Home Search Collections Journals About Contact us My IOPscience

Comparative study of illite clay and illite-based geopolymer products

This article has been downloaded from IOPscience. Please scroll down to see the full text article.

2011 IOP Conf. Ser.: Mater. Sci. Eng. 18 222027

(http://iopscience.iop.org/1757-899X/18/22/222027)

View the table of contents for this issue, or go to the journal homepage for more

Download details:
IP Address: 200.69.149.82
The article was downloaded on 27/09/2012 at 14:32

Please note that terms and conditions apply.

ICC3: Symposium 16: Innovation in Refractories and Traditional Ceramics IOP Publishing
IOP Conf. Series: Materials Science and Engineering 18 (2011) 222027 doi:10.1088/1757-899X/18/22/222027

Comparative study of illite clay and illite-based geopolymer

products

I Sperberga1, G Sedmale1, G Stinkulis2, K Zeila1 and D Ulme1

1
Riga Technical University, Institute of Silicate Materials, Azenes Str. 14/24, Riga,
LV 1007, Latvia
2
University of Latvia, Faculty of Geography and Earth Sciences, Raina Blvd. 19,
Riga, LV 1586, Latvia

E-mail: sperberga@ktf.rtu.lv

Abstract. Quaternary (Q-clay) clayey deposits are one of the dominating parts of mineral raw
materials of the sedimentary cover at present area of Latvia. These clays can be characterised
by illite content up to 75-80 %. Two ways for use of illite clays were studied: conventional and
geopolymers method. Purpose of the second mentioned method was showing the influence of
alkali (KOH) on the transformation of Q-clay/illite structure. Obtained products were
investigated by IR–spectroscopy, DTA and XRD, pore size distribution was determined as
well. Some ceramic properties and compressive strength were determined and compared. IR-
spectrum showed the effect of alkali on the transformation of Q-clay/illite structure in three
main absorption bands: 3620-3415 cm-1 which is related to the vibrational modes of adsorbed
water between SiO4 and AlO6 layers; new stronger absorption bands at 1635 cm-1 and 1435 cm-
1
indicate on the appearance of vibrations in Q-KOH and are related to the K-O-Si bonds; the
most essential changes are vibrations at 850 cm-1 showing the changes in the coordination
number of Al from 6 to 4 for Q-KOH. Investigations of the bulk density in dependence on
temperature showed the small increase of bulk density for Q-clay while - the relatively
remarkable decrease for Q-clay/KOH. Mentioned values correlate with the compressive
strength of Q-clay and Q-KOH products.

1. Introduction
Geopolymers are mineral polymers from the geochemistry process. Geopolymer starting materials
have to consist of specified amount of silica and alumina which is dissolved in alkaline medium.
Consequently stable polymeric networks of alumosilicates are forming [1].
Geopolymeric materials possess good mechanical properties, including fire and acid resistance.
Mentioned properties make geopolymers as alternative construction material. It is reasonable to
emphasize that the type and nature of the used starting material will directly affect the final physical
and chemical properties of geopolymer [2]. Kaolinite is the most often used raw material because of
its high content of alumina [3,4]. It is thermally activated to transform into amorphous metakaolinite
which is more soluble in basic solution. Searching for another low cost materials are leading to illite
clays - materials wide accessible. Illite clay deposits are one of the dominating mineral raw materials
in the sedimentary cover at present area of Latvia. Quaternary clay deposits mostly are of
glaciolacustrine origin and formed in the Pleistocene glacial meltwater basins. Their grain-size is
various, content of clay minerals are dominated by illite (75-80%) with admixture of chlorite. The
Quaternary clay of Latvia is useful for various kinds of traditional ceramic production such as bricks,
building blocks, roof tiles as well as sorbents and precursors for promoting of sinterability of new


c 2011 Ceramic Society of Japan. 1
Published under licence by IOP Publishing Ltd
ICC3: Symposium 16: Innovation in Refractories and Traditional Ceramics IOP Publishing
IOP Conf. Series: Materials Science and Engineering 18 (2011) 222027 doi:10.1088/1757-899X/18/22/222027

ceramic products [5]. The aim of this study was to synthesize geopolymer product from illite clays of
Latvia under alkaline and alkaline/thermal activation. The effect of KOH solution with different
concentration on the compressive strength were investigated and compared.

2. Materials and methods

Quaternary illite clay of Latvia (Apriki deposit) used for geopolymer synthesis were characterized by
means of chemical analysis (table 1), X-ray diffraction (model Rigaku, Japan, with CuKα radiation at a
scanning interval from 2θ = 10-60o and speed 4 o/min.) and thermal analysis (SeteramTMSETSYS
Evolution-1750) (heating rate 6 oC/min).

Table 1. Chemical composition (wt.sh.) for Apriki clay.

Deposit / Oxides SiO2 Al2O3 Fe2O3 CaO MgO
Apriki clay - Q 49.39 16.60 9.30 5.72 4.25

X-ray diffraction analysis showed that studied clay is mainly composed of illite and quartz with
admixtures of kaolinite, calcite and dolomite.
In order to investigate the effect of the activator (2-8mol/l KOH solution) on the properties of the
material, some series (Q–without activator and Q-KOH- with KOH) were tested. Thus the activator
was added to the clay powder and mechanically mixed. Afterwards cylindric samples (h=25 mm, d=16
mm) were made in plastic way with 23-25 % of average moisture content. At first calcination was
carried out from 700 - 900 oC with step of 100 oC (for Q–without activator and Q-KOH- activated by
2 mol/l KOH solution). Further it was used 4-8 mol/l KOH (K4, K6, K8) solution for clay activation
and treated at 20, 100 and 700 0C temperature (K4 20, K6 20, K8 20, K6 100, K8 100, K4 20+700,
K6 20+700, K8 20+700).
Bulk density and apparent porosity of samples were tested by the Archimedes method using a
distilled water medium. Pore size distribution was determined by means of Hg porosimeter Autopore
IV 95 9500. Compressive strength - by means of the “Toni-Technic by Zwick”.

3. Results and discussion

Geopolymers were synthesized by treatment of natural Quaternary clay with 2mol/l KOH solution.
Differential thermal analysis of both products (Q and Q-KOH) were taken and compared, figure 1.
DTA of both products have the endothermic effects within the temperature range 400-700oC and show
that the loss of crystallization water takes place. This causes the crystalline structure to collapse.
The main differences in
DTA of Q and Q-KOH are
in the temperature range
from 800-900 oC. It is
observed the more
expressive endothermic
effect for Q-KOH which
could be related to
rearragement of the
structure.

Figure 1. DTA and TG of

activated (Q-KOH) and
untreated clay.

IR-spectra of both products are demonstrated in figure 2.

2
ICC3: Symposium 16: Innovation in Refractories and Traditional Ceramics IOP Publishing
IOP Conf. Series: Materials Science and Engineering 18 (2011) 222027 doi:10.1088/1757-899X/18/22/222027

Differences among absorption

frequencies for the untreated clay
and activated one are an
indication of the transformations
taking place during synthesis.
Peaks around 3620-3415 cm-1 are
attributed to the OH- „penetra-
tion” among SiO4 and AlO6
layers. Peak at 2359 cm-1 (only
for untreated clay Q) could be
related to the vibrational modes
of adsorbed water. Formation of
K-O-Si bond could cause peaks
to appear at 1636 and 1435 cm-1
for sample Q-KOH.

Figure 2. IR spectra of Q and Q-KOH samples in the range 600-4000 cm-1.

Characteristic vibrations at 1026 cm-1 (for sample Q-KOH) and 1029 cm-1 (for sample Q) have been
assigned to asymmetric stretching of Al-O and Si-O bonds originating from within individual
tetrahedra. The fact that vibrational frequency is a little bit lower in the geopolymer matrice than in
untreated clay signifies that changes has taken place in the bonding structure within individual
tetrahedra. The possible change in the coordination number of Al from 6 to 4 could cause small peak
to appear at approximately 850 cm-1 for Q-KOH (this peak wasn’t observed for sample Q).
Pore size distribution of thermally treated at 700 oC samples Q and Q-KOH shows the figure 3.

Figure 3. Pore size distribution of thermally treated at 700 oC samples Q (a) and Q-KOH (b).

It is shown that pores of 0,01-0,1 μm size and of 100-1000 μm size are dominating in the sample Q.
Whereas medium size pores (in the range 1-50 μm) developed in the sample Q-KOH as well.
Apparent porosity, bulk density and compressive strength of samples Q and Q-KOH obtained at
700-900 oC temperature shows Table 2.

Table 2. Apparent porosity, bulk density and compressive strength of starting and activated material.
Apparent porosity, % Bulk density, g/cm3 Compressive strength, MPa
Sample
700 oC 800 oC 700 oC 800 oC 700 oC 800 oC
Q 18.4 16.8 2.08 2.10 20 33
Q-KOH 26.1 25.6 2.04 1.95 17 13

3
ICC3: Symposium 16: Innovation in Refractories and Traditional Ceramics IOP Publishing
IOP Conf. Series: Materials Science and Engineering 18 (2011) 222027 doi:10.1088/1757-899X/18/22/222027

Activating of Quaternary clays by 2 mol/l KOH solution, final material showed larger apparent
porosity and smaller compressive strength than that of sample obtained from untreated clay.
Effect of both different concentration of KOH solution (4-8 mol/l or 4-8 M) and following
treatment (20 oC, 100 oC and 700 oC) on results of compressive strength of samples shows Figure 4.
The best compressive
strength (62,59 and 59,06
MPa, respectively) show
products from samples
activated by 6 mol/l KOH
solution and treated at
room (K6 20) and 100 oC
(K6 100) temperature.

Figure 4. Compressive
strength of material: K4,
K6, K8 – sample activated
by 4, 6 and 8 mol/l KOH
solution; 20, 100 and
20+700 – treatment
temperature (oC).

Obviously higher concentration of KOH solution facilitates the dissociation of different silicate and
aluminate species, thus promoting further polymerisation resulting in higher compressive strength.
However, if a very high alkaline environment is used, the connectivity of silicate anions may be
reduced resulting thus in poor polimerisation and lower compressive strength (for sample activated by
8 mol/l KOH solution). Low compressive strength (11,07-11,36 MPa, respectively) demonstrated all
materials obtained by thermal treatment at 700 oC temperature.

4. Conclusions
Illite-based geopolymer product through activating of illite clay by KOH solution was investigated.
Apparent porosity, bulk density and mechanical strength of obtained geopolymer material were
determined and compared with that ones of untreated clay. It was stated that compressive strength of
the geopolymers are greatly dependent on the concentration of KOH solution, but not so - on
treatment (20 and 100 0C) conditions.
It is established that thermal treatment of samples at elevated temperatures (700 oC and higher) greatly
decreases the compressive strength of illite-based geopolymer product while final strength of
kaolinite-based geopolymer could be significantly affected by the alkaline solution concentration apart
from curing method and temperature.

References
[1] Duxon P, Fernández-Jiménez A, Provis JL, Lukey GC, Palomo A and van Deveter JSJ 2007 J.
Mater. Sci. 42 2917-33
[2] Palomo A, Macias A, Blanco MT and Puertas F 1992 Proc. of the 9th Int. Conf. on the Chemistry
of Cement (New Delhi) vol 5 p 505
[3] Zibouche F, Kerdjoudj H, d’Espinose de Lacaillerie J-B and van Damme H 2009 Appl. Clay Sci.
43 453-8
[4] Wang H, Li H and Yan F 2005 Colloids and Surfaces: Physicochemical and Engineering Aspects
268 1-6
[5] Sedmale G, Sperberga I, Hmelov A, Sedmalis U and Actins A 2008 Mat. Sci. Forum 575-
578 953-8