidovits, Polymère Mineral, French Patent application 7922041 (8018970).
[4] J. Davidovits, Geopolymer Chemistry and Applications, Geopolymer Institute,
2008.
[5] J.M. Aldred, J. Day, Is geopolymer concrete a suitable alternative to traditional
concrete? in: 37th Conference on Our World in Concrete & Structures, 2012.
[6] P. Krivenko, Why alkaline activation – 60 years of the theory and practice of
alkali-activated materials, J. Ceram. Sci. Technol. 8 (3) (2017) 323–334.
[7] P. Duxson, A. Fernández-Jiménez, J.L. Provis, G.C. Lukey, A. Palomo, J.S.J. van
Deventer, Geopolymer technology: The current state of the art, J. Mater. Sci. 42
(9) (2007) 2917–2933.
[8] M.W. Barsoum, A. Ganguly, G. Hug, Microstructural evidence of reconstituted
limestone blocks in the great pyramids of Egypt, J. Am. Ceram. Soc. 89 (12)
(2006) 3788–3796,
[9] J. Davidovits, L. Huaman, R. Davidovits, Ancient organo-mineral geopolymer
in South-American monuments: Organic matter in andesite stone. SEM and
petrographic evidence, Ceram. Int. 45 (6) (2019) 7385–7389.
[10] C.G. Papakonstantinou, P.N. Balaguru, Geopolymer protective coatings for con-
crete, in: International SAMPE Symposium and Exhibition, Society for the
Advancement of Material and Process Engineering, Baltimore, 2007.
[11] S.K. Saxena, M. Kumar, N.B. Singh, Fire resistant properties of alumino silicate
geopolymer cement mortars, Mater. Today: Proc. 4 (4, Part E) (2017) 5605–5612.
[12] Z. Zhang, J.L. Provis, A. Reid, H. Wang, Mechanical, thermal insulation, thermal
resistance and acoustic absorption properties of geopolymer foam concrete, Cem.
Concr. Compos. 62 (2015) 97–105.
[13] K. Goretta, J. Fuller, E. Crawley., Geopolymers, Report OSR-H- 05-05, Air Force
Office of Scientific Research, 2006.
12
Construction and Building Materials 309 (2021) 124974
[14] J. Bell, M. Gordon, W. Kriven, Use of Geopolymeric Cement as a Refractory
Adhesive for Metal and Ceramic Joins, Wiley-Blackwell, 2008, pp. 407–413, Ch.
46.
[15] A. Palomo, M.W. Grutzeck, M.T. Blanco, Alkali-activated fly ashes: A cement for
the future, Cem. Concr. Res. 29 (8) (1999) 1323–1329.
[16] P.V. Krivenko, Synthesis of Cementitious Materials of the
Me2 O – MeO – Me2 O3 – SiO2 – H2 O System with Required Properties (Ph.D.
thesis), Kiev Civil Engineering Institute, Kiev, Ukraine, 1986.
[17] N. Ye, Y. Chen, J. Yang, S. Liang, Y. Hu, B. Xiao, Q. Huang, Y. Shi, J. Hu, X. Wu,
Co-disposal of MSWI fly ash and bayer red mud using an one-part geopolymeric
system, J. Hard Mater. 318 (2016) 70–78.
[18] H. Shi, Characterization and Modification of the Secondary Copper Smelting
Slag for Smooth Operation and Slag Valorization (Ph.D. thesis), Katholieke
Universiteit Leuven, 2017.
[19] J. He, G. Zhang, Geopolymerization of red mud and fly ash for civil infrastructure
applications, in: Geo-Frontiers Congress, ASCE, 2011.
[20] P. Sturm, G.J.G. Gluth, H.J.H. Brouwers, H.-C. Kühne, Synthesizing one-part
geopolymers from rice husk ash, Constr. Build. Mater. 124 (2016) 961–966.
[21] N. Ye, J. Yang, S. Liang, Y. Hu, J. Hu, B. Xiao, Q. Huang, Synthesis and strength
optimization of one-part geopolymer based on red mud, Constr. Build. Mater. 111
(2016) 317–325.
[22] N.A. Pambudi, R. Itoi, R. Yamashiro, B. Alam, L. Tusara, S. Jalilinasrabady, J.
Khasani, The behavior of silica in geothermal brine from dieng geothermal power
plant, Indonesia, Geothermics 54 (2015) 109–114.
[23] A. Karrech, M. Dong, M. Elchalakani, M.A. Shahin, Sustainable geopolymer using
lithium concentrate residues, Constr. Build. Mater. 228 (2019) 116740.
[24] N.A. Lloyd, B.V. Rangan, Geopolymer concrete with fly ash, in: Second Inter-
national Conference on Sustainable Construction Materials and Technologies,
2010.
[25] M.Z.N. Khan, F.uddinA. Shaikh, Y. Hao, H. Hao, Synthesis of high strength
ambient cured geopolymer composite by using low calcium fly ash, Constr. Build.
Mater. 125 (2016) 809–820.
[26] J.L. Provis, J.S.J. van Deventer, Alkali Activated Materials, Springer, Dordrecht,
Heidelberg, New York, London, 2014.
A. Karrech et al.
[27] C.K. Yip, G.C. Lukey, J.S.J. van Deventer, The coexistence of geopolymeric gel
and calcium silicate hydrate at the early stage of alkaline activation, Cem. Concr.
Res. 35 (9) (2005) 1688–1697,
[28] T.S. Qiu, J.Z. Kuang, F. Shi, Effect of alkali on the geopolymer strength,
Advanced Materials Research 168–170 (2010) 1827–1832.
[29] A.M.M. Bakri, H. Kamarudin, M. Bnhussain, A.R. Rafiza, Y. Zarina, Effect
of Na2SiO3/NaOH ratios and NaOH molarities on compressive strength of
fly-ash-based geopolymer, ACI Mater. J. 109 (5) (2012) 503–508.
[30] T. Alomayri, F.U.A. Shaikh, I.M. Low, Mechanical and thermal properties of
ambient cured cotton fabric-reinforced fly ash-based geopolymer composites,
Ceram. Int. 40 (9, Part A) (2014) 14019–14028,
[31] S.-D. Wang, K.L. Scrivener, P.L. Pratt, Factors affecting the strength of
alkali-activated slag, Cem. Concr. Res. 24 (6) (1994) 1033–1043,
[32] T. Luukkonen, Z. Abdollahnejad, J. Yliniemi, P. Kinnunen, M. Illikainen, One-part
alkali-activated materials: A review, Cem. Concr. Res. 103 (2018) 21–34.
[33] B. Nematollahi, J. Sanjayan, F.U.A. Shaikh, Synthesis of heat and ambient cured
one-part geopolymer mixes with different grades of sodium silicate, Ceram. Int.
41 (4) (2015) 5696–5704,
[34] M. Dong, M. Elchalakani, A. Karrech, Development of high strength one-part
geopolymer mortar using sodium metasilicate, Constr. Build. Mater. 236 (2020)
117611.
[35] J.G. Jang, N.K. Lee, H.K. Lee, Fresh and hardened properties of alkali-activated
fly ash/slag pastes with superplasticizers, Constr. Build. Mater. 50 (2014)
169–176.
[36] J. Xie, O. Kayali, Effect of superplasticiser on workability enhancement of class F
and class C fly ash-based geopolymers, Constr. Build. Mater. 122 (2016) 36–42.
[37] L. Carabba, S. Manzi, M.C. Bignozzi, Superplasticizer addition to carbon fly ash
geopolymers activated at room temperature, Materials 9 (7) (2016) 586.
[38] A.I. Laskar, R. Bhattacharjee, Effect of plasticizer and superplasticizer on
rheology of fly-ash-based geopolymer concrete, ACI Mater. J. 110 (5) (2013)
513–518.
[39] M. Albitar, P. Visintin, M.S. Mohamed Ali, M. Drechsler, Assessing behaviour of
fresh and hardened geopolymer concrete mixed with class-f fly ash, KSCE J. Civ.
Eng. 19 (5) (2015) 1445–1455,
13
Construction and Building Materials 309 (2021) 124974
[40] M. Palacios, Y.F. Houst, P. Bowen, F. Puertas, Adsorption of superplasticizer
admixtures on alkali-activated slag pastes, Cem. Concr. Res. 39 (8) (2009)
670–677.
[41] N. Ranjbar, M. Mehrali, A. Behnia, A. Javadi Pordsari, M. Mehrali, U.J.
Alengaram, M.Z. Jumaat, A comprehensive study of the polypropylene fiber
reinforced fly ash based geopolymer, PLoS One 11 (1) (2016) e0147546.
[42] M. Reed, W. Lokuge, W. Karunasena, Fibre-reinforced geopolymer concrete with
ambient curing for in situ applications, J. Mater. Sci. 49 (12) (2014) 4297–4304.
[43] F.U.A. Shaikh, Deflection hardening behaviour of short fibre reinforced fly ash
based geopolymer composites, Mater. Des. 50 (2013) 674–682.
[44] N. Ranjbar, M. Mehrali, M. Mehrali, U.J. Alengaram, M.Z. Jumaat, High tensile
strength fly ash based geopolymer composite using copper coated micro steel
fiber, Constr. Build. Mater. 112 (2016) 629–638.
[45] N. Ranjbar, M. Mehrali, M. Mehrali, U.J. Alengaram, M.Z. Jumaat, Graphene
nanoplatelet-fly ash based geopolymer composites, Cem. Concr. Res. 76 (2015)
222–231.
[46] M. Alzeer, K.J.D. MacKenzie, Synthesis and mechanical properties of new fibre-
reinforced composites of inorganic polymers with natural wool fibres, J. Mater.
Sci. 47 (19) (2012) 6958–6965,
[47] AS 3583.2, Methods of Test for Supplementary Cementitious Materials for Use
with Portland Cement – Determination of Moisture Content, Australian Standard,
2016.
[48] AS/NZS 3582.1, Supplementary Cementitious Materials – Part 1: Fly Ash,
Australian/New Zealand Standard, 2016.
[49] AS/NZS 3582.2, Supplementary Cementitious Materials – Part 2: Slag—Ground
Granulated Blast-Furnace, Australian/New Zealand Standard, 2016.
[50] S.-D. Wang, K.L. Scrivener, P.L. Pratt, Factors affecting the strength of
alkali-activated slag, Cem. Concr. Res. 24 (6) (1994) 1033–1043,
[51] J.J. Chang, A study on the setting characteristics of sodium silicate-activated slag
pastes, Cem. Concr. Res. 33 (7) (2003) 1005–1011,
[52] H.E. McGannon, The Making, Shaping and Treating of Steel, ninth ed., United
States Steel, Pittsburgh, United States, 1971.
[53] T. Bakharev, Alkali Activated Slag Concrete: Chemistry, Microstructure and
Durability (Ph.D. thesis), Monash University, Melbourne, Australia, 2000.
[54] A. Karrech, M. Dong, J. Skut, M. Elchalakani, M.A. Shahin, Management and val-
orisation of delithiated 𝛽-spodumene and its processing stream, Case Stud. Constr.
Mater. 15 (2021) e00671, http://dx.doi.org/10.1016/j.cscm.2021.e00671.
[55] A.M. Humad, Shrinkage and Related Properties of Alkali Activated Binders Based
on High MgO Blast Furnace Slag (Ph.D. thesis), Lulea University of Technology,
Lulea, Sweden, 2019.
[56] A.M. Humad, J.L. Provis, A. Cwirzen, Effects of curing conditions on shrinkage of
alkali activated high mgo swedish slag concrete, Frontiers in Materials 6 (2019)
287.