Applied Clay Science 180 (2019) 105192

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Applied Clay Science

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Synthesis, thermal properties and electrical conductivity of phosphoric acid- T

based geopolymer with metakaolin
⁎
Mouna Sellamia, , Maud Barreb, Mohamed Toumia
a
Laboratoire Physico-chimie de L'Etat Solide, Université du Sfax, Faculté des Sciences de Sfax, Route de Soukra Km 3.5, BP 802, Sfax 3018, Tunisia
b
Institut des molécules et Matériaux du Mans (IMMM), CNRS UMR 6283, Le Mans Université, Avenue Olivier Messiaen, F-72085 LE MANS Cedex 9, France

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

Keywords: In this work, kaolin was used to prepare a geopolymer from a phosphoric acid solution. Microstructural prop-
Geopolymer erties were investigated by X-ray powder diffraction, while thermal properties were evaluated by differential
Thermal analysis thermal analysis and thermogravimetry. Finally, the electrical conductivity of the geopolymer and its dielectric
Electrical conductivity properties were investigated.
The results showed that the onset temperature of crystallization of the zeolite phase occurred at 180 °C. This
phase was converted into phosphocristobalite phase at 300 °C and persisted until 1400 °C. From the temperature
of 700 °C, a new crystalline phase was observed: the tridymite SiO2.
The amount of phosphocristobalite and tridymite crystals reached a maximum at approximately 1100 °C,
then, at 1400 °C, the X-ray diagram showed that the peak presented a weak intensity due to the partial dis-
solution of two solid crystalline phases: tridymite and cristobalite. The electrical conduction properties of the
geopolymer indicated first a very low solid-state conductivity (σ ≈ 10−10 S.cm−1), and then above 625 °C, the
conductivity began to rise rapidly, reaching 10−7 S.cm−1.

1. Introduction
Geopolymerization can basically be described as a transformation of
a solid aluminosilicate precursor into an alkali aluminosilicate in-
organic polymer (Duxson et al., 2007; Khale and Chaudhary, 2007), the
resulting material is an amorphous structure consisting of [SiO4]4− and
[AlO4]5− tetrahedra sharing all the corners with each other (Duxson
et al., 2007), that can form tectosilicates. Positive ions Na+ and K+
must be present in the framework cavities to balance the excess of
negative charges of Al3+ in IV- fold coordination (Davidovits, 1991)
([AlO4]5− compared to [SiO4]4−), however, the low dielectric prop-
erties of the alkali-activated geopolymers are not ideal because of the
presence of alkali ions (Cui et al., 2008).
The metakaolin can be activated with a phosphoric acid solution to
prepare a new kind of geopolymers known as phosphoric acid-based
geopolymers (Cui et al., 2008). The metakaolin is formed when kaolin
is calcined within a temperature range of 450–900 °C (Badogiannis
et al., 2005; Ptáĉek et al., 2010).
If in alkali-activated geopolymers, the excess of negative charges on
the [AlO4]5− tetrahedra is compensated by Na+ and K+ ions, in
phosphoric acid-based geopolymer, this excess is balanced by the po-
sitive charges on the [PO4]3− tetrahedra, so that neutrality is
maintained. Thus, this new geopolymer shows better performance than
the alkali-activated geopolymer due to its good mechanical, thermal,
and low dielectric properties (Liu et al., 2010, 2011, 2012; Cui et al.,
2011).
Metakaolin is used with a phosphoric acid solution for producing
geopolymer cements or ceramics, the geopolymer cements are obtained
after curing the fresh samples for 24 h in an oven at about 60 °C (Cao
et al., 2005), while, the geopolymer ceramics are synthesized at room
temperature and they set rapidly like conventional polymers (Singh
et al., 2012).
Few research has been conducted to study different properties of
phosphoric acid-based geopolymers (Liu et al., 2010, 2012) especially
the dielectric ones (Cui et al., 2011). Because of their low dielectric
properties (Liu et al., 2010), geopolymers are used as electronic
packaging materials and insulated encapsulating materials (Cui et al.,
2011).
Douiri et al. (2014, 2016) have recently studied the dielectric
properties of the metakaolin phosphoric acid-based geopolymers at
room temperature, they have demonstrated that the geopolymer ma-
terials were characterized by low dielectric parameters. Some dielectric
phenomena were detected such as proton conduction of free water in
the geopolymers and dipolar polarization at low and high frequency.

⁎
Corresponding author.
E-mail address: mounasellami1@gmail.com (M. Sellami).

https://doi.org/10.1016/j.clay.2019.105192
Received 24 November 2018; Received in revised form 18 June 2019
Available online 26 June 2019
0169-1317/ © 2019 Elsevier B.V. All rights reserved.
M. Sellami, et al. Applied Clay Science 180 (2019) 105192

The aim of the present work was to obtain phosphoric acid-based

geopolymer with low dielectric properties, for this our material was
dried at 300 °C to remove free proton charges provided by water, in this
study, in addition to structural and thermal studies of the phosphoric
acid-based geopolymers, the dielectric properties were investigated.

2. Materials and experimental techniques

The metakaolin (Al2O3.2SiO2) was obtained from well-crystallized

commercial kaolin. Thermal activation of the kaolin was performed at
700 °C for 5 h. The chemical composition of kaolin was determined by
X-Ray fluorescence with Thermo Nitron FXL. The phosphoric acid used
in this study was a commercial phosphoric acid H3PO4 85% provided by
the PROLABO society.
The geopolymer was prepared by mechanically mixing distilled
water, phosphoric acid solution, and metakaolin to form a homogenous
slurry. This specimen was synthesized with molar ratio Si/P = 1. The
slurry was vibrated for 5 min to remove any trapped air before being
transferred into cylindrical molds with a diameter of 25 mm and a Fig. 1. Mineralogical compositions of kaolin, metakaolin and geopolymer.
height of 100 mm, and sealed from the atmosphere. They were then
kept at room temperature for 36 days.
The phase identification of the geopolymer was performed by X-ray Table 1
diffractometry (BRUKER-AXS-D8-Advance) with CoKα radiation Chemical composition of kaolin (mass %).
(λ = 0.178 nm) on geopolymer heated at different temperatures and a SiO2 Al2O3 Fe2O3 MgO Na2O CaO K2O
scanning rate of 10°/min from 10° to 60° (2θ) (step = 0.066, time/
44.17 36.55 1.69 0.27 1.43 0.81 2.13
step = 100 s), the same type of diffractometer working with CuKα ra-
diation (λ = 0.154 nm) on a PANalytical X'pert Pro diffractometer
equipped with the X'celerator detector in the 2θ range from 5 to 60
and Fe2+, and K+ in the interlayer spaces was replaced with Na+ and
(step = 0.033, time/step = 50 s) was used to analyze the kaolin, me-
Ca2+. The proposed chemical formula of this 2:1 phyllosilicate is:
takaolin and unheated geopolymer.
(K0.82Na0.83Ca0.25)(Mg0.1Fe0.36Al3.52)(Al2.07Si5.93)O20(OH)4.
The thermal behaviors were characterized by differential thermal
The great variety of 2:1 phyllosilicates is classified into separate
analysis and thermogravimetry (TG-DTA). This analysis was performed
groups on the basis of the layer charge and interlayer material. The
by Instrument: SDT Q600 V8.1 Build 99, the temperature was raised
charge is between 1.8 and 2.0 in muscovite, and between 1.2 and 1.7 in
from room temperature up to 1400 °C at a heating rate of 10 °C%min−1
illite (Guggenheim et al., 2006), in this case, the layer charge of the
under dry air flow (100 mL·min−1) with α-Al2O3 as reference.
phyllosilicate was about 2, thus, it was a muscovite, hence, the mass %
Electrical conductivity measurements were performed on geopo-
of muscovite and kaolinite in the mixture sample was about 17 wt% and
lymer pellet, the prepared powder was dried at 300 °C for 1 h and
83 wt% respectively.
pressed into a pellet (diameter ≈5 mm and thickness ≈2.4 mm). Thin
The metakaolin comes from the calcination at 700 °C of the kaolin,
platinum layers (≈10 nm) were deposited on each face of the pellet
metakaolin consists of a glassy matrix with a noticeable crystalline
using a Sputter Coater Polaron SC7620 apparatus. The impedance
phase of muscovite.
spectra were recorded over the frequency range from 1 MHz to 1 Hz
The geopolymer XRD diagram shows an important amount of ty-
every 50 °C from 75 °C to 725 °C, under dry air flow, using a
pical amorphous structure. In addition, characteristic diffraction peaks
Schlumberger Solartron 1260 frequency response analyzer connected to
of muscovite remained after geopolymerization with a notable de-
a Schlumberger Solartron 1296 dielectric interface. An AC voltage of
gradation of their intensities. That suggests that muscovite partially
350 mV was used, and a waiting time of 20 min was necessary to reach
participated in the geopolymerization reaction. The partial dissolution
thermal equilibrium after each 50 °C heating or cooling step.
of muscovite in a variety range of acid was reported by Carroll et al.
Equivalent circuits modeling was used to analyze the impedance
(2016).
spectra and the corresponding parameters were obtained by complex
The XRD (with radiation CoKα) data of geopolymer material heated
nonlinear least squares (CNLLSQ) fitting (Moguš-Milanković et al.,
at various temperatures is presented in Fig. 2.
2016) performed on commercial software (Zview) (Moguš-Milanković
It was noticed that peaks correlated to zeolite appeared after firing
et al., 2016).
at 180 °C (Poojary and Clearfield, 1993) with the berlinite phase AlPO4,
this phase was converted into phosphocristobalite phase at 300 °C and
3. Results and discussions
persisted until 1400 °C. From 700 °C, a new crystalline phase tridymite
SiO2 appeared and remained until 1400 °C. Similar behavior was ob-
3.1. X-Ray diffraction analysis
served in the phosphoric acid-based geopolymers synthesized with a
sol-gel method (Liu et al., 2012).
The mineralogical composition of kaolin, metakaolin, and geopo-
lymer determined by XRD (with radiation CuKα) is given in Fig. 1.
Semi-quantitative analysis using the RIR (reference intensity ratio) 3.2. Thermal properties
method showed that the commercial kaolin was a mixture of 85 wt% of
kaolinite and 15 wt% of muscovite. 3.2.1. Heating
The chemical composition of the kaolin, determined by X-ray The results of the thermal analyses on acid-activated geopolymer
fluorescence, is reported in Table 1, the clay was rich in silica, alumina are presented in Fig. 3. Two intensive endothermic peaks appeared on
and contained an amount of iron, calcium, magnesium and potassium the DTA curve at 75 °C and 140 °C with a small peak at 220 °C due to
oxides indicating the probable presence of muscovite or illite, in the 2:1 dehydration of absorbed water in geopolymer (Liu et al., 2012) with a
phyllosilicate, Al3+ in the octahedral sheets was replaced with Mg2+ mass loss of approximately 16%.

2
M. Sellami, et al.
Fig. 2. Phase evolution of geopolymer at elevated temperature.
Fig. 3. TG-DTA thermograms of geopolymer.
In the TG trace, a continuous mass loss of approximately 6% was
observed between 220 °C and 800 °C corresponding to the dihydrox-
ylation of the OH groups.
An interesting observation was a slight weight loss of approximately
2% between 1100 °C and 1400 °C corresponding to the evaporation of
P2O5 (Rokita et al., 1998).
3.2.2. Cooling
Two exothermic peaks appeared on the DTA curve, the first large
peak at 1050 °C corresponds to the polymorphic transition from cris-
tobalite to tridymite and the second sharp peak at 170 °C, corresponds
to the transformation from the high to the low temperature variety form
of phosphocristobalite AlPO4 (Rokita et al., 1998), this agrees with the
X-Ray diffraction powders. During cooling, the sample mass remained
almost constant.
3.3. Electrical conductivity of geopolymer
Even after the sample was heated 1 h at 300 °C, free water was
eliminated out of the sample. From the TG curve, there was a con-
tinuous loss of weight about 6% observed between 220 °C and 800 °C
resulting from the structure water loss, the weight of geopolymer sta-
bilizing after 800 °C. In fact, the structural water of the geopolymer can
impact the dielectric properties (Liu et al., 2011)
Below 575 °C (σ = 4.10−9 S.cm−1), the electrical conductivity va-
lues were so low that it was impossible to explain satisfactorily the
complex impedance diagrams and to model them by an electrical
equivalent circuit.
3
Applied Clay Science 180 (2019) 105192
At low temperatures, the total resistance was estimated from the
intersection of the spectra with the real axis in the Nyquist plane.
The electrical conductivity values from 75 °C to 575 °C were in the
range of 10−9 S.cm−1 and 10−10 S.cm−1. The conductivity was slightly
higher around 575 °C which can be correlated to the mobility of small
amount of the alkali ions Na+ and K+ (Table 1) presented in the fra-
mework cavities of the amorphous structure. The mechanism for the
reaction of Al2O3.2SiO2 powder and phosphoric acid was believed to
involve bonding between the PO4 tetrahedra1 units in phosphoric acid
and the active AleO layer in the aluminosilicate, thus forming a three-
dimensional network consisting of [SiO4]4−, [AlO4]5− and [PO4]3−
tetrahedra sharing all the corners with each other (Cao et al., 2005).
This geopolymer, which was a chain of amorphous mineral molecules
linked together through covalent bonds, presented low dielectric
properties (Liu et al., 2010, 2011, 2012; Cui et al., 2011). However, the
geopolymer was produced from water, H3PO4 and Al2O3.2SiO2 powder
with muscovite as an impurity. It initially contained various amounts of
free Na+ and K+. Before 575 °C, the alkali ions were blocked, there
were no regular conduction paths (due to the absence of periodicity and
symmetry in the amorphous network) thus the geopolymer was an in-
sulating material. The crystallization of the tridymite phase from 575 °C
was accompanied by the structure rearrangement into the amorphous
phase. This new arrangement improved the alkali metal ion transfer
rate and electrical conductivity.
The XRD data of geopolymer material heated at a different tem-
perature (Fig. 3), demonstrated that the tridymite phase appeared from
500 °C to 700 °C.
After 575 °C, it was possible to refine the data with an electrical
equivalent model. The polarization part of the sample and the electrode
polarization were modeled by a constant phase element (CPE), while
the migration part was represented by a resistance R. The complex
impedance spectra were characterized by the appearance a semicircle
centered below the x-axis. The semicircle arc corresponds to ion mi-
gration through the grains (bulk) of the geopolymer and was modeled
by a parallel R//CPE circuit.
From these results, the temperature dependence of the electrical
conductivity could be analyzed following an Arrhenius plot (Fig. 4),
between 575 °C and 725 °C, the conduction properties seem to ap-
proximately follow an Arrhenius law both on heating and cooling with
deduced activation energies which were respectively 0.58 eV and
0.47 eV.
The real part of dielectric permittivity (ε') and the loss factor tangent
(tan δ) as a function of frequency for geopolymer are presented in
Fig. 5. The measurements were performed at different temperature.
On Fig. 5(a) representing the evolution of the dielectric permittivity
with frequency and temperature, the results were in agreement with the
Fig. 4. Temperature dependence of ln(σT) versus 1000/T for geopolymer.
M. Sellami, et al.
Fig. 5. the real permittivity (a) and the loss factor tangent (b) of geopolymer at various temperatures.
previous results and consistent with ionic conduction properties. At
high frequency, the dielectric permittivity remained low at all the
temperatures, indicating a region of dispersion resulting from the re-
laxation of a polarization process within the system (McCarter et al.,
2003), while at low frequency, a significant increase of the dielectric
permittivity was observed at 575 °C. This phenomenon is well evi-
denced on the inset of Fig. 5(a) showing that the permittivity increased
considerably from ε’ ≈ 0.187 at 75 °C to 0.57 at 725 °C at low fre-
quency.
In Fig. 5(b) the loss factor tan δ is plotted for different temperatures
of geopolymer as a function of the frequency.
ε“
tan δ =
ε‘
ε”: dielectric loss.ε’: dielectric constant.
The loss factor tangent or the loss energy of the sample decreased as
the frequency increased, the decrease was rapid at lower frequencies
and became slow at higher frequencies. The decrease tan δ took place
when the jumping frequency of electric charge carriers could not follow
the alternation of the applied electric field beyond a certain critical
frequency (Abdeen, 1999).
A peak appeared at high temperature and was absent at low tem-
perature, which was probably related to the conduction phenomenon
(Douiri et al., 2014).
4. Conclusion
A new phosphoric acid-based geopolymer was synthesized by me-
chanically mixing distilled water, phosphoric acid solution, and meta-
kaolin with molar ratio Si/P = 1. The metakaolin (Al2O3.2SiO2) was
obtained from well-crystallized commercial kaolin. The clay was a
mixture of kaolinite and muscovite.
The geopolymer was studied by X-ray diffraction powder, thermal
analysis, and electrical conductivity.
It was proven that the geopolymer crystallized at low temperature.
During calcination, the change of volume cell of different phases in-
dicated the synthesis of AlPO4-SiO2 solid solutions.
The dielectric parameter values increased as a result of the increase
of temperature. This increase was a result of the enhancement of ionic
conduction phenomenon that was observed at low frequency range.
For the highest temperature, the conductivity did not exceed
10−7 S.cm−1. Therefore, phosphoric acid based geopolymer was a good
insulator and was stable at high temperature.
By decreasing or eliminating the free water, the dielectric loss re-
sulting from ion transfer was negligible, hence, this amorphous material
could have potential applications for use as insulated packaging ma-
terials at high temperatures and also in the aviation industry. Therefore,
4
Applied Clay Science 180 (2019) 105192
an appropriate heat-treatment temperature can ensure the best di-
electric performance of phosphate-based geopolymers, and as such,
phosphate-based geopolymers could likely have different applications.
Acknowledgments
The authors would like to thank the staff of ‘Laboratoire des oxydes
et fluorures, Institut des molécules et Matériaux du Mans (IMMM),
CNRS UMR 6283’ Le Mans Université, France, and the staff of
‘Laboratoire physico-chimie de l'état solide, Faculté des Sciences de
Sfax, Sfax 3018, Tunisia’ for the facilities and support for experimental
work.
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