Dan S Perera and Rachael L Trautman Abstract

A geopolymer was prepared by dissolving metakaolinite in a solution of K 2SiO3 and KOH and curing at 80C for 24 h. It was progressively heated from ambient to 1400C in air and the phase changes were studied by X-ray diffraction analysis, scanning electron microscopy and energy dispersive X-ray spectroscopy. Only an amorphous geopolymer phase was observed on heating up to 800C. Kalsilite was the major phase at 1000 C and 1250-1400C. At 1200C leucite was the major phase formed. At 1400C there was no sign of significant melting. The open porosity of the material was ~ 38% at 1000 C, which is sufficiently porous for it to be used as a heat insulation material for continuous use at this temperature.

Keywords
Geopolymer, Refractory Castable, Insulating Refractory, Kaolinite, Refractory Coatings

Introduction
Inorganic polymers formed from naturally occurring aluminosilicates have been termed geopolymers by Davidovits [1]. Various sources of Si and Al, generally in reactive glassy or fine ground forms, are added to concentrated alkali solutions for dissolution and subsequent polymerisation to take place. Typical precursors used are fly ash, ground blast furnace slags, metakaolinite made by heating kaolinite at ~ 750C for 6-24 h, or other sources of Si and Al. The alkali solutions are typically a mixture of hydroxide (e.g. NaOH, KOH), or silicate (Na2SiO3, K2SiO3). The solution dissolves Si and Al ions from the precursor to form a condensation reaction [2]. The OH- ions of neighbouring molecules condense to form an oxygen bond between metal atoms and release a molecule of water. Under the application of low heat (20-90C) the material polymerises to form a rigid polymer containing interstitial water. The polymers consist of amorphous to semicrystalline two or three dimensional aluminosilicate networks, dependent on the Si to Al ratio [1]. Their physical behaviour is similar to that of Portland cement and they have been considered as a possible improvement on cement in respect of compressive strength, resistance to fire, heat and acidity, and as a medium for the encapsulation of hazardous or low/intermediate level radioactive waste [3-6]. Although they have been used in several applications their widespread use is restricted due to lack of long term durability studies, detailed scientific understanding and lack of reproducibility of raw materials. However, if they are to be used as refractory coatings and as low temperature (1000C) refractories, then the lack of long term durability studies will not be a hindrance. Use of geopolymers for these applications have been mentioned in the literature [7]. We have previously heated geopolymers made using Na-alkali up to 1200C and studied their phase formation and microstructure [8]. In the present work we investigated briefly a geopolymer which was much more refractory than those studied before, based on metakaolinite precursor additions. The phase formation and microstructure are discussed.

Experimental
A ~ 30 g batch of geopolymer was made, consisting of 29.1 wt% metakaolinite, 4.9 wt% Ca(OH)2 (Merck, Germany), 11.0 wt% KOH (Sigma Aldrich, Australia), 44.7 wt% Kasil 1552 (PQ Corporation, Australia, composition in wt%: K 2O 21; SiO2 32; H2O - 47) and 10.3 wt% added demineralised water. Metakaolinite was produced by heating kaolinite (Kingwhite 80, Unimin, Australia) at 750C for 15 h in air. An X-ray diffraction (XRD) trace showed a broad diffuse peak centred at a d-spacing ~ 0.36 nm indicative of amorphous material, and a minor amount of quartz. The original clay contained ~ 1 wt% TiO2 but the presence of a Ti-containing phase was not seen by XRD. The dry mixed powders were added to this solution and mixed by hand to ensure a smooth viscous liquid was formed. This was cast in sealed polycarbonate containers and vibrated for 5 min on a vibrating table to remove air bubbles. After holding for 2 h at ambient they were cured for 24 h at 80C. After 5 d at ambient they were removed from the moulds and tests were performed after further 2 d. To study the effect of heating on the microstructure and loss of water and other species, the cured pastes were heated at 500, 800, 1000, 1200, 1300 and 1400C for 3 h in an electric furnace with heating and cooling rates of 5C /min. The density and porosity of each of the geopolymers were determined according to the Australian Standard [9] by evacuating under vacuum and introducing water to saturate the pores. The time of saturation and the immersion in water was kept to less than 15 min to inhibit reaction with water (mainly dissolution of alkali, unpublished work). All samples were analysed by X-ray diffraction (XRD: Model D500, Siemens, Karlsruhe, Germany) using CoK radiation on crushed portions of material. Selected samples were cross sectioned, mounted in epoxy resin and polished to a 0.25 m diamond finish and examined by scanning electron microscopy (SEM: Model 6400, JEOL, Tokyo, Japan) operated at 15 kV and fitted with an X-ray microanalysis system (EDS: Model: Voyager IV, Tracor Northern, Middleton, WI, USA).

Results and Discussion

The values of density and porosity are listed along with XRD analyses of the samples in Table 1. The open porosities of all the geopolymers increase and then decrease with increase of heat-treatment temperature. The most likely explanation is that the increase in porosity is due to the removal of water and breaking of silanol bonds at 500 C, causing the opening of pores. The porosity decrease from 800-1400C is attributed to sintering possibly by assistance from a liquid phase. It is quite feasible to envisage the presence of a liquid phase at 800C for a system consisting of K2O-CaO-Al2O3-SiO2, when the lowest eutectic temperature for the K 2O-CaO-SiO2 alone is 710C [10].

Table 1. Porosity and XRD analysis of Heated Geopolymers Temperature 0C 20 500 800 1000 Open porosity % 29.5 58.5 50.4 37.8 XRD analysis Am (m), Q, Ca8Si5O18 Am (m), Q, Ca8Si5O18 Am (m), Q, Ca8Si5O18 K (m), Q, G, Ca8Si5O18, L (trace)

1200 1250 1300 1350 1400

37.7 30.5 27.6

L (m), K distorted K (m), L distorted K (m), L (trace) distorted K distorted K

Key: m=major; Am= amorphous; Q=quartz; G=gehlenite (2CaO.Al 2O3.SiO2); K=kalsilite (K2O.Al2O3.2SiO2); L=leucite (K2O.Al2O3.4SiO2). The XRD traces of all the geopolymers heated up to 800C showed a broad diffuse hump centred at d ~0.32 nm characteristic of an amorphous phase (Table 1). Trace amounts of quartz and the calcium silicate phase, Ca8Si5O18 were also present. At 1000C, kalsilite was the major phase. Apart from the above crystalline phases, gehlenite was also observed. The SEM image for the geopolymer heated to 1000C shows (Figure 1) a calcium silicate phase with Ca to Si ratio of 8:5 and another one close to the gehlenite composition. The EDS analysis of the matrix indicated the composition was close to that of kalsilite.

Figure 1. SEM image for the geopolymer heated to 1000C shows a calcium silicate phase with Ca to Si ratio of 8:5 and another one close to the gehlenite composition. At 12000C the major phase was leucite and it decreased at 1250 C (Table 1). At 1250C and above kalsilite was the major phase and no leucite was detected at 13501400C. The SEM image (not shown) of the 1400C heated sample confirmed this, but in addition it showed a trace of calcium aluminium silicate in which the Ca:Al:Si ratio was 2:1:2. The d-spacings of the kalsilite phase above 1250C had shifted indicating the possible incorporation of another cation such as Ca (also confirmed by EDS). Similar results have been shown for a metakaolinite/K-alkali system by solid state nuclear magnetic resonance [7]. Kalsilite has a melting point of ~ 1750C [11] and that of leucite is 1686C [11], so both are quite refractory. Although the liquid forms at ~750C, the presence of two refractory phases should be sufficient to make the geopolymer sufficiently refractory at 1000C for continuous use at this temperature. Heating the

geopolymer at 1000C for 5 h did not show any slump and this is an empirical indication of refractoriness. The high porosity of the geopolymers should make them suitable for use as thermal insulators. The pore distribution at 1000C is shown in the secondary SEM image at 1000C (Figure 2). Refractory castables are made by mixing high-alumina cement with chamotte (calcined fireclay). When required water is added and cast to the required shape. Geopolymers could also be used similarly with chamotte. The geopolymers produced in this work had no expansion or shrinkage after curing which is also an advantage.

Figure 2. The pore distribution at 1000C is shown in the secondary SEM image at 1000 A geopolymer made without any aggregate gave a compressive strength of ~ 80 MPa which is sufficiently high compared to alumino silicate thermal insulators used at ~ 1000C (~ 15 MPa at 50% porosity [12]). Thermal insulators are used for lining structurally supporting refractories or as mortars in such structures. Hence, a high temperature high strength is not a pre-requisite for their use.

Conclusions
The geopolymers heated up to 1400C did not show any major melting. The presence of two refractory phases kalsilite and leucite should make them sufficiently refractory at 1000C for its continuous use. High porosity of the geopolymers should make them suitable for use as thermal insulators.

Acknowledgements
Authors thank Joel Davis for unpublished SEM work and Lou Vance for making valuable suggestions.

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