Applied Clay Science 196 (2020) 105773

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Applied Clay Science

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

Research Paper

Reaction kinetics and rheological behaviour of meta-halloysite based T

geopolymer cured at room temperature: Effect of thermal activation on
physicochemical and microstructural properties
⁎
Cyriaque Rodrigue Kazea,e,f, , Thamer Alomayrib, Assaedi Hasanc, Sylvain Tomed,
Gisèle Laure Lecomte-Nanaf, Juvenal Giogetti Deutou Nemaleue, Herve Kouamo Tchakoutea,
⁎⁎
Elie Kamseue, , Uphie Chinje Meloa, Hubert Rahierg
a
Laboratory of Applied Inorganic Chemistry, Faculty of Science, University of Yaoundé I, P.O. Box 812, Yaoundé, Cameroon
b
Department of Physics, Umm-Al-Qura University, Makkah 21955, Saudi Arabia
c
Department of Physics, University College in AlJumum, Umm Al-Qura University, P.O. Box 715, Makkah 21955, Saudi Arabia
d
Department of Chemistry, Faculty of Science, University of Douala, P.O. Box 24157, Douala, Cameroon
e
Laboratory of Materials, Local Materials Promotion Authority, MINRESI/MIPROMALO, P.O. Box 2396, Yaoundé, Cameroon
f
Institut de Recherche sur les Céramiques (IRCER, UMRCNRS 7315), ENSIL-ENSC ENSCI, Université de Limoges, CEC, 12 rue Atlantis, 87068 Limoges Cedex, France
g
Department of Materials and Chemistry, Vrije Universiteit Brussel, Pleinlaan 2, 1050 Brussels, Belgium

A R T I C LE I N FO A B S T R A C T

Keywords: In this paper, four samples of meta-halloysite from widely available Cameroon halloysite clay calcined at 600,
Halloysite 650, 700 and 750 °C, respectively, and the resultant geopolymer binders were systematically characterized.
Thermal activation Isothermal conduction calorimetry (ICC) was used to measure the reaction kinetics of meta-halloysite geopo-
Meta-halloysite lymers at room temperature during 48 h. The increase in reaction rate and in heat released correlates with the
Kinetic reaction
thermal activation temperature. It was typically found that the increase of thermal activation temperature (from
Rheology
Geopolymer
600 to 750 °C) enhances the amorphous or reactive phase content from MH600 to MH750 samples. This results
Mechanical properties in an improvement of rheological behaviour and setting time of the fresh meta-halloysite based geopolymer
pastes. The hardened meta-halloysite based geopolymers were amorphous, compact and dense according to X-
ray diffractometry (XRD) and Scanning Electron Microscopy (SEM). The compressive strength of resultant
products increased with the activation temperature, up to 750 °C (74 MPa at 180 days). Therefore, the best
temperature in view of the highest strength of meta-halloysite geopolymer cured at room temperature is 750 °C,
although the lower increase in mechanical performance (7.3%) gained between GPMH700 and GPMH750 is
limited. Thus, thermally activated halloysite clay appears to be a promising candidate for geopolymer synthesis.

1. Introduction
Geopolymer binder is a rather new class of cementitious material
resulting from a mixture of aluminosilicate powder with an alkaline or
acid solution cured at a temperature less than 100 °C (Davidovits,
2015). Their structure consists of repeating units of Si-O-Al or Si-O-Si
bonds, and are thus inorganic polymers. These materials attracted a lot
of attention because of their interesting properties. Since about one
decennium they find applications in several areas such as construction
and civil engineering, fire–resistant materials, insulation, various types
of refractories, etc. (Leonelli et al., 2017; Yankwa Djobo et al., 2016;
Bakharev, 2006; Brachhold and Aneziris, 2013; Tome et al., 2019). In
literature, most papers on geopolymers deal with the precursors me-
takaolin, by-products resulting from power production and metallurgy
(fly ash and slag), and some with volcanic ash (Kamseu et al., 2010;
Provis and Bernal, 2014; Vinai and Soutsos, 2019; Patrick N. Lemougna
et al., 2013). Particularly metakaolin has been studied, obtained from
calcined kaolin clay known as 1/1 clay type, dehydroxylated between
550 and 800 °C. However, few studies were carried out on halloysite
which is a homologue 1/1 clay type. Halloysite is a two-layered clay
and has a structure and chemical composition similar to that of kaoli-
nite except for its higher water content (Hofmann et al., 1934). The
main difference is the shape of halloysite particles that can be platelet-
like or tube-like depending on the pH value of the medium where it was

⁎
Corresponding author at: Laboratory of Applied Inorganic Chemistry, Faculty of Science, University of Yaoundé I, P.O. Box 812, Yaoundé, Cameroon.
⁎⁎
Corresponding author.
E-mail addresses: cyriaque.kaze@uy1.uninet.cm (C.R. Kaze), kamseuelie2001@yahoo.fr (E. Kamseu).

https://doi.org/10.1016/j.clay.2020.105773
Received 2 January 2020; Received in revised form 10 July 2020; Accepted 12 July 2020
0169-1317/ © 2020 Published by Elsevier B.V.
C.R. Kaze, et al.
formed (Peng et al., 2008b; Lecomte-Nana et al., 2017). Peng et al.
(2008a) modified the surface of natural halloysite clay nanotubes with
γ-Aminopropyltriethoxysilane (APTES) and compared the untreated
and modified samples using characterization techniques such as ni-
trogen absorption, XRD, FTIR, TG/DTA, TEM and AFM. These authors
found that the extend of modification is strongly affected by the mor-
phological parameters of the original clay which demonstrated that the
chemistry surface of halloysite nanotubes is readily modified, enabling
applications in nanocomposites, enzyme immobilization and controlled
release. Recently due to their superior thermal stability, high aspect
ratios, biocompatibility, mechanical properties, and ease of availability,
halloysite nanotubes exhibiting one dimensionality and hollow tubular
nanostructures have attracted global interests due to their potential
utilization in polymer nanocomposites (Idumah et al., 2019). In the
West Region of Cameroon in Balengou locality, halloysite clay is widely
available and can be valorized for the development of alternative bin-
ders (Pemunta, 2014). Referring to chemical composition, silicon and
aluminium oxides are the major components present in halloysite thus
rendering this aluminosilicate a possible candidate for the geopolymer
synthesis (Zhang et al., 2012; Lázaro, 2015). Several authors have
thermally activated halloysite at different temperatures in order to
produce geopolymers. Peng et al. (2008b) and Baifa et al. (2020) found
that the halloysite crystals were completely destroyed and an amor-
phous phase was formed between 650 and 850 °C improving their re-
activity in alkaline solution. MacKenzie et al. (2007) recommended a
temperature of 800 °C to produce dehydroxylated halloysite from which
geopolymers can be synthesized showing X-ray diffraction and Nuclear
Magnetic Resonance (NMR), characteristics similar to that of meta-
kaolin based geopolymer. Zhang et al. (2012) showed that kaolin
containing some halloysite heated at 700 °C possessed higher Si and Al
species dissolution rate than the purer kaolin and its metakaolin which
improved their mechanical performances. Recently Kaze et al. (2018)
produced geopolymer from Cameroon halloysite clay calcined at 600 °C
mixed with silicates with different moduli (1.10, 1.25, 1.41 and 1.56)
and the highest compressive strength of 27.5 MPa was reached at 1.25.
Notwithstanding the satisfactory strength achieved, some residual
halloysite was still present after the reaction, proving that after one
hour at 600 °C the transformation of halloysite to meta-halloysite has
not yet completed and that the remaining halloysite was not reactive
enough. Bayiha et al. (2019) replaced calcined halloysite at 700 °C with
limestone up 45 wt%. They found that the use of limestone as additive
contributed in physical packing of the matrix leading to an improve-
ment of mechanical properties. The authors mentioned above, obtained
geopolymer binders from raw or calcined halloysite clays with various
characteristics. From the literature it is well known that thermal acti-
vation is among the parameters which can affect the geopolymerization
reaction from clayey aluminosilicate materials. Thermal activation was
widely applied to kaolin clay for geopolymer synthesis and has shown a
significant increase in final properties of resulting products (Rahier
et al., 2000; Wang et al., 2010; Elimbi et al., 2011; Kenne et al., 2014).
Compared to kaolinite, halloysite has higher specific surface areas due
to their lower crystallinity induced by the insertion of water molecules
which produces different basal spacings in their structure (Lázaro,
2015, Peng et al., 2008a; Baifa et al., 2020). This limited structural
disorder that occurred in halloysite clay could be of great interest
during the thermal activation of halloysite compared to that of kaoli-
nite. This paper is the second in a series of articles describing the use of
Cameroonian halloysite for the development of geopolymer binders. It
was carried out with an objective to increase the reactivity of halloysite
clay using thermal activation and compare the final properties of syn-
thesized products to its homologue kaolin clay described in literature.
The following temperatures 600, 650, 700 and 750 °C were used for
thermal activation of halloysite clay. This work firstly deals with the
effect of thermal activation on dehydroxylation of halloysite clay he-
ated between 600 and 750 °C on the production of amorphous phase.
Thus, the samples were tested by thermal analysis and
2
Applied Clay Science 196 (2020) 105773
thermogravimetric analysis (DTA/TG), X-ray diffractometry (XRD) and
fourier transform infra-red spectroscopy (FTIR) in order to determine
their mineralogical phases and dehydroxylation. Secondly to correlate
the dehydroxylation temperature of halloysite clay to the reactivity, the
reaction kinetics of geopolymerization and rheological behaviour of
geopolymer binders resulting from halloysite clays calcined at different
temperatures were monitored using isothermal conduction calorimetry
(ICC) and rheometery. The characteristics of hardened meta-halloysite
based geopolymer products are interpreted correlating the effect of
thermal activation and development strength to the microstructure.
Hence the effect of calcination temperature on physicochemical and
mechanical properties of meta-halloysite based geopolymers cured at
room temperature are reported and discussed with the purpose of
finding the best calcination temperature of halloysite clay to synthesize
geopolymer products with desired mechanical and microstructural
properties.
2. Materials and methods
2.1. Materials
Halloysite clay used in this study was previously studied by Kaze
et al. (2018) and represents about 80 wt% of halloysite clay. The che-
mical composition was 56.0 wt% SiO2 and 29.3 wt% Al2O3. Whereas
the mineral phases were halloysite (Al2Si2O5(OH), PDF #13–375);
quartz (SiO2, PDF #5–349); hematite (Fe2O3, PDF #13–5) and anatase
(TiO2, PDF #4–447). The halloysite clay was oven dried at 105 °C,
ground and sieved at 80 μm. The resulting powders were calcined at
600, 650, 700 and 750 °C for 4 h (heating/cooling rate 5.0 K/min) in a
programmable electric furnace MIC (Muntatges Industrials per ceramic
S.L type mini 51A N° 2,350,507). The obtained meta-halloysite powders
were labelled MH600, MH650, MH700 and MH750. The sodium silicate
solution used in this study was supplied by Ingessil s.r.l. Verona (Italy)
and its chemical composition was; 14.37 wt% Na2O, 29.54 wt% SiO2,
56.09 wt% H2O. Sodium hydroxide solution (10 M) was obtained by
dissolving analytical grade sodium hydroxide pellets (BRAND) in dis-
tilled water. The alkaline activator was prepared by mixing of sodium
hydroxide solution and sodium silicate solution with a mass ratio
Na2SiO3/NaOH of 2.4 corresponding to final molar ratios SiO2/Na2O of
1.45 and H2O/Na2O of 10. The hardener was cooled and kept at room
temperature for 24 h before using. This allowed the full depolymer-
ization of sodium silicate in order to improve its reactivity.
2.2. Meta-halloysite geopolymer synthesis
The meta-halloysite geopolymer pastes were prepared by means of
mixing the alkaline solution with each meta-halloysite powder ac-
cording to a liquid/solid mass ratio of 0.83 used in our previous work
(Kaze et al., 2018) in an automatic Hobart mixer for 5 min. This mass
ratio allowed good workability of the paste. The geopolymer pastes
obtained were then poured into cubic moulds (40 × 40 cm) and sealed
into plastic bags to prevent water evaporation. The moulded specimens
were cured at 23 ± 2 °C, and 98% relative humidity (RH). After 24 h
the cubic specimens were demoulded, covered with a thin film of
polyethylene and stored at room temperature (23 ± 2 °C) and 98%
RH. The cubic specimens labelled, GPMH600, GPMH650, GPMH700,
and GPMH750, were used to measure the compressive strength after 7,
28, 90 and 180 days.
2.3. Physical properties
The compressive strength of the samples was measured with an
Instron 1195 Compression machine with a displacement of 5 mm/min.
The results shown are an average of five replicate cubic specimens. Dry
density (ρd) was calculated according to European Standard EN
12390–7. Three samples (of each formulation) were oven dried at
C.R. Kaze, et al.
105 °C for several days until stabilization of the mass. The total ap-
parent volume V, dry density (ρd) and wet density (ρwater) is then
evaluated using following equations, (1) to (2), where Md: mass dry;
Msat air: saturated mass in air (g); Msat water:immersed saturated mass in
water (g);
Msat air − Msat water
V=
ρwater (1)
Md
ρd =
V (2)
2.4. Physico-chemical characterization methods
The specific surface areas of halloysite clay heated at 600, 650, 700
and 750 °C were determined according to Brunauer–Emmet–Teller
(B.E.T.) method based on nitrogen adsorption using a Micromeritics
GEMINI 2360 instrument. The particle size distributions (cumulative
and density distribution) were investigated by means of a Mastersizer
2000 Ver. 5.22 (Malvern Instruments Ltd). Simultaneous Differential
Thermal Analysis- Thermogravimetric analysis (DTA/TG) was per-
formed on the four calcined halloysite and geopolymer samples, using a
Netzsch STA 429 CD in air atmosphere. The analyses were carried out
on ground powders (sieved below 80 μm) at a heating rate of 20 K/min
in platinum‑rhodium crucibles using calcined alumina as a reference.
Meta-halloysite, and geopolymer specimens aged for 28 days were
crushed and sieved through a sieve of mesh 80 μm. The obtained
powders were subjected to X-ray powder diffractometry (XRD; applying
a PW3710, Phillips) using CuKα, and Ni-filtered radiation (the wave-
length was 1.54184 Å). The radiation was generated at 40 mA and
40 kV. Each analysis was performed on fine grains of ground samples.
Random powder specimens were step-scanned from 5° to 70°, 2θ range,
and integrated at the rate of 2 s per step. Pieces collected from the
mechanical testing were polished, gold coated for microstructural ob-
servations using a JEOL JSM-6500F Scanning Electron Microscope
(SEM) coupled with Energy Dispersive X-ray spectroscopy (EDX) with
an acceleration voltage of 10.0 kV. The apparatus was equipped with
high resolution W filament gun (LaB6 option). An integrated camera
allowed intuitive navigation to the area of interest of different samples.
The initial setting time was measured on the fresh geopolymer pastes
obtained from calcined halloysite clay (600 and 750 °C), with alkaline
solution using Vicat apparatus. The needle used was
1.000 ± 0.005 mm in diameter. The initial setting is verified from
10 min after the preparation of geopolymer pastes every minute until
the first resistance is detected. This was done in the laboratory with
60% of relative humidity and the room temperature was 17 ± 2 °C.
This test was performed according to the EN196–3 standard. The
Fig. 1. Granulometry of calcined halloysite clays MH600, MH650, MH700 and MH750.
3
Applied Clay Science 196 (2020) 105773
rheology of the geopolymer pastes was characterized using a stress-
controlled rheometer-ARG2 from TA Instruments. The measuring geo-
metry consisted of a 25 mm upper and lower plate temperature regu-
lated with a Peltier. The viscoelastic parameters of fresh paste were
investigated by simple shear flow and dynamic oscillatory tests carried
out at 21 °C in the linear viscoelastic domain. The geopolymer pastes
were prepared by hand mixing outside the rheometer and then in-
troduced into the rheometer between the plates. Rheological steady
state flow measurements consisted in performing a series of creep ex-
periments with varying stress, where the equilibrium shear rate is ob-
tained when the curve reaches a linear regime. The linear viscoelastic
region (LVER) was determined by oscillatory strain sweep from 0.002%
to 20% at a fixed frequency of 1 Hz. Herschel-Bulkley law (Eq. 3) has
been used to determine the viscoelastic parameters:
τ = τo + K γn (3)
where τo is the yield stress, K the consistency and n the rate index.
Viscoelastic properties of the geopolymer binders were investigated by
oscillatory measurements. The basis of these measurements is the ap-
plication of a sinusoidal strain (γ) and the measurement of the corre-
sponding stress (τ). The loss modulus (tanδ) defined by
G′ ′
tan δ =
G′ (4)
was also analyzed during the geopolymerization. Isothermal (heat
conduction) calorimetry was used to study the steps related to the
geopolymerization of cement pastes at 27 °C on the early age (48 h).
The rate of heat evolution during the reaction (dq/dt) was evaluated
using an eight-channel isothermal conduction calorimeter (TAM AIR,
Thermometric AB, Jarafalla, Sweden). The main steps of the sample
preparation were: the preparation of the alkaline activator solution,
followed by the mixing of the alkaline activator with the powder
sample and loading of the mixture in calorimeter. 7 g of each calcined
halloysite powder and the ratio of liquid/solid was 0.83 according to
our previous work (Kaze et al., 2018) for all the samples. The time-
dependent degree of reaction α(t) was determined with the calorimetry
data following the Stutter method, according to Eq. 5:
α(t) = Q(t ) / Qmax (5)
Where Q(t) is the cumulative heat, released at time t, and Qmaxis the
total or the maximum heat released hear after 48 h.
C.R. Kaze, et al. Applied Clay Science 196 (2020) 105773

Table 1
Particle size, specific surface areas and bulk density of calcined halloysite clay MH600, MH650, MH700 and MH750 s1samples.
Samples Initial setting Compressive strength (7, 28, 90 and 180 days) Bulk density (g/cm3) (7, 28, 90 and Water absorption (%) (7, 28, 90 and 180 days)
time (min.) 180 days)

7 28 90 180 7 28 90 180 7 28 90 180

GPMH600 326 18.30 28.82 31.30 32.30 1.90 1.87 1.67 1.67 24.74 20.23 19.50 18.20
GPMH650 245 28.90 58.40 62.40 66.80 1.97 1.86 1.86 1.86 19.15 15.80 14.62 13.50
GPMH700 196 29.90 61.50 65.50 68.70 1.97 1.86 1.86 1.86 17.23 14.30 10.20 9.23
GPMH750 210 30.23 68.50 70.34 73.70 1.95 1.87 1.87 1.86 16.13 13.40 9.20 10.40

3. Results
3.1. Characterization of raw materials
The effect of thermal activation on granulometry of calcined hal-
loysite clay at 600, 650, 700 and 750 °C is depicted in Fig. 1. No sig-
nificant change in particles size of d0.1 and d0.5 is observed with in-
creasing of calcination temperature from 600 to 750 °C. However, a
slight increase of particle size was noted on d0.9 (Table 1) from 42 to
58 μm. This trend could be explained by the beginning agglomeration
or sticking of particles due to the increase of the calcination tempera-
ture from 700 to 750 °C. In all calcined halloysite samples labelled
MH600, MH650, MH700 and MH750, the particle size distribution is
characterized by a multimodal distribution. The first mode varies from
0.1 to 1 μm with a maximum around a size of 0.34 μm. In the second
mode, particles range from 1 to 19 μm with a maximum around 5.7 μm.
Finally, the last mode, situated between 19 and 183 μm has a maximum
around 58 μm. Fig. 2 presents the SEM images of raw halloysite clay
(HA) and calcined halloysite (MH700) at 700 °C. This was carried out at
higher magnification to show in detail the morphological shapes of
halloysite clay before and after calcination (700 °C). The particles of
raw halloysite clay have platelet shapes, thus not similar to nanotubes
as observed with TEM by others (Peng et al., 2008a; Peng et al., 2008b;
Xiaoguang et al., 2019; Baifa et al., 2020). If the halloysite is heated at
700 °C, the meta-halloysite exhibited spherical form and fine particles
consistent with the findings of Kouamo et al. (2020). Heating halloysite
clay from 600 to 750 °C changed their crystalline structure by trans-
forming into amorphous phases attributed to the dehydroxylation in-
dicated on TG/DTA analyses. The fine particles observed on heated
samples would be beneficial during the geopolymerization reaction,
because the fine particles have a large surface area and could more
rapidly dissolve in an alkaline solution. No diffusion control is expected
either, thus the particles can completely react. Hence with this kind of
particles one can expect a completely reacted solid phase, with a dense
microstructure and good mechanical properties of the end products. X-
ray patterns of calcined halloysite clay from 600 to 750 °C are reported
in Fig. 3. From Fig. 3 one can observe the disappearance of the hal-
loysite mineral reflection from 650 °C to 750 °C indicating the total
transformation or dehydroxylation of halloysite clay to meta-halloysite.
The mineralogical phases were (Q) (SiO2, PDF #5–349); hematite (He)
(Fe2O3, PDF #13–5), except halloysite (H) (Al2Si2O5(OH), PDF
#13–375) that was still present in calcined halloysite at 600 °C. On the
other hand the X-ray diffractograms of all calcined halloysite clays la-
belled MH600, MH650, MH700 and MH750 showed a diffuse halo peak
with 2θ ranging between 15° and 35° which is known as characteristic
of amorphous and thus reactive phase present in calcined halloysite

Halloysite b c
a
(HA)

Platelets
Shape

Meta-halloysite d e f
(MH700)
Fine particles

Fig. 2. SEM images of raw (HA) and calcined halloysite (MH700) observed at different magnifications (1200x, 3000x and 6000x).

4
C.R. Kaze, et al.
Fig. 3. X-ray patterns of calcined halloysite clays MH600, MH650, MH700 and MH750. Key: (Q) (quartz, SiO2, PDF #5–349); (He) (hematite, Fe2O3, PDF #13–5) and
(An) (anatase, TiO2, PDF #4–447).
clays. This halo confirms the conversion of halloysite clay to meta-
halloysite after calcination. Fig. 4A highlights the simultaneous DTA/
TG thermogram of raw halloysite clay. The thermogram shows two
endothermic phenomena. The first, about 2 wt% is situated around
82 °C and corresponds to elimination of water. The second one, 11 wt%,
centered at 542 °C, is attributed to the dehydroxylation of halloysite
(Peng et al., 2015). The exothermic phenomenon at about 997 °C cor-
responds to the transformation of meta-halloysite into mullite (Peng
et al., 2015). With the simultaneous differential thermal and thermo-
gravimetric analysis (TG/DTA) carried out on calcined halloysite, it was
possible to observe the major transformations which take place be-
tween 50 and around 500 °C (Fig. 4B). The first endothermic situated
around 50 °C is related to the loss of the non-structural water (Fig. 4B).
The second one at 465 °C on MH600 curve corresponds to loss of water
of Al-OH groups of residual halloysite that did not totally transform to
meta-halloysite when the halloysite clay was calcined at 600 °C
(Fig. 4B) (Peng et al., 2015). This demonstrates that halloysite clay
should be calcined above 600 °C as reported by the findings of Peng
et al. (2008b) and Baifa et al. (2020), who reported that the halloysite
crystals were completely destroyed and an amorphous phase formed
between 650 and 850 °C. It is also noticed that the thermal treatment at
650, 700 and 750 °C does not change the thermograms of halloysite
clay a lot. This observation can be confirmed with Fig. 4C): at 650, 700
and 750 °C the mass loss is within 2 wt% mainly due to absorbed water
after the dehydration, and a small residual dehydroxylation step,
starting each time at a higher temperature. The endotherm (in DTA
curve) that appeared at 573 °C is linked to the transformation of α-
quartz to β-quartz (Rickard and van Riessen, 2010). The last one around
980 °C is due to the formation of mullite phase (Peng et al., 2015;
Xiaoguang et al., 2019; Emmanuel et al., 2020; Martine et al., 2020)
(Fig. 4B). The infrared spectra of raw halloysite (HA) and calcined
halloysite labelled MH600, MH650, MH700 and MH750 are plotted in
Fig. 5. For the raw halloysite clay (Fig. 5A), the absorption bands
5
Applied Clay Science 196 (2020) 105773
located at 3619 and 3694 cm−1 are attributed to OeH stretching linked
to halloysite mineral and axial asymmetric and symmetric deformation
of Al-OH (Kaze et al., 2018a). Those situated at 910, 998 and
1118 cm−1 are assigned to the stretching vibration modes of Si-O-Si
and Si-O-Al bonds (Fig. 5A). The last bands at about 750–788 cm−1 and
676 cm−1 are linked to the distorted Al(VI) of octahedra of halloysite
structure and vibration mode of SieO bond, respectively (Kaze et al.,
2018; Tchakoute et al., 2015). The broad absorption bands at interval
1043–1053 cm−1 (Fig. 5B) are assigned to internal vibration of Si-O-Si
and Si-O-Al bindings (Lemougna et al., 2014; Baenla et al., 2020). The
ones located between 773 and 784 cm−1 correspond to the AleO
bending mode of AlO6 (Muayad et al., 2015) octahedra in halloysite
and meta-halloysite respectively in all samples (Fig. 5B). The intensity
of these bands decreases with thermal activation from 600 to 750 °C,
indicating the breakdown of the octahedral Al structure of the halloy-
site particles (Bich et al., 2009). The absorption bands at 663, 676, 678
and 692 cm−1 are attributed to the stretching of SieO of quartz
(Tchakoute et al., 2015; Elie et al., 2020). The last absorption bands
situated in the range of 436–447 cm−1 correspond to Si-O-T(Al or Si)
stretching and deformation vibration (Joussein et al., 2005; Paulo et al.,
2009).
3.2. Reactivity study
The different reaction steps during the first 48 h of geopolymer-
ization reaction are shown in Fig. 6A. According to this figure, three
major peaks of heat evolution were detected during the first 48 h of
geopolymerization reaction. The first step (I) appearing almost im-
mediately on calorimetric curves when each calcined halloysite powder
was mixed with alkaline solution, represents the dissolution of the
glassy or amorphous phase contained in solid precursors. While the
second peak (II) which is more distinct in all samples used for the ca-
lorimetry study depicts reorganization, diffusion of dissolved ions with
C.R. Kaze, et al. Applied Clay Science 196 (2020) 105773

Fig. 4. DTA/TG curves of raw (A) and calcined halloysite (B and C) at 600, 650, 700 and 750 °C.

formation of small, coagulated structures via condensation to build up
an aluminosilicate gel phase. The third step (III) is the polycondensa-
tion thus the formation of the solid state due to the agglomeration of
oligomer species corresponding to the hardening of geopolymer pastes
using the Vicat test. The aforementioned phenomena (I) and (II)
increase with the rise of calcination temperature. However, the increase
is prominent from 600 to 700 °C and less from 700 to 750 °C. The
reaction (II) reaches its maximum rate during ~4 h in all the samples.
The degree of reaction (α) (determined according to the Eq. 5 in section
2.4) at this maximum is 0.34, 0.37, 0.4 and 0.41 for MH 600, 650, 700

Fig. 5. Infrared spectra of raw halloysite clay (A) and calcined calcined halloysite (B).

6
C.R. Kaze, et al. Applied Clay Science 196 (2020) 105773

Fig. 6. Isothermal conduction calorimetry plot of alkali activation and heat-evolution released of dissolution of meta-halloysite labelled MH600, MH650, MH700 and
MH750 with time.

Table 2 210 min for geopolymer labelled GPMH750. This increase was not
Setting time and physical properties of meta-halloysite based geopolymers. expected based on the calorimetry results where MH750 is not slower
Particles size distribution than MH700. This small increase in setting time might be due to the
further rearrangements in the meta-halloysite, which decreased the
Meta- d0.1 (μm) d0.5 (μm) d0.9 (μm) B.E.T surface Bulk density (g/ solubility again. This will lead to a lower availability of Al-species in
halloysite areas (m2/g) cm3) alkaline medium required to polymerize or polycondensate with Si-
samples
species during the geopolymerization reaction. To further clarify the
MH600 0.32 4.72 42.53 28.20 ± 0.12 2.82 ± 0.02 exact reasons for this slow down, extra investigations are needed such
MH650 0.31 5.03 43.98 29.52 ± 0.13 2.95 ± 0.02 as Nuclear Magnetic Resonance (NMR) spectroscopy to investigate the
MH700 0.34 5.54 51.59 25.92 ± 0.11 2.01 ± 0.02 surroundings of 29Si and 27Al in the meta-halloysite and in the geopo-
MH750 0.34 5.69 58.29 25.83 ± 0.10 2.01 ± 0.02
lymer binder, but this is not the main target of this research. A similar
trend was observed by Elimbi et al. (2011) on the effect of calcination
temperature on the reactivity of metakaolin based geopolymer. These
and 750 °C, respectively. The increase of calcination temperature from
authors concluded that the increase in setting on samples heated above
600 to 700 °C considerably improved the reactivity of halloysite clay by
700 °C is linked to the decrease of reactive or amorphous phase ne-
the transformation of crystalline aluminosilicate (halloysite) to amor-
cessary for geopolymer synthesis.
phous aluminosilicate (meta-halloysite). However, every material has
the limit of the activation temperature. Up to this limit the contrary
effect can be observed. Notice that from 700 to 750 °C the variation of
3.3. Rheological behaviour
energy and the reactivity is low. Based on calorimetry it is not necessary
to activate the halloysite above 700 °C as the thermogram for 750 °C is
Fig. 7 depicts the oscillatory strain sweep of meta-halloysite geo-
the same within the margin of uncertainty. The shape of the heat re-
polymer pastes at 1 Hz. In all geopolymer formulations, namely:
leased curves during these reactions is depicted in Fig. 6B. The total
GPMH600 (Fig. 7A), GPMH650 (Fig. 7B), GPMH700 (Fig. 7C) and
heat released recorded on different calcined powders activated with
GPMH750 (Fig. 7D), the elastic modulus (G') is higher than the viscous
alkaline solution after 48 h of reaction (obtained by integrating the heat
modulus (G") in the linear viscoelastic region (LVER) describing the gel-
flow according to the time) is 237, 241, 257 and 259 J/g for MH600,
like behaviour. The LVER is the region where G' and G" do not change
650, 700 and 750 °C, respectively. This heat released drastically in-
with the amplitude. This region is below a strain of 0.01% in all cases.
creased from 600 to 700 °C, but is almost the same at 700 or 750 °C. The
In this region the interaction between different constituents is related to
heat released is typical of exothermic reaction. The progress of heat
predominance of geopolymer gel (N-A-S-H) network formation even
released corroborates with the above observations. The results of initial
before hardening of different sample pastes (Poulesquen et al., 2013).
setting time as a function of the calcination temperature of the meta-
Similar trend was observed by Martin et al. (2018) and Poulesquen
halloysite based geopolymer pastes from the calcined halloysite clays
et al. (2013) on rheological properties of alkali-activated brick powder-
between 600 and 750 °C using Vicat needle are reported in Table 2. It is
based pastes and metakaolin based geopolymer using different activa-
observed that the setting time varies between 326 and 196 min: it de-
tors, respectively. These authors concluded that the solid properties of
creases when thermal activation is carried out from 600 to 700 °C for
alkali activated materials are linked to first step (dissolution of solid
GPMH600, GPMH650 and GPMH700 geopolymer samples. This de-
precursor into oligomers formation) and second step (polycondensation
crease is due to the increase in reactive fraction, but also in reactivity.
of oligomers into rigid block) of geopolymerization mechanism. These
The link between these two is not so obvious as the reaction is het-
observations are in agreement with the ICC study. At the crossover
erogenous, thus the first step of the reaction takes place at the interface
point where G' = G”, G" quickly exceeds the elastic modulus in all
between solid and liquid. It is clear from ICC (Fig. 6A, inset) that also
geopolymer samples GPMH600, GPMH650, GPMH700 and GPMH750,
the first step (dissolution) is faster, finally leading to an overall faster
indicating the consistency of a rigid amorphous solid 3-D geopolymer
reaction. The available reactive phases that allowed the decrease of
network resulting from polycondensation of silicate and aluminate
setting time might be explained by the almost total transformation of
oligomers during the geopolymerization reaction (Palacios et al., 2018;
halloysite clay to meta-halloysite which can provide more reactive si-
Puertas et al., 2018; Pavel et al., 2018). At this point the strain de-
licates and aluminates. Above 700 °C, a small increase is noticed till
creases from 0.23% to 0.08% with calcination temperature from 600 to

7
C.R. Kaze, et al.
(A)
(C)
Fig. 7. Oscillatory strain sweep at 1 Hz of GPMH600 (A), GPMH650 (B), GPMH700 (C) and GPMH750 (D) meta-halloysite-based geopolymers.
700 °C. This trend could be justified by the increase of reactive or
amorphous fraction within calcined halloysite clay. A slightly increase
in strain noticed on GPMH750 (0.14%) confirms the aforementioned
reduction of reactive phase. The values of yield stress of specimens were
obtained using the Herschel-Bulkley model fitted to the data. The va-
lues were 5.43, 3.70, 2.50 and 5.54 Pa for GPMH600, GPMH650,
GPMH700 and GPMH750 samples, respectively. As seen in Fig. 7, the
yield stresses decrease from 5.43 Pa (GPMH600) to 2.45 (GPMH700)
indicating the increase of reactive phase within calcined halloysite re-
sulting in fast setting in contact of alkaline solution, and increased from
2.45 to 5.54 Pa (GPMH750) related to the formation of coarse particles
after calcination at 700 °C leading to high interactions in alkaline
medium linking to low reactivity. When G" pass over G' at gel point, the
loss modulus (Tanδ) increased in samples and reached a peak at 12% of
strain then decreased (Fig. 7a-d). This corresponds to the gradual ge-
lation of geopolymer microstructure pastes (Rovnaník et al. 2018).
Fig. 8A presents the evolution of compliance of geopolymer formula-
tions as function as time. It is shown that the deformations (com-
pliances) undergone by GPMH600, GPMH650, GPMH700 and
GPMH750 geopolymer pastes decrease with increasing of calcination
temperature from 600 to 750 °C. The increase in deformation is char-
acteristic of high interaction between different phases in geopolymer
GPMH650, GPMH700 and GPMH750 pastes related to the important
amount of reactive phase compared to lower compliances undergone by
geopolymer GPMH600 paste where the interparticle bonds are weak. In
all curves it is noted that the compliance increases, reaches the max-
imum and remain almost constant with time indicating the hardening
8
Applied Clay Science 196 (2020) 105773
(B)
(D)
of geopolymer paste. For the all formulations a residual strain in pastes
was observed. The values were 0.02, 0.15, 0.07 and 0.10 Pa−1, re-
spectively for GPMH600, GPMH650, GPMH700 and GPMH750. These
values were achieved at 1393, 1116, 1065 and 1015s, respectively.
Thus, the increase in calcination temperature improved the meta-hal-
loysite based geopolymer pastes rheological behaviour resulting in
competition between dissolution of amorphous phase and geopoly-
merization process that could affect the rheology evolution of the ela-
borated geopolymers. This trend is in line with the setting time results
and ICC analysis. These results confirm those obtained from the oscil-
latory tests.
3.4. Phases evolution
Fig. 8B displays the infrared spectra of meta-halloysite based geo-
polymer GPMH600, GPMH650, GPMH700 and GPMH750 samples. The
broad absorption bands that appears in the range of 1618–1634 cm−1
and 3379–3419 cm−1 correspond to the stretching and deformation
vibration modes of H-O-H and OeH of water molecules. The bands that
appear at 1043–1053 cm−1 in the meta-halloysite IR spectrum after
activated with alkaline solution shifted toward lower wavenumbers
973, 976, 979 and 990 cm−1 for GPMH600, GPMH650, GPMH700 and
GPMH750, respectively. This displacement indicates the change of
structure that occurred during depolymerization and polycondensation
process resulting in incorporation of Al tetrahedra into silicate footprint
(Rahier et al., 1997; Madi et al., 2018). On the other hand these ab-
sorption bands are attributed to the asymmetric stretching of Si-O-Al
C.R. Kaze, et al. Applied Clay Science 196 (2020) 105773

Fig. 8. Compliance as function of time for fresh meta-halloysite-based geopolymer pastes cured at room temperature at 3600 s (A); infrared spectra (B) and DTA/TG
curves of (C and D) of consolidated meta-halloysite-based geopolymers.

Fig. 9. X-ray patterns of hardened meta-halloysite based geopolymers labelled GPMH600, GPMH650, GPMH700 and GPMH750. Key: (Q) (quartz, SiO2, PDF
#5–349); (He) (hematite, Fe2O3, PDF #13–5) and (An) (anatase, TiO2, PDF #4–447).

9
C.R. Kaze, et al.
bonds in geopolymer network, known as characteristic peak of in-
organic polymer network in literature (Aldabsheh et al., 2015; Rees
et al., 2007; Peys et al., 2016). The small bands at 774–775 cm−1 are
linked to AleO bending. The bands situated at 670–699 cm−1 and
415–431 cm−1 are assigned to asymmetrical and symmetrical
stretching vibration modes of bridge bonds of Si-O-Si, Si-O-Al and SieO
bonds respectively (Kaze et al., 2018; Rodrigue et al., 2017; Nana et al.,
2019). The thermal analysis performed on different consolidated meta-
halloysite based geopolymer binders are shown in Fig. 8C-D. From the
DTA curves (Fig. 8C) the endothermic peaks in all geopolymer samples
at 50 °C accompanied with 2.0 and 4.0% of weight loss on TG curves
(Fig. 8D), are linked to the evaporation of free water (Alomayri et al.,
2014; Hasan et al., 2020). While the second one centred about 105 °C
which accounted for about 70% of the total weight loss in 25–1200 °C
in all meta-halloysite thermograms is assigned to the release of water
chemically or physically bounded to Na-aluminosilicate binder phase
within geopolymer matrix resulting in denaturation or break down of
geopolymer network (Rashad and Ouda, 2018). The exothermic peaks
located at 875 and 954 °C (Fig. 8C) imply the reorganization of non-
reactive meta-halloysite particles in alkaline medium which allowed
the formation of mullite phase (Lecomte-nana et al., 2013; Deutou
Juvenal et al., 2020). These peaks are more noticeable in the TG/DTA
curves of calcined halloysite at different temperatures (600, 650, 700
and 750 °C) compared to those of meta-halloysite based geopolymer
binders (GPMH700 and GPMH750) which are less significant. This in-
dicates that a major part of alumina particles from meta-halloysite had
reacted with sodium activating solution to form sodium-alumino-silico-
hydrated (N-A-S-H) binder and less amorphous or semi-crystalline
aluminium compounds. The X-ray patterns of meta-halloysite based
geopolymer binders are reported in Fig. 9. It is observed the dis-
appearance of residual halloysite presents in calcined halloysite at
600 °C after alkaline activation. This could be due to their dissolution
resulting into zeolite in alkaline medium. However, the main minerals
like hematite, anatase and quartz present in all calcined halloysite
(from 600 to 750 °C) are still present after geopolymerization reaction,
suggesting that these minerals had not altered in alkaline medium thus
would behave as micro aggregates or fillers by reinforcing the geopo-
lymer matrix. The displacement of broad hump situated between 2θ =
15° and 35° (Fig. 3) in calcined halloysite clay at different temperatures
to 20° and 40° (Fig. 9) for all meta-halloysite based geopolymers, in-
dicates the formation of amorphous binder (Na-aluminosilicate) phase
responsible to the strength development gained on samples mechani-
cally tested. The intensity of amorphous phase increases with thermal
activation from 600 to 750 °C is in agreement with the reactive degree
observed by kinetic reaction analysis.
3.5. Mechanical and physical properties
The compressive strengths of hardened geopolymer binders as a
function of the thermal activation of the halloysite clay were reported
in Table 2. As can see from this Table (Table 2) the mechanical per-
formance increases from 600 to 700 °C then drops afterward. The
compressive strengths of hardened meta-halloysite-based geopolymer
specimens were 18.30/28.82/31.30/32.30 MPa; 28.90/58.40/62.40/
66.80 MPa; 29.90/61.50/65.50/68.70 MPa; 30.23/68.50/70.34/
73.70 MPa respectively for geopolymer binders made from calcined
halloysite clay (at 600, 650, 700 and 750 °C) cured at 7, 28, 90 and
180 days. However, no large change in strength development was no-
ticed between the samples made from calcined halloysite between 700
and 750 °C. The increase of compressive strength of meta-halloysite
based geopolymers made from calcined halloysite clay from 600 to
750 °C is justified by the increase of reactive phase within calcined
powders which can easily dissolve into alkaline solution by producing
an extend geopolymer network resulting in a compact structure. It is
obvious that the increase in thermal activation from 600 to 750 °C
improves the amorphous phase content (within meta-halloysite)
10
Applied Clay Science 196 (2020) 105773
leading to better mechanical performances of geopolymer specimens. It
is noteworthy that the obtained fine particles from calcined halloysite
played an important role during the geopolymerization reaction con-
tributing to a high dissolution of solid precursor resulting in high de-
gree of polymerization or polycondensation between Al- and Si- oli-
gomer species. This favours the cohesion and bonding strength between
different particles in geopolymer matrix suggesting a compact end
product. The increase in compressive strength of meta-halloysite based
geopolymer with calcination temperature from 600 to 750 °C is con-
sistent with observation Baifa et al. (2020) who found that 750 °C is the
optimal temperature to ensure a high strength (58.7 MPa) from cal-
cined halloysite clay favourable for geopolymerization. However, cal-
cination above 700 °C does not remarkably improve the strength de-
velopment even though the compressive strength achieved on samples
made of MH750 is still high. Only at longer times, the MH750 based
samples have still significant higher strengths. This trend might be re-
lated either to less available Al for polycondensation or decrease of the
amorphous phase content, resulting to less performant strength be-
tween geopolymer products GPMH700 and GPMH750 cured at 7, 28,
90 and 180 days. Only 2, 7 and 5 MPa gained in compressive strength
from GPMH700 to GPMH750 samples cured at 28, 90 and 180 days.
This result is in line with the one of kinetic reaction explained earlier
(section 3.2) where low total heat (about 2.20 J/g) was recorded be-
tween GMH700 and GPMH750 samples even this later had more total
heat released than GPMH600, GPMH650 and GPMH700 specimens
suggesting higher reaction degree. The bulk density of meta-halloysite
based geopolymers is reported in Table 2. The density ranges from 1.98
to 1.67 g/cm3; 1.97 to 1.86 g/cm3; 1.96 to 1.88 g/cm3; 1.95 to 1.86 g/
cm3, for specimens GPMH600, GPMH650, GPMH700 and GPMH750,
respectively. As listed in Table 2 it is noticed that the bulk density
decreases considerably from 7 to 90 days for GPMH600 sample, and
from 7 to 28 days for samples GPMH650, GPMH700 and GPMH750,
and then becomes almost constant from 28 to 180 days. The high de-
crease of bulk density observed on GPMH600 sample can be justified by
either the loss of the extra water that has not taken part in geopoly-
merization or water evaporation during the drying which makes the
sample lighter with time. This also proves that the thermal activation at
600 °C does not produce a sufficient amount of reactive phase available
for the well geopolymerization process. This behaviour is in agreement
with the one of Djobo et al., 2016, who attributed the decrease of bulk
density to the increase of apparent porosity. Table 2 also shows the
evolution of the amount of absorbed water in the function of curing
time. The water absorption varies from 18% to 24%; 15% to 19%; 12%
to 17% and 12% to 16%, for specimens labelled GPMH600, GPMH650,
GPMH700 and GPMH750, respectively. The maximum water absorp-
tion was recorded between 7 and 28 days while after 90 days, it is no
significant variation and remains almost constant with curing time
where these values decreased and ranged from 24% to 18%; 19% to
13%; 17% to 9% and 16% to 10%, respectively for geopolymers
GPMH600, GPMH650, GPMH700 and GPMH750. The high values of
water absorption observed on samples GPMH600 are attributed to the
presence of residual halloysite clay within calcined halloysite at 600 °C,
which can retain much water when the specimens were immersed in
water for the water absorption test.
3.6. Scanning electron microscope (SEM)
Fig. 10 presents the selected fractures of SEM micrographs detailing
the internal microstructure of meta-halloysite based geopolymer bin-
ders made from calcined halloysite clay between 600 and 750 °C. The
geopolymer matrix appears to exhibit an inhomogeneous structure. In
Fig. 10A, it is observed a typical semi-spherical pore on the fractured
surface, surrounded by geopolymer matrix with microcracks on geo-
polymer sample GPMH600, while the GPMH650, GPMH700 and
GPMH750 specimens are more compact. These pores are likely caused
by the air bubbles that are introduced into the geopolymer pastes
C.R. Kaze, et al.
Fig. 10. SEM images of meta-halloysite based geopolymers at lower (A) and higher (B) magnification.
through mixing or trapped inside the geopolymer binder when pouring
into moulds. On the other hand, the presence of microcracks might be
obviously formed after mechanical testing where collected pieces were
used for SEM analysis. Therefore, the less dense and compact sample
would be more affected by exhibiting more fissure after mechanical
testing measurements, it is the case of MH600 sample compared to
other specimens. This proves the lower reactivity and mechanical
strength gained on sample labelled GPMH600 obtained from calcined
halloysite at 600 °C. At higher magnification images (≤ 1 μm), it is also
observed that the GPMH600 specimen contains a greater quantity of
microspheres than GPMH650, GPMH700 and GPMH750 samples, while
the opposite was observed for platy films belonging to non-reactive
meta-halloysite powders (Fig. 10B). It is believed that the platy films
appearing on microstructure, are geopolymer binders which embed
other particles as unreactive phases within matrix. The increase of the
thermal activation from 600 to 750 °C leads to enhancement of reactive
phase (amorphous) in calcined halloysite, which release more reactive
silica and alumina in contact of alkaline solution during the dissolution
step, resulting in good polycondensation allowing a very compact and
dense structure justifying the high strength gained in this study. This
trend is in agreement with the work done by Davidovits (1991); Palomo
et al. (1999), and Cioffi et al. (2003), conducted on calcined kaolinite
clay in the range of 550–800 °C. These authors stated that the increase
of calcination temperature improves the compressive strength resulting
in compactness of metakaolin based geopolymers. Similar trend was
recently noticed by Baifa et al. (2020) on thermally halloysite clay used
as solid precursor for geopolymer synthesis.
4. Discussion
Halloysite clay belongs to 1/1 clay type as kaolinite. It contains
majority of silicon and aluminium oxides which are fundamental in-
gredients of geopolymerization reaction (Davidovits, 2008) thus sui-
table for making inorganic polymers (geopolymers). The thermal
treatment of halloysite clay from 600 to 750 °C enhances the reactivity
(amorphous phase) of resulting meta-halloysite powder. This would
favour a high dissolution of reactive phase followed by polycondensa-
tion of Si- and Al-oligomers giving geopolymer binders with optimum
11
Applied Clay Science 196 (2020) 105773
mechanical strength compared to that of metakaolin based geopolymers
found in literature (Selmani et al., 2017; Sun and Vollpracht, 2018).
From FTIR spectra the degree of dehydroxylation (DIR) was evaluated
using a formula DIR = 1-S/So (where S and So represent peak area and
maximum peak area respectively) as reported by Rahier et al. (2000). It
was found that the degree of dehydroxylation increases with the rise of
calcination temperature. These values ranged from 0.98 to 1. For the
calcined halloysite MH650, MH700 and MH750 DIR = 1, indicating the
total transformation of halloysite clay to reactive or amorphous meta-
halloysite at these temperatures. This result is in agreement with TG/
DTA analysis carried earlier on different calcined halloysite samples. In
previous work carried on dehydroxylation of kaolinite studied by
Rahier et al. (2000), they showed that during the calcination of kaoli-
nite, the degree of dehydroxylation slightly increases from 550 to
700 °C and remained almost constant and equal to 1 above 700 °C.
Whereas in our case studied here from 650 to 750 °C the controversy
effect was observed. This could be explained by the disposition or shape
of minerals phase in halloysite which seem to reduce the calcination
temperature ≤ 700 °C as compared to that of standard metakaolin
based geopolymer. The final properties gained on meta-halloysite based
in this research are in agreement with their fine particles compared to
that of standard metakaolin which seem to well behave in alkaline
solution. This finesse of particles might favour the high dissolution of
solid precursor in alkaline medium resulting in an important geopo-
lymer binder content required for the good cohesion between different
components in the geopolymer matrix leading to compact and dense
structure as previously reported by Kaze et al., 2018; Rodrigue et al.,
2020; Kouamo et al., 2020; and Tchakoute et al., 2015. As the com-
pressive strength increased as well as thermal activation, the use of
Nuclear Magnetic Resonance (NMR) spectroscopy needs to be con-
ducted to assess the behaviour of Si and Al during the formation of
geopolymer network at different calcination temperatures. The little
increase in mechanical strength and setting time between GPMH700
and GPMH750 °C geopolymer samples would be assessed using NMR
spectroscopy.
C.R. Kaze, et al.
5. Conclusions
This study aimed to investigate the use of meta-halloysite powders
from calcined halloysite clay from 600 to 750 °C in light to correlate the
thermal activation with reactivity and the strength development. The
following conclusions carry on meta-halloysite based geopolymers
cured at room temperature can be drawn.
1. The increase of calcination temperature from 600 to 750 °C con-
siderably improved the reactivity of halloysite clay by the increase
of amount of amorphous phase within meta-halloysite.
2. From isothermal conduction calorimetry (ICC) it was observed that
GPMH750 and GPMH700 had almost the more total heat released
compared to that of GPMH600 GPMH650 samples indicating higher
reaction degree. Thus, 750 °C appears here as the suitable tem-
perature for the thermal activation of the halloysite clay to ensure
high strength.
3. The mechanical properties of meta-halloysite based geopolymers
remarkably increased with calcination temperature from 600 to
700 °C and slightly between 700 and 750 °C.
4. The microstructure of resultant geopolymer products GPMH650,
GPMH700 and GPMH750 are more compact and denser compared
to that of GPMH600. This trend is line with the increase in amount
of reactive or amorphous phase responsible to higher poly-
condensation of geopolymer network resulting in high development
strength.
5. Although a little increase in compressive strength and setting time
between 700 and 750 °C, the utilization of 750 °C as calcination
temperature would not be economical and sustainable for the geo-
polymer binder in high scale.
Apart from the above findings, further attention would be paid to
measurement of NMR spectroscopy analysis for more details in-
vestigation to optimise the study.
Declaration of Competing Interest
The authors whose names are listed immediately below certify that
they have NO affiliations with or involvement in any organization or
entity with any financial interest (such as honoraria; educational
grants; participation in speakers' bureaus; membership, employment,
consultancies, stock ownership, or other equity interest; and expert
testimony or patent-licensing arrangements), or non-financial interest
(such as personal or professional relationships, affiliations, knowledge
or beliefs) in the subject matter or materials discussed in this manu-
script.
Declaration of Competing Interest
None.
Acknowledgments
RCK gratefully acknowledges Department of Physics, Umm Al-Qura
University, Makkah 21955, Saudi Arabia for running characterization
of the geopolymers products made in this research paper. The authors
are grateful to Ingessil S.r.l., Verona, Italy, for providing sodium silicate
used. Thankful would also be addressed to Mr. Michaël LACROIX for his
helping during the Rheological measurements at the University of
Limoges during my internship.
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