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Production of refractory chamotte particle-reinforced geopolymer composite

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2016 IOP Conf. Ser.: Mater. Sci. Eng. 123 012041
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3rd International Conference on Competitive Materials and Technology Processes (IC-CMTP3) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 123 (2016) 012041 doi:10.1088/1757-899X/123/1/012041

Production of refractory chamotte particle-reinforced

geopolymer composite
T Kovk, L Kullov, D Rieger
New Technologies - Research Centre, University of West Bohemia, Plze, Czech
Republic
E-mail: toko@ntc.zcu.cz
Abstract. Geopolymer resins are obtained by alkaline activation of aluminosilicate sources
where raw calcined clays are one of the suitable potentialities. Besides the fact that chemical
composition has an essential effect on final properties of the geopolymer binder, the type of
filler strongly affected resulting properties of such granular composite. However, very few
comparative studies have been done on detail description of composite systems: binder
granular filler, in relation to aggregate gradation design and rheology properties of the mixture.
The aim of this work is to develop and describe granular composite concerning workability of
the mixture and kinetics of geopolymerization/polycondensation through flow behaviour. The
rheological measurements indicated that initial viscosities of the mixtures and their evolution
are different for various proportions of the filler. Moreover, it was demonstrated that increase
in complex viscosity responds to the creation of chemical bonds and the formation of structural
network. Finally, a correlation of the mechanism of geopolymer formation was carried out by
differential scanning calorimetry (DSC).

1. Introduction
Geopolymer binders can be considered as a class of inorganic polymers having predominantly
amorphous structure consisting of tetrahedrons SiO4 and AlO4 mutually bonded by oxygen bridges
1]. Thus, the complex structure of polymer network is formed based on Si-O-Al chains. The negative
charge in the aluminosilicate network is balanced by alkali cations (mostly Na+, K+, Ca2+) in the
cavities of framework [2,3]. Geopolymers are generally prepared via alkaline solutions by mixing of
an aluminosilicate raw material in form of powder derived from natural minerals (calcined clays,
natural pozzolans) or industrial products (fly ash, blast-furnace slag, silica rich waste sludge) [4-6].
The mechanism for geopolymer formation involves a reaction between aluminosilicates and alkali
metal hydroxides/silicates [7]. The first disaggregation process entails the severance of the MeO
(where Me is Na+ or K+), SiOSi, AlOAl and AlOSi bonds on the surface of solid particles.
Dissolution of the solid aluminosilicate source by alkaline hydrolysis produces aluminate and silicate
species [8]. Also, the effect of hydroxy groups on the Al-O-Si and Si-O-Si bonds results in
disaggregation/dissolution of aluminates-silicates and formation of hydroxylated complexes such as
Si(OH)4 , Al(OH)4 or Al(OH)36 [9]. Once, the species and complexes are released and
incorporated in aqueous phase by dissolution, the accumulation enhances contact among the
disaggregated products and coagulated structure is formed [10]. This results, in concentrated solutions,
into the gel precipitation through oligomers networking in aqueous phase by condensation process.

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3rd International Conference on Competitive Materials and Technology Processes (IC-CMTP3) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 123 (2016) 012041 doi:10.1088/1757-899X/123/1/012041

The geopolymer binders with a cured rigid structure are represented by good resistance to high
temperatures, acid resistance and mechanical properties [11,12]. Hence, it is an attractive alternative to
standard Portland cement where advanced technical properties of binders are requested. The physical
properties of geopolymer mixtures are strongly dependent on the type and chemical composition of
raw materials, Si/Al molar ratio of prepared slurry and cured conditions [13-15]. The processing
properties of geopolymer binders also depend on the rate of water add to the mixture, proportion of
raw materials and stirring conditions. Also, plate/lamellar-like particle shape of clay minerals affects
rheological properties of the fresh paste, such as thixotropic behaviour with a relatively high yield
stress [16]. The rheology of fresh geopolymer pastes is highly complex process because of the mutual
interactions such as surface forces during dissolution including chemical and mineralogical factors,
contact forces between particles, ratio of water, mixing conditions as well as proportion and type of
filler [17].
The aim of the present study was to investigate the effect of granular filler of ceramic grog on the
rheological properties of variously filled geopolymer paste based on potassium silicate solution.
Differential scanning calorimetry (DSC) was used to study the curing process at elevated temperature
through reactions of heat change.
2. Experimental and methods
The geopolymer paste was synthesized as a two component system consists of alkaline potassium
silicate solution with silica modulus 1.6 and reactive schistous clay residues as a main source of solid
silica and alumina as presented in Table 1 with particle size distribution details as follows: d50 at 3.98
m, d90 at 6.87 m and BET surface area 12.99 m2 g-1. The mixture was formulated by molar ratios:
SiO2/Al2O3 = 2.5, SiO2/K2O = 6.80, Al2O3/K2O = 2.80, H2O/K2O = 19.00. The ceramic grog as
granular filler was used with maximum grain size 1 mm and specific aggregates gradation design as
presented in Figure 1.
Table 1. Main chemical composition of solid and liquid components (mass %)
SiO2
Al2O3
CaO
MgO
TiO2
K2O
Clay residues
50.20
45.10
0.12
0.15
1.45
0.62
Silicate solution
17.57
17.10

Fe2O3
1.00
-

The geopolymer paste was prepared in the mass ratio 1/0.8 (solid/liquid). The materials were
proportioned by weight ratio for optimum workability and the mixing was conducted in a laboratory
automatic blender for 6 min (1000 rpm). After that the batch of A111 filler was added and the final
mixture was blended for an additional 5 min.
The filler gradation design was applied with various proportion of ceramic grog to clay residues
expressed as mass% in the range 260 320 mass%.
Dynamic rheological measurements were performed using a rotary rheometer (Ares G2, TA
Instruments) operated in oscillation mode with small amplitude. Time sweep experiments were
performed at an angular frequency 10 rad/sec (1.59 Hz) and strain rate 0.01% in plain-plain geometry
as presented in Figure 1, detail (a, b). The curing kinetic at 30, 60 and 80C was evaluated by
differential scanning calorimetry (DSC Q200, TA Instruments) using Tzero hermetic alodined
auminum pans/lids. The purge gas was nitrogen at flow rate 50 mL min-1.
3. Results and Discussion
3.1. Rheology
As shown in Figure 2, the rheological time sweep measurements indicate the increasing of viscosity in
time for all filled mixtures. The time zero is taken as a + 15 min in virtue of preparation of the mixture
for each measurement at 30 C 0.1C. The higher proportion of granular filler increased viscosity
rapidly in comparison with the other states, as presented in the Figure 2 (4). This evolution

3rd International Conference on Competitive Materials and Technology Processes (IC-CMTP3) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 123 (2016) 012041 doi:10.1088/1757-899X/123/1/012041

corresponds to the creation of chemical bonds within the reactive mixture [18] and evidently to the
rapid desiccation of the gel infilled by fine particles of ceramic grog. As presented in Figure 2 (0), the
unfilled paste indicates minimal viscosity change in setting time (8000 s). Whereas, the filled mixtures
started notable increasing their viscosities after 2000 s. The geopolymer mixture filled of 260 mass%
reached its viscosity value to 5 GPa.s at 8000 s. Trend indicates that the increasing of proportion of the
filler led to increasing of viscosity value and shorter setting time. As presented in Figure 2 (4), the
highly filled paste increased its ultimate viscosity value to 7.5 GPa.s during 5000 s. The mixture was
spontaneously detached plain-plain geometry after viscosity value reached its maximum.

Figure 1. Gradation curve for ceramic grog with a detail of plain-plain geometry
(a, b) for dynamic rheological measurements

Figure 2. Viscosity curves in function of time of filled mixtures (1) 260 mass %, (2)
280 mass %, (3) 300 mass %, (4) 320 mass % and (0) unfilled paste

3rd International Conference on Competitive Materials and Technology Processes (IC-CMTP3) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 123 (2016) 012041 doi:10.1088/1757-899X/123/1/012041

3.2. Curing kinetics

The geopolymer paste based on potassium silicate solution was measured by differential scanning
calorimetry and started at a time + 10 min in virtue of stirring and moulding/setting the DSC run. The
obtained thermographs indicate curing reactions as a heat evolution under isothermal conditions at 30,
60 and 80C. The exothermic peaks appeared immediately after starting the measurements indicating
the process of partial dissolution/disaggregation of solid particles in the strong alkaline aqueous
solution as presented in Figure 3 (A1, B1, C1) [19]. Further, the formation of alumina/silica-hydroxy
species and consolidation of larger network started as showed in Figure 3 (B2, C2) [20].
It is evident that the elevated temperature affects the mixture to release more heat within the
increasing temperature. Also, the reaction rate in Figure 3 (C1) at 80C is higher than that of A1 at
30C implying that dissolution of raw material is accelerated by elevated temperature. This indicates
that elevated temperature 60-80C speed up curing time to ~ 20 min and both mechanism
disaggregation and reorganization proceeds in short time period.

Figure 3. The effects of heat evolution under isothermal conditions at

(A) 30 C, (B) 60 C, (C) 80C
4. Conclusion
In this investigation, the influences of the proportion of granular filler to geopolymer paste were
studied. Therefore, the ceramic grog with specific aggregate gradation design was applied in various
proportions. It was showed, that increasing of proportion of the filler led to increasing of viscosity
value and shorter setting time. Moreover, it was demonstrated that increasing of complex viscosity
indicates the formation of structural network and gradual desiccation of the gel.
The curing kinetic of experimental mixture was described by effects of heat evolution at normal and
elevated temperatures under isothermal conditions. The exothermic effects indicating acceleration of
structural changes by elevated temperature in the range 60-80C.

3rd International Conference on Competitive Materials and Technology Processes (IC-CMTP3) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 123 (2016) 012041 doi:10.1088/1757-899X/123/1/012041

Acknowledgements
The result was developed within the CENTEM project, reg. no. CZ.1.05/2.1.00/03.0088, cofunded by
the ERDF as part of the Ministry of Education, Youth and Sports OP RDI programme and, in the
followup sustainability stage, supported through CENTEM PLUS (LO1402) by financial means from
the Ministry of Education, Youth and Sports under the National Sustainability Programme I.
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