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Alkali activation of kaolinite for production of bricks and tiles

Conference Paper · January 2011

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H. Rahier Muayad Esaifan

Vrije Universiteit Brussel University of Jordan
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 ALKALI ACTIVATION OF KAOLINITE FOR
PRODUCTION OF BRICKS AND TILES
Hubert Rahier, Muayad Esaifan, Jan Wastiels, Faten Slatyi, Islam
Aldabsheh, Hani Khoury

Abstract

New low cost building materials were developed by alkali activation of Jordanian Hiswa
kaolinite. The optimum amount of NaOH, water and added sand were determined.
Physical, thermal, mineralogical and microstructural properties were investigated. A
compressive strength of 32 MPa was obtained for a geopolymer mixture cured at 80 ˚C
for 24 hours. The petrography results indicate that the geopolymerization process has
increased the compaction and decreased the porosity. The mineralogical and
microstructural results on the hardened geopolymer indicate the formation of sodium
zeolite phases and feldspathoids. The high compressive strength is directly related to the
formation of the new phases that fill the pore spaces and bind the matrix.

Keywords: kaolinite, NaOH, geopolymer, alkali activation, durability

1 Introduction

The purpose of this study is to use local raw materials with a low energy impact to
produce construction materials. Since some years research is going on in Jordan to
produce construction materials, starting from local raw materials. Geopolymers have the
benefit that they have a smaller environmental impact than concrete, but also the main
raw material, for instance kaolinite, is often locally available. To minimize the production
cost, the kaolinite will be used as such and thus not be dehydroxylated.

Geopolymerization is the reaction of solid aluminosilicate with a liquid alkali component

as an activator agent, forming an inorganic polymeric network of alkali aluminosilicates
[i,ii]. The solid aluminosilicate can be kaolinite, metakaolinite, fly ash, blast furnace slag,
or waste products from power stations and mining processes. The terminology is not
normalized yet. Besides geopolymers, also inorganic polymers [iii], mineral polymers
[iv,v] and alkali activation [vi] are used by different authors. Geopolymers can be
amorphous to crystalline products (analogues of natural zeolites) and are produced at
low-temperature. The alkaline liquids contain alkali metal ions usually sodium and/or
potassium. The water in the geopolymer mixture provides a reaction medium and assures
the workability of the mixture during mixing and handling. Filler materials may be used
to enhance desired properties including mechanical strength and density.

Geopolymers are an attractive alternative to Portland cement, characterized by a

comparable compressive strength, hardness, and chemical stability. Less energy is
consumed however and less greenhouse gases are emitted during production [vii]. Some
researchers studied the reaction mechanism occurring at temperatures lower than 100 ˚C,
and concluded that the aluminosilicate is attacked by OH-, giving rise to some species
going into solution. These recombine in a polycondensation reaction resulting in the
geopolymer [viii-xi]. The Si and Al atoms in the framework of aluminosilicate
geopolymers are tetrahedrally coordinated and linked via oxygen bridges [xii]. The
negative charge on the AlO4- group is charge-balanced by alkali cations (typically Na+
and/or K+).

The main goal of this research is to characterize the geopolymers using kaolinite as such.
Next to kaolinite some other minerals weere screende on there usefullness for alkali
activation. The clay deposits in Jordan are widely used and the extracted clays have a low
price [xiii]. It must be stressed that in this study the kaolinite is not thermally activated,
but used as such. Thermal activation increases the reactivity [xiv] but also induces the
need for firing and increases the ecological impact of the material. The fact that zeolites
can be formed from kaolinite and NaOH solutions is known for longtime [xv]. It is
however not widely known that decent construction materials can be produced at ambient
temperatures from these components. The aim of this research is to optimize the
production (composition, curing ).

2 Experimental
The different Jordanian raw materials are: Jordanian Hiswa kaolinite, smectite rich clay,
and volcanic tuff. To check the reactivity the samples were sieved to <63 µm. The
kaolinite as selected for further investigation. The composition of the geopolymer
specimens was: Jordanian Hiswa kaolinite (JHK) as aluminosilicate source, Jordanian
silica sand (90 to 250 µm) from south Jordan as a filler material (JSS), and NaOH from
Merck (99 %). Preparation of the geopolymer specimens was done in three steps:
1- Mixing: the amount of kaolinite and sand were mixed using a laboratory mixer. The
alkali solution was prepared by mixing NaOH and distilled water in a closed plastic
bottle to avoid evaporation. The cooled NaOH solution was added gradually to the
kaolinite/sand mixture and mixed for 10 minutes to get an optimum homogeneity.
2- Moulding: the mixture was put into a stainless steel cylinder mould (50*25 mm) and
compacted with a pressure of 16 MPa by using a hydraulic compressor, then de-
moulded and weighed. With one mixture at least 3 specimens were prepared.
3- Curing: the uncovered specimens were placed in a ventilated oven at 80 ˚C for 24
hour, unless specified otherwise.

The compressive strength of the geopolymer specimens was measured by using a

CONTROLS testing machine (Model T106 modified to suit standard testing), where the
load was applied and increased by a displacement rate of 3 mm/min. An average of three
specimens per measurement was taken.
2.1 Optimization of ratio and curing conditions
The optimal components ratio was studied by preparing series of specimens with
different ratios. In this work, the amount of distilled water added was taken as the
plasticity limit for the mixture of kaolinite and sand. The optimal ratio of the other
components in the mixture was determined depending on the best compressive strength
as will be highlighted in the part results and discussion. Six series were prepared using
different mass ratios of NaOH (8, 12, 14, 16, 18, and 20) and 100 JHK, 50 JSS, and 22
H2O, parts in mass. The specimens were cured at 80 ˚C for 24 h. Four series of samples
with a composition of 100 JHK, 22 H2O, and 16 NaOH, parts in mass, were prepared
with different sand ratios (25, 50, 100, and 150) and cured at 80 ˚C for 24 h.

The compressive strength of the geopolymer specimens was measured by using a

modified motorized CBR device, at a displacement rate of 3 mm/min. An average of
three specimens per measurement was taken.

2.2 Characterization of the raw materials and optimized geopolymer

The thermal behavior was determined by TG/DTA analysis. The analysis was done by
using a Netzsch STA 409 thermal analyzer. The samples (approximately 36 mg, size <
425 μm) were heated in an alumina cup at a rate of 20 ˚C/min, starting from 50 ˚C up to a
maximum temperature of 1000 ˚C using N2 as a purge gas [xvi].

3 Results and discussion

To make a selection of possible raw materials for geopolymerization, the different raw
materials were subjected to a leaching procedure in a 10 M NaOH solution. Fig 1 shows
the amount of Si and Al in solution after 7 days. These amounts were related to the total
amount of the element in the raw material. It is clear that for the kaolinite and for the
smectite rich clay more than 30% of the initial Si and Al went into solution. For the tuff
the values were lower, especially for Al. This indicates a lower reactivity. The kaolinite
and smectite rich clays mainly contained kaolinite and quartz[xiv]. Since quartz is much
more stable than kaolinite, it is obvious that the Si in the solution originated from the
break-down of kaolinite.
Fig. 2 shows the weight loss of the Jordanian Hiswa kaolinite till 1000°C. A small
amount of adsorbed water is present (about 2wt%). The step at about 500°C is due to the
dehydroxylation of kaolinite. Comparing the height of this step (9.5wt% between 300 and
800°C) to the weight loss found for pure kaolinite in the same temperature interval
(13.76%12) shows that the Jordanian Hiswa kaolinite contained about 69wt% of kaolinite
by weight. If the amount of Si leached out is related only to the kaolinite, then the amount
of kaolinite dissolved would be approximately 45wt%. Thus according to this leaching
test the residual sample would still contain 24wt% of kaolinite after 7 days in 10M NaOH
solution.
 40
Al

Extent of dissolution (%)

35
Si Al Si
30
25
20 Si
15 Al

10
5
0
K

Vt
Sc

Figure 1 Extent of dissolution of Si and Al in solution after leaching of kaolinite (K),

smectite rich clay (Sc) and volcanic tuff (Vt) in 10M NaOH for 7 days at 25°C

100.0
fresh
Weight (%)

90.0
7 days

80.0

70.0
0 500 1000
Temperature (°C)
Figure 2 TGA thermograms of Jordanian Hiswa kaolinite before (top, fresh) and after
leaching (bottom) for 7 days in 10M NaOH

The weight loss of the residue after the leaching consists of two well separated steps. The
first step at about 100°C is due to free water. The second step consists of some
overlapping phenomena. The first starts around 300°C and counts for 2wt%. It is
probably due to new phases formed. The next step lies in the temperature ranges of the
dehydroxylation of kaolinite, although a tail at the high temperature side is remarked. If
this step were only due to the dehydroxylation of remaining kaolinite, this amount can be
calculated. The height of the step is 8.8%. The remaining kaolinite is therefore estimated
to be more than 60%. This value is much higher than expected, since according to the
leaching test only 24wt% of kaolinite remains. This weight loss step is thus also due to
other new phases than kaolinite.
The fact that new phases are formed during the leaching process implies that the
concentrations measured in the solution (Fig.1) do not give a complete picture of the
chemical break down of the mineral. The concentration in the solution will be lowered by
the precipitation of the new phases.
The leaching out of Si and Al is the first step of the geopolymerisationxv, xvi. At least the
first part of the DSC thermogram (Fig. 3) is thus due to this process. The height of the
DSC signal reflects the reaction rate (heat released per unit of time). The smaller
reactivity of the tuff is clear from these data. The tuff only starts to react visibly above
100°C where the kaolinite (JHK) already reacts from 80°C. The smectite-rich clay also
starts reacting at 80°C but shows a smaller reactivity below 100°C.
Heat Flow (W.g -1)

0.05 Wg-1

exo up

0 100 200
Temperature (°C)

Figure 3 DSC thermograms of tuff, Jordanian Hiswa kaolinite and Jordanian smectite
rich clay with 10 M NaOH

It can also be remarked that the reactivity of these clays is much smaller compared to the
reactivity of thermally treated clays such as metakaolinite or fly ash [xii].
Figure 4 indicates that an optimum compressive strength is obtained for an amount of 16
parts of NaOH to 100 parts of kaolinite by weight.
 40

Compressive strength (MPa)

35
30
25
20
15
10
5
0
8 12 16 20
NaOH (parts)

Figure 4 Compressive strength of geopolymers with different amounts of NaOH (in

parts/100 parts of Hiswa kaolinite).

Filler materials like sand reduce cracking and decrease the porosity of the composite.
Fillers also reduce the quantity of binder paste making the resultant material less
expensive. The effect of adding sand grains to the geopolymer mixture on the
compressive strength is shown in Figure 6. Increasing the sand content has also shown
good workability of the mixture. The best compressive strength values are obtained for a
JSS:JHK ratio of 0.5 to 1.

Figure 5 NaOH ratio vs. compressive strength. Samples with composition 100 JHK, 50
JSS and 22 H2O and cured for 24h at 80 ˚C.
Figure 6 shows the X-ray diffractogram of the optimized geopolymer. The chart indicates
that the reaction of kaolinite with NaOH results mainly in new alkaline sodium
aluminosilicate phases. These phases are Na-zeolitic minerals namely: phillipsite
((Na,K,Ca)1-2(Si,Al)8O16.6(H2O)) and natrolite ( Na2Al2Si3O8.2(H2O)). A feldspathoid
phase of hydroxysodalite (Na2Si2Al2O5(H2O)6) is also identified. Quartz occurs as a
major phase in the specimen due to the added JSS filler along with the remains of
kaolinite, muscovite/illite, and hematite from the raw material.

Q: Quartz
K: Kaolinite
H: Hematite
M/I: Muscovite/ Illite
Q P: Phillipsite
S: Hydroxysodalite
N: Natrolite
Q A: Alunite
Q
+ Q
Q N Q Q
M/I K M/I Q
S + K S+ Q
K+ S +
N + N Q
P S Q H
M/I N H H
P H K AH

2 10 20 30 40 50 60 70
2-Theta (°)
Figure 6: XRD spectrum of the optimized geopolymer. Samples with composition 100
JHK, 100 JSS, 16 NaOH, and 22 H2O and cured at 80 ˚C for 24 h

4 Conclusions
The dissolution procedure of minerals in an alkaline solution can give an indication of the
reactivity of the minerals. However, since precipitation occurs, even if only 25g of
mineral in 1L of solution is used, the concentrations in the solution do not tell exactly
how much Si or Al has been leached out. In the case of dissolution of kaolinite containing
minerals, it is clear that precipitation of hydrated phases occurs. The kaolinite- and
smectite-rich clays dissolve at a comparable rate. The tuff sample dissolves slower. This
order is confirmed by DSC. DSC also shows that the reaction starts at about 80°C for the
kaolinite- and smectite-rich clay. Since the reactivity at room temperature of the
kaolinite/NaOH system is rather low, the materials need to be produced at a higher
temperature. This is in contrast to geopolymers produced from metakaolinite, which set
in a few hours time at room temperature. For this reason the specimens were cured at
80°C for 24h. The optimum compression strength was found for a mixing ratio of 16g
NaOH/100g kaolinite. The mechanical properties of the geopolymers formed from the
Jordanian Hiswa Kaolinite are good enough for the construction of water ponds but also
for other small constructions.

Acknowledgements
This paper was elaborated with the financial support of the VLIR (Flanders-Belgium,
project nr ZEIN2006PR33).
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 Hubert Rahier, prof., Dept. Materials and Chemitry at Vrije Universiteit Brussel,
Pleinlaan 2, 1050Brussels, Belgium
Tel. +32-2-6293277, fax +32-2-6293278 e-mail: hrahier@vub.ac.be
Muayad Esaifan, ir., Dept of mechanics and constructions at Vrije Universiteit Brussel,
Pleinlaan 2, 1050Brussels, Belgium
Tel. +32-2-6292955, fax +32-2-6293278 e-mail: Muayad.Esaifan@vub.ac.be
Jan Wastiels, prof., Dept of mechanics and constructions at Vrije Universiteit Brussel,
Pleinlaan 2, 1050Brussels, Belgium
Tel. +32-2-6292924, fax +32-2-6292928 e-mail: jwastiel@vub.ac.be
Faten Slatyi, Ph.D., Materials Research Laboratory at University of Jordan, 11942
Amman, Jordan.
Tel.+ 962-6-5341879, fax +962-6-5348932, e-mail: fmastergeo@gmail.com
Islam Aldabsheh, Ph.D., Materials Research Laboratory at University of Jordan, 11942
Amman, Jordan.
Tel.+ 962-6-5341879, fax +962-6-5348932, e-mail: islam.aldabsheh@gmail.com
Hani Khoury, prof., Materials Research Laboratory at University of Jordan, 11942
Amman, Jordan.
Tel.+ 962-6-5341879, fax +962-6-5348932, e-mail: khouryhn@ju.edu.jo

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