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New inorganic polymeric materials from industrial solid wastes

Conference Paper · June 2007

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Ioanna Giannopoulou Dimitrios Panias

National Technical University of Athens National Technical University of Athens
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 New inorganic polymeric materials from industrial solid wastes
I. Giannopoulou and D. Panias*
National Technical University of Athens, School of Mining and Metallurgical
Engineering, Laboratory of Metallurgy
Iroon Polytechniou 9, 15780 Zografos Campus - Athens, Greece
*
e-mail address: panias@metal.ntua.gr
ABSTRACT
This paper investigates the use of coal-fired fly ash and mine overburdens from the
exploitation of bentonite ores on the development of inorganic polymeric materials
with advanced physical and mechanical properties. The production of these new
materials is based on the geopolymerization technology. The inorganic polymeric
materials produced from the geopolymerization of fly ash developed a compressive
strength up to 40 MPa, while the materials produced from the geopolymerization of
mine overburdens possessed excellent fire resistance. According to these results, the
produced inorganic polymeric materials may be considered as alternatives for
industrial applications in the sectors of construction and building materials.
1. INTRODUCTION
The development of new inorganic polymeric materials from industrial solid wastes
of aluminosilicate composition is subject of an extended research that is taking place
during the last decades. The process according to which these materials are
produced is named “geopolymerization”, because it is similar to geosynthesis [1]
and thus, the produced inorganic polymeric materials are also called “geopolymers”.
Geopolymerization involves a chemical reaction between alumino-silicate oxides
and alkali metal silicate solutions under highly alkaline conditions yielding a three-
dimensional polymeric structure that comprises Si-O-Si and/or Si-O-Al bonds [2].
The geopolymerization reaction is exothermic and is carried out under atmospheric
pressure and at temperatures below 100 oC. The most proposed mechanisms for
geopolymerization include the following four stages [3-5] that proceed in parallel
and thus, it is difficult to be distinguished: (i) dissolution of Si and Al from the solid
alumino-silicate materials in a strong alkaline aqueous solution, (ii) formation of
oligomers species (geopolymers precursors) consisting of Si-O-Si and / or Si-O-Al
polymeric bonds, (iii) polycondensation of the oligomers to form a three-
dimensional aluminosilicate framework (geopolymeric framework) and (iv) bonding
of the undissolved solid particles into the geopolymeric framework and hardening of
the whole system into a final solid polymeric structure.
The produced inorganic polymeric materials are amorphous to semi-crystalline and
possess excellent physical and mechanical properties, including high strength, low
density, micro- or nano- porosity, negligible shrinkage, thermal stability, high
surface hardness, fire and chemical resistance [1,4-7]. Due to these properties,
geopolymers are viewed as alternatives for several industrial applications, mainly in
the sectors of construction and building materials. Therefore, geopolymerization is
considered as an economic and viable technology for the utilization of industrial
solid wastes [3,5,7].
In this direction, the use of several industrial solid wastes, such as fly ash, blast-
furnace slag, mine overburdens, red mud and residues from the processing of
aluminosilicate minerals in the development of geopolymeric materials for
construction purposes has been and continues to be subject of several research
studies. Recent works on the geopolymerization of fly ash [8-12] reported the
production of materials with good mechanical strength, low density, sufficient water
absorption and significant fire resistance. Besides, geopolymerization of blast
furnace slag and red mud in mixtures with slag achieved the development of
materials that presented adequate mechanical strength, fire resistance, resistance to
chemical attacks and low porosity [6, 13] while, geopolymerization of kaolinitic
residue resulted in durable materials with good mechanical properties [7].
The present paper aims at studying the development of inorganic polymeric
materials based on coal-fired fly ash and mine overburdens from bentonite ores
exploitation, according to the geopolymerization technology. In particular, the main
factors affecting the compressive strength of the fly ash-based geopolymers are
summarized and the fire resistance of the overburdens-based geopolymers is
investigated.
2. EXPERIMENTAL
The solid wastes used in this investigation for the development of inorganic
polymeric materials are coal-fired fly ash and overburdens from the exploitation of
bentonite ores. Fly ash (FA) was obtained from the Greek Public Power Corporation
S.A. while, overburdens (OB1 and OB2) originated from the exploitation of
bentonite ores on the Greek island of Milos. The chemical composition of these
solid wastes is presented in Table 1.
Table 1: Chemical analysis of solid wastes
Metal oxide
FA OB1 OB2
(%)
SiO2 48.95 75.71 85.18
Αl2O3 18.61 10.98 3.61
Fe2O3 9.99 1.26 0.81
CaO 10.91 1.21 0.50
K2O 1.73 2.22 0.42
Na2O 0.8 0.73 2.04
Mg O 2.76 0.20 0.78
TiO2 0.97 0.20 0.10
MnO 0.05 - -
SO3 4.12 0.432 0.172
CO2 1.63 - -
L.o.I. 4.03 7.50 6.56
Total 100.52 100.44 100.17
Except for the aforementioned solid wastes, sodium hydroxide of analytical grade
(Merck, anhydrous pellets), sodium silicate solution (Merck, Na2O:SiO2 = 3.4, Na2O
= 7.5-8.5%, SiO2 = 25.5-28.5% and d = 1,346 g/l) and deionized water were used in
the synthesis of the inorganic polymers.
In order to prepare the samples of the inorganic polymeric materials, sodium
hydroxide was diluted in deionised water and mixed with sodium silicate solution
producing the aqueous phase of the synthesis, in which the solid phase of the
synthesis was added. Solid phase of the synthesis comprised the studied solid waste.
The two phases were mixed in a mechanical mixer for 5 minutes in order to produce
homogeneous pastes. Then, pastes were transferred into moulds and cured in an
oven under atmospheric pressure at 60 oC for 72 hours. After this time, samples
were demolded and left 7 days at ambient temperature for more hardening, before
the performance of tests. For samples of the compressive strength test, metallic
cubic moulds (50x50x50 mm) were used, while plastic cylindrical moulds (210x10
mm) were used for the samples of the fire resistance tests.
Compressive strength tests were performed on a testing machine of the
STRUCTURAL BEHAVIOR ENGINEERING LABORATORIES Inc. (PTL-10
model). Two samples of each synthesized material were tested with the average of
the compressive strength values reported as result. For the fire resistance tests, the
front-side of a 10 mm thick sample was exposed at a propane flame with
temperature higher than 1100 oC for 90 min. The reverse-side temperature of the
sample was measured every 5 min using a laser, high performance infrared
thermometer (RAYTEK, Raynger MX4).
3. RESULTS AND DISCUSSION
3.1 Compressive strength
Synthesis parameters of geopolymers, such as the water, sodium hydroxide and
silicate solution content are considered as the main factors affecting the compressing
strength that materials developed [4,5,11-13]. Water content determines the solid to
liquid ratio (S/L) of the starting materials in the synthesis of geopolymers. In Fig. 1,
the compressive strength of the fly ash-based geopolymers prepared for the current
study is plotted as a function of solid/liquid ratio (S/L) in their synthesis.

30
Compressive Str., MPa

25
20
15
10
5
0
1,5 1,6 1,7 1,8 1,9 2 2,1
S/L, g/l

Figure 1: Compressive strength as a function of Solid to Liquid ratio (S/L).

As it is obvious in Fig. 1, compressive strength of geopolymers increased almost
exponentially as the S/L ratio was increased from 1.52 to 2.05 g/ml. Given that the
sodium hydroxide and sodium silicate contents (% mass) of the synthesis are
constant, decrease of the water content results in a substantially increase of the
sodium hydroxide and the initially soluble silicate concentrations in the aqueous
phase of the system. These increases involve the significant acceleration of Si and
Al dissolution from fly ash [10,12] promoting this way the Si and / or Si-Al
oligomers formation and subsequently, the oligomers polycondensation and the
hardening of the geopolymeric system. Besides, the decrease of the water content
favours directly the polycondensation and hardening stages of geopolymerization, as
they are related to the removal of water molecules from the geopolymeric system
[4,5]. Therefore, decrease of the water content in the synthesis of geopolymers
affects positively the whole geopolymerization process improving the mechanical
strength of the geopolymeric materials (Fig. 1). In general, the higher the degree of
polymerization in the geopolymeric structures, the higher the obtained compressive
strength. However, the continuous decreasing of the water content in the synthesis
may causes insufficient wetting of fly ash particles, affecting negatively the paste
workability and making extremely difficult its moulding. In this study, this behavior
was observed for pastes produced with S/L ratio higher than 2.05 g/l.
In Fig. 2, the compressive strength of the fly ash-based geopolymers versus the
sodium hydroxide concentration is presented.
According to Figure 2, compressive strength increased as NaOH concentration in the
aqueous phase was increased from 4.47 M to 6.6 M and then, decreased with farther
increase of NaOH concentration, until 10.25 M that is the highest value of NaOH
concentration examined in the present study.
 30
Compressive Str., MPa 25
20
15
10
5
0
4 5 6 7 8 9 10 11
[NaOH], M

Figure 2: Compressive strength as a function of sodium hydroxide concentration.

As it is mentioned above, increase of NaOH concentration in the aqueous phase of
the synthesis results in direct increase of the dissolution rate of Si and Si-Al phases
of fly ash improving the effectiveness of the geopolymerization process. Increased
Si and Al contents in the aqueous phase of the geopolymeric system are essential for
the initiation of the formation of oligomers and in turn, for polycondensation. Thus,
the increase of NaOH concentration in the aqueous phase of the synthesis shall
affect positively the mechanical strength of the obtained materials. However, this is
not in accordance with the experimental results shown in Figure 2. Although the
formation of oligomers is enhanced by the increased contents of Si and Al in the
aqueous phase, is inhibited under extremely high NaOH concentrations. In these
conditions, the oligomeric silicate species that promote the geopolymerization
process loose their stability in favor of mononuclear silicate species inhibiting the
process [12]. As a result, the concentration of oligomers is minimized decelerating
the polycondensation process and its effectiveness measured with the compressive
strength of the produced materials.
Concluding, the increased NaOH concentration in the aqueous phase of the synthesis
affects positively, as well as negatively the mechanical strength of the geopolymers.
Thus, a compromise of the NaOH concentration in the aqueous phase is claimed.
For the case under study this compromise is set at the value of 6.6 M.
In Figure 3, the compressive strength of the fly ash-based geopolymers is plotted as
a function of the soluble silicate concentration in the aqueous phase of the synthesis.

50
Compressive Str., MPa

40

30
20

10

0
0,5 1 1,5 2 2,5
[SiO2 ], M

Figure 3: Compressive strength as a function of soluble silicate concentration.

As it is shown in Figure 3, the compressive strength of geopolymers was increased
almost linearly with the increase of silicon content in the aqueous phase of the
synthesis from 0.69 M to 2.31 M. Under constant NaOH content in the aqueous
phase, the continuous addition of soluble silicates increases the SiO2 to Na2O ratio.
This increment results in the gradually shift of the chemical system to species with
large rings and then to complex structures and polymers giving rise to the three-
dimensional polymeric framework and consequently, increasing the mechanical
properties of the resulted geopolymeric materials [12]. The beneficial effect of the
increased SiO2 to Na2O ratio on the mechanical properties of the geopolymers is
limited by the viscosity of the produced pastes, which increases substantially under
especially high SiO2 to Na2O ratios causing inefficient pastes workability and
difficulties during their molding. In the case of the fly ash studied in the present
work, this limit was determined by a silicate concentration equal to 2.31 M.
3.2 Fire resistance
In order to study the fire resistance of the overburdens-based inorganic polymeric
materials, the inorganic polymeric materials G-OB1 and G-OB2 were prepared from
the mine overburdens OB1 and OB2, respectively. The samples G-OB1 and G-OB2
were synthesized under optimal composition conditions and developed compressive
strength, equal to 10.30 MPa and 20.10 MPa, respectively.
The behavior of materials G-OB1 and G-OB2 under exposure to a flame of high
temperature is shown in Fig. 4, where the reverse-side temperature of the exposed
samples is plotted as a function of time.

300
Temperature, oC

250
G-OB2
200
150
G-OB1
100
50
0
0 10 20 30 40 50 60 70 80 90
Time, min

Figure 4: Reverse-side temperature versus time of 10mm thick geopolymeric panels

exposed at a propane flame of temperature higher than 1100 oC.
According to Fig. 4, during the first 20 minutes of exposure at the propane flame
with temperature higher than 1100 oC, the temperature of the reverse-side of both
geopolymer samples was about 100 oC. The reverse-side temperature of G-OB1 rose
to ~ 200 oC after 60 min and remained constant for the rest 30 min of exposure at the
flame. In the case of G-OB2, the reverse-side temperature rose to ~275 oC after 40
min and remained almost constant for the following 50 min of exposure in the
flame. The front-side temperature of samples was constant during the tests, ranged
in between 750 oC to 800 oC. Neither cracks nor melts, was observed in both cases
of materials during the whole duration of the test. Comparing these results to the fire
resistance of commercial products or of materials reported in similar researches [6,
14], it is obvious that geopolymerization of the overburdens OB1 and OB2
examined in the present study may lead to the development of fire proofing
materials. However, further investigation is necessary for the optimization of these
materials and their properties.
4. CONCLUSIONS
Water, sodium hydroxide and silicate solution contents were proved as crucial
synthesis parameters of geopolymers for the development of mechanical properties,
as they affect directly or indirectly all the stages of the geopolymerization process.
 Fly ash-based geopolymers developed a compressive strength of 41.3 MPa for S/L
ratio equal to 2.05 g/ml, sodium hydroxide concentration in the aqueous phase equal
to 6.6 M and soluble silicate concentration in the aqueous phase equal to 2.3 M.
Geopolymerization of overburdens originated from bentonite ores exploitation may
lead to the development of fire resistant materials. Geopolymer samples produced
under optimal synthesis conditions from these overburdens, presented a temperature
gradient of 550 oC – 600 oC between the front- and the reverse-side upon their
exposure to propane flame with temperature higher than 1100 oC.
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