Materials Letters 116 (2014) 9–12

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Structural, thermal and dielectric properties of phosphoric acid-based

geopolymers with different amounts of H3PO4
Hanen Douiri a,n, Soumaya Louati b, Samir Baklouti b, Mourad Arous a, Zouhir Fakhfakh a
a
Laboratoire des Matériaux Composites Céramiques et Polymères, faculté des sciences de Sfax, Université de Sfax, BP 3000, Tunisia
b
Laboratoire de Chimie industrielle (II), Ecole Nationale d'Ingénieurs de Sfax, Université de Sfax, BP.W 3038, Tunisia

art ic l e i nf o a b s t r a c t

Article history: Phosphoric acid-based geopolymers were synthesized using metakaolin (Al2O3–2SiO2) and different
Received 29 March 2013 amounts of phosphoric acid (H3PO4) at an ambient temperature. Structural and thermal properties of
Accepted 20 October 2013 geopolymers with different molar ratios SiO2/H3PO4 (Si/P ¼1.25, 1.5 and 1.75) were investigated to study
Available online 28 October 2013
the effect of the molar ratio SiO2/H3PO4 (Si/P¼ 1.25, 1.5 and 1.75). The results showed that an increase in
Keywords: the amount of phosphoric acid leads to an augment in the amorphous nature of samples and to a change
Geopolymers in their thermal behaviors. Dielectric measurements at a range frequency of 1–106 Hz revealed that the
Thermal properties permittivity, the dielectric loss and the electrical conductivity of geopolymers at room temperature were
Dielectrics found to be strongly dependent on the H3PO4 concentration. In fact, the addition of phosphoric acid
Proton conduction
improved the ionic conduction resulting in a great change in the dielectric properties.
Dipolar relaxation
& 2013 Elsevier B.V. All rights reserved.

1. Introduction
Geopolymers first developed by Davidovits in the late 1970s
[1], represent a new class of network materials with amorphous to
semi-crystalline nature. These inorganic polymers have recently
attracted much attention because of their excellent fire resistance,
low density, low cost, easy processing, environmentally friendly
nature and excellent thermal properties [2,3]. Therefore, they are
useful in a diverse range of potential applications including
immobilization of toxic and hazardous radioactive wastes,
advanced structural tooling, etc. [1,4–6].
In the preparation of geopolymers, metakaolin is usually used
as a raw material since its chemical composition is simple,
compared to other common precursor materials. Metakaolin can
be activated with a strong alkaline solution (NaOH, KOH, etc.) to
get a traditional alkali based geopolymer. These geopolymers are
known as high ionic conductors used for all solid-state batteries,
electrochemical sensors, etc. [7].
Metakaolin can be also activated with a phosphoric acid
solution to prepare a new kind of geopolymers known as phos-
phoric acid-based geopolymer. They present different mechanical,
thermal and low dielectric properties compared to alkali-based
geopolymers [8]. They are used as electronic packaging materials
and insulated encapsulating materials [9].
Few research have been conducted to study different properties
of phosphoric acid-based geopolymers [10,11] especially the
n
Corresponding author. Tel.: þ 216 97489060; fax: þ216 74 676 610.
E-mail addresses: hanendouiri@yahoo.fr, mouradarous@yahoo.fr (H. Douiri).
dielectric ones [9]. Among these research, the effect of heat
treatment on the dielectric properties of these geopolymers was
studied.
In the present work, in addition to structural and thermal
studies, the dielectric properties have been used to explore the
effect of the variation of phosphoric acid-based geopolymer molar
ratio Si/P.
2. Materials and experimental techniques
Metakaolin (Al2O3–2SiO2) was obtained from well-crystallized
kaolin, named codex kaolin, supplied by the CHEMI-PHARMA
society. Thermal activation of the kaolin was performed at
700 1C for 5 h to form metakaolin. Chemical composition of kaolin
is presented in Table 1. The phosphoric acid used in this study
was a commercial phosphoric acid H3PO4 85% provided by the
PROLABO society.
Geopolymer samples were prepared by mechanically mixing
distilled water, phosphoric acid solution, and stechiometric
amounts of metakaolin forming a homogenous slurry. The molar
ratio solid/liquid (S/L) was maintained constantly and it was equal
to 1. The slurry was vibrated for 5 min to remove any trapped air
before being transferred to cylindrical molds with a diameter of
25 mm and sealed from the atmosphere. They were then kept at
room temperature for 2 h before curing in a laboratory oven at
60 1C for 24 h. Thereafter, samples were maintained at ambient
temperature and pressure for 7 days before demoulding. Speci-
mens used for dielectric measurements were produced with a
diameter of 13 mm and a thickness less than 1 mm. In order to

0167-577X/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matlet.2013.10.075
10 H. Douiri et al. / Materials Letters 116 (2014) 9–12

stop the geopolymerization reaction at 7 days, each specimen was
immersed in acetone for 24 h. Three specimens were synthesized
with different molar ratios x ¼Si/P (x¼1.25, x¼1.5 and x ¼1.75).
Samples differing by the amount of phosphoric acid solution were
added to the metakaolin. For example for x¼ 1.25, the number of
moles of Silicium Si is equal to 1.25 times the number of moles of
the phosphor P.
Phase identification and crystal structure of geopolymers were
performed by X-ray diffractometry (BRUKER-AXS-D8-Advance)
with CuKα radiation (λ¼ 0.154 nm) and a scanning rate of 101/min
from 101 to 601 (2θ). The thermal behaviors of each specimen were
characterized by differential thermal analysis (DTA). This analysis
was performed in a Lynseis Apparatus type L92/095, in the
temperature range of 30–1150 1C, with a heating rate of 5 1C/min.
Dielectric constant, conductivity and loss tangent were mea-
sured by a Novocontrol Dielectric Alpha analyzer at an oscillation
voltage of 1 V. In dielectric analysis, the sample is placed between
two parallel gold electrodes. A sinusoidal voltage is applied,
creating an alternating electric field. This produces polarization
in the sample. Measurements were made in a frequency range of
1 Hz–1 MHz at room temperature.
3. Results and discussions
X-ray diffraction patterns of metakaolin and phosphoric acid
geopolymers with the Si/P ratios of 1.25, 1.5 and 1.75 are given in
Fig. 1. Metakaolin consists of a glassy matrix with noticeable
crystalline phases of quartz and illite. Some new crystalline phases
appeared in geopolymers such as monetite, auguelite and alumi-
num phosphate. The attack of the illite and the quartz resulted in
the formation of a high amount of amorphous aluminosilicate gel.
Then, as the amount of phosphoric acid increases the geopolymer
structure becomes more amorphous.
Table 1
Chemical composition of kaolin (% of mass).
SiO2 Al2O3 Fe2O3 MgO Na2O
44.17 36.55 1.69 0.27 1.83
The results of the thermal analysis DTA are presented in Fig. 2.
For geopolymers, large endothermic peaks appeared correspond-
ing to the dehydration of the absorbed water in geopolymer [10].
A small endothermic peak appeared between 500 1C and 650 1C in
the metakaolin curve corresponding to the elimination of residual
OH groups. At the temperature of 990 1C, small exothermic peaks
appeared on the DTA curve. They correspond to the structural
reorganization of metakaolin and the residual metakaolin in
geopolymers. With the increasing of the molar ratio Si/P, the
amount of the residual metakaolin more important results in an
increase in the intensity of the exothermic peak.
The frequency dependence of the dielectric constant ε′ and the
conductivity s of metakaolin and geopolymers with three different
Si/P ratios are presented in Fig. 3 and its inset, respectively.
The dielectric constant values of sample pastes decreased with the
increase in frequency. This indicates a region of dispersion resulting
from the relaxation of a polarization process within the system [12].
For the dielectric constant and the conductivity, they were improved
and increased with the decreasing of the molar ratio Si/P, i.e. with
increasing rate of phosphoric acid. The ac-conductivity values for
phosphoric acid-based geopolymers are higher than the based
material (metakaolin). Enhancement in the dielectric permittivity
as well as the conductivity of geopolymers may be due to the
presence of additional charge centers caused by the donation of an
extra proton by the phosphoric acid molecule [13]. The mechanism
that contributes to the proton conductivity in phosphoric acid
based geopolymers is almost the structural diffusion (the Grotthuss
mechanism) in which the conductivity is mainly controlled by proton
transport through phosphate ions, i.e. H4PO4 þ and H2PO4  [14].
Fig. 4 presents the variation of the dissipation factor tan δ
versus frequency for different molar ratios. Two peaks appeared in
all the spectra of geopolymers and were absent for the metakaolin.
The first one located in the low frequency range was probably
related to the conduction phenomenon. In fact, phosphoric acid is
a good proton conductor because of its extensive self-ionization
and low acid dissociation constant pKa [14]. The second one
located in the high frequency range suggests the presence of
relaxing dipoles in the specimens [15] such as water dipoles. In
CaO K2O fact, water existing in the geopolymers is a polar molecule
1.81 0.73
characterized by a non-straight H–O–H bonding angle. This means
that it can be easily polarized by an electric field [16].

360
340
320
300
280
260
240
220
Intensity (a.u)

200
180
160
140
120
100
80
60
40
20
0

0 10 20 30 40 50 60
2 Theta (degree)

Fig. 1. Mineralogical compositions of metakaolin and metakaolin geopolymers with different Si/P molar ratios.
 H. Douiri et al. / Materials Letters 116 (2014) 9–12 11

80

metakaolin

Endothermic
60
x = 1.25
x = 1.5
40 x = 1.75

DTA / µV 20

-20

-40

-60
0 100 200 300 400 500 600 700 800 900 1000 1100
Temperature (C )
Fig. 2. DTA curves of metakaolin and metakaolin geopolymers.

1000
1E-06
metakaolin
x = 1.25
1E-07
Conductivity (S / cm)

x = 1.5
x = 1.75
1E-08

100 1E-09
Dielectric constant

1E-10

1E-11
0 1 2 3 4 5 6
log f (Hz)
10

metakaolin

x = 1.25

x = 1.5

x = 1.75

1
0 1 2 3 4 5 6
log f (Hz)
Fig. 3. Dielectric permittivity ε′ and the inset is the conductivity s of metakaolin and phosphoric acid-based geopolymers measured at room temperature.

The intensity of the two peaks increased with the increase of geopolymers as well as their thermal behaviors have been affected
phosphoric acid rate. It resulted from the increase of free protons by the amount of H3PO4 added to metakaolin. For dielectric
as well as dipoles in geopolymers. measurements, experiment results indicate that dielectric para-
meter values increased as a result of the decrease of the molar
ratio Si/P. This increase was a result of the enhancement of ionic
4. Conclusion conduction phenomenon that was observed at low frequency
range. For the highest amount of H3PO4 the conductivity did not
A systematic study of phosphoric acid-based geopolymers exceed 10  6 S/cm. Therefore, whatever is the molar ratio Si/P
properties fabricated from metakaolin and phosphoric acid was (1.25, 1.5 or 1.75), phosphoric acid based geopolymers can serve as
highlighted in this paper. The structures of phosphoric acid based insulating materials.
12 H. Douiri et al. / Materials Letters 116 (2014) 9–12

metakaolin
Conduction
x = 1.25

x = 1.5
2
Dielectric loss x = 1.75

Dipolar relaxation

0
0 1 2 3 4 5 6
log f (Hz)
Fig. 4. Dielectric loss tan δ of metakaolin and geopolymers with different molar ratio Si/P measured at room temperature.

Acknowledgments
The authors would like to thank M.P.F. Graça and L.C. Costa for
realizing DTA analysis.
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