Materials Research Bulletin 38 (2003) 319331

Thermal behaviour of inorganic geopolymers and composites derived from sodium polysialate
Valeria F.F. Barbosa, Kenneth J.D. MacKenzie*
New Zealand Institute for Industrial Research and Development, P.O. Box 31-310, Lower Hutt, New Zealand Received 21 June 2002; accepted 25 October 2002

Abstract Inorganic polymers based on alumina and silica polysialate units were synthesised at room temperature from metakaolinite and sodium silicate in a highly alkaline medium, followed by curing and drying at 65 8C. When properly cured, these polymers exhibit remarkable thermal stability; after losing their hydration water at about 200 8C, they retain their X-ray-amorphous tetrahedral Al and Si network up to the onset of melting at 1300 8C. A small amount of mullite and corundum formed at 12001300 8C may result from the presence of a trace of unreacted metakaolinite. Similar experiments with poorly-curing formulations containing higher Na and Si contents show that their unpolymerised components form crystalline nepheline (NaAlSiO4) at 800 8C, prior to melting at about 1100 8C. A series of geopolymer composites were prepared containing 1020 vol.% of various granular inorganic llers ranging from waste demolition materials through mineral tailings to engineering ceramics. The physical and thermal properties (bulk density, compressive strength and thermal expansion) of these composites were measured. The thermal expansion is inuenced by the properties of the ller, but all the samples showed only slight expansion up to 800 8C on the rst heating cycle. Microcracking of the composite bodies during drying can be minimised by the addition of a small amount of glycerol. # 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Inorganic compounds; Polymers; Nuclear magnetic resonance (NMR); X-ray diffraction; Thermal expansion

1. Introduction A new family of inorganic polymeric materials, the polysialates and polymers based on related aluminosilicate units, has emerged in the last few years. Their physical properties make them viable alternatives for many conventional cements and plastics, and their synthesis at low temperatures is energy-efcient and more environmentally-friendly than many older materials [1].
Corresponding author. Tel.: 64-4-5690513; fax: 64-4-5690142. E-mail address: k.mackenzie@irl.cri.nz (K.J.D. MacKenzie). 0025-5408/02/$ see front matter # 2002 Elsevier Science Ltd. All rights reserved. PII: S 0 0 2 5 - 5 4 0 8 ( 0 2 ) 0 1 0 2 2 - X
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The polysialates are based on aluminosilicate units such as sialate [SiOAlO], sialate siloxo [SiOAlOSiO] or sialate disiloxo [SiOAlOSiOSiO]. The polymerised materials contain almost exclusively tetrahedral Al, charge balance being achieved by the presence of Na or K. The polymers are synthesised by reacting dehydroxylated aluminosilicate (kaolinite) with the correct proportion of an alkali metal silicate under strongly alkaline conditions and with strict control of the water content. The polymers, which can be formed to net shape, cure and harden at temperatures between ambient and 65 8C. Although X-ray amorphous, they have been studied by FTIR and solid state MAS NMR spectroscopy [1], which conrms the presence of a range of silicon environments similar to glasses or hydrated silicate minerals, but predominantly the Al-saturated framework structure SiQ4(3Al). After drying for 1 h at 65 8C, polymers based on sodium polysialate units typically display compressive strengths of about 48 MPa. Mohs hardness >7 and Vickers hardness of about 54 [1]. These polymers can also be used as a matrix for the preparation of composites containing a variety of granular inorganic llers. Since both the polymers and inorganic polymer composites have potential high temperature applications as heat-resistant substitutes for ammable organic materials, their behaviour at elevated temperatures is of interest. This paper reports the thermal behaviour (high-temperature reactions, phase changes on melting and thermal expansion properties) of sodium polysialate. Another property of these polymers is their reported ability to act as a bonding agent or matrix for composites with other inorganic materials such as mineral wastes, bres or woven mats [2]. The thermal behavior was, therefore, investigated for a series of polysialate composites containing granular inorganic materials ranging from crushed demolition materials and mining debris to oxide and non-oxide engineering ceramics. 2. Experimental program The polymers were synthesised from Brazilian kaolinite dehydroxylated at 700 8C for 6 h, sodium silicate (Gessy Lever) and sodium hydroxide pellets (grade P.A, Vetec). Most of the present work was carried out using a composition previously found [1] to cure and harden well; this formulation, designated Na-PSS1 is dened by the compositional ratios SiO2/Al2 O3 3:3, Na2O/SiO2 0:25 and H2O/Na2 O 10. For comparison, a few experiments were done on two other formulations previously found not to cure or harden well [1], with the aim of shedding light on the differences in their behaviour and to explore the possibility that their properties might be improved by thermal treatment at higher temperatures. One of these, designated Na-PSS2, differs from Na-PSS1 in containing more water (H2O/Na2 O 25); the other, designated Na-PSS7 has SiO2/Al2 O3 3:8, Na2O/SiO2 0:3 and H2O/ Na2 O 17:5. The reagents were mixed in the calculated proportions, placed in 35-mm diameter 70-mm high cylindrical plastic moulds, allowed to mature at room temperature for 60 min, cured at 65 8C for 90 min and dried at 65 8C for 60 min. The water was retained in the system during the curing stage by sealing the top of the mould with thin plastic lm, which was removed prior to the drying stage. A series of composites were also made, using geopolymer Na-PSS1 as the matrix and containing 1020 vol.% of the following inorganic llers:  Crushed brick, prepared from standard commercial red brick pavers ground to pass a 152-mm sieve. The mineralogical components (determined by XRD) were quartz > albite @ mullite, and the density, determined using xylol, was 2.67 g ml1.

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 Powdered stone, the residue from commercial crushing operations of Brazilian granite rock, found by XRD to contain phlogopite > albite @ quartz. The particle size was 0.15 mm and the density was 2.52 g ml1.  Kaolinite, Brazilian, containing a small amount of quartz impurity, particle size <6 mm, density 2.51 g ml1.  Ironsand, from the West coast of the North Island of New Zealand, consisting of black magnetic titanomagnetite containing 7.0% TiO2, ground to pass a 152-mm sieve, density 4.7 g ml1.  Alumina, BDH reagent grade a-alumina (corundum), calcined at 1000 8C for 1 h to remove volatiles. The density was 3.89 g ml1.  b-Sialon, prepared by carbothermal synthesis from halloysite clay [3], composition corresponding to z 2:45 (from XRD cell parameter measurements). The mean particle size was <6 mm and the density was 3.0 g ml1. The compressive strengths of these cylindrical geopolymer composite samples were determined using a 100-ton testing machine (Alfred J. Amster). The testing was carried out in the manner of compressive testing of concrete samples, with an axial load applied on the cylinder face at a rate of 25 mm min1. Measurements of thermal expansion were made of composition Na-PSS1 and the Na-PSS1 composites in ambient atmosphere using a Harrop Laboratories dilatometer at a heating rate of 1 8C min1 on bar-shaped samples 50 mm 7 mm 7 mm cured and dried in a similar manner in a mold of the correct dimensions. Samples of the other compositions were too soft to permit dilatometry. Differential scanning calorimetry (DSC) and thermogravimetry (TGA) was carried out on the cured and dried sample Na-PSS1 in owing nitrogen (20 ml min1) at heating rates of 20 8C min1 (TGA) and 10 8C min1 (DSC) using a Shimadzu thermal analyser with DSC-50 and TGA-50 attachments. Pieces of the cured and dried samples were heated in alumina boats in an electric furnace for 1 h at various temperatures up to 1300 8C. The samples were then crushed and examined by X-ray diffractometry (Philips PW 1700 computer-controlled goniometer with a graphite monochromator and Cu Ka radiation) and by 27 Al, 29 Si and 23 Na MAS NMR at 11.7 T using a Varian Unity 500 spectrometer with a 5-mm Doty MAS probe in which the sample was spun at 1012 kHz. The 27 Al spectra were acquired at 130.244 MHz using a p/10 pulse for solution and a recycle delay of 1 s, the spectra referenced to Al(H2O)63. The 29 Si spectra were acquired at 99.296 MHz using a 6-ms (p/2) pulse with a 10-s recycle delay, the spectra referenced to tetramethylsilane (TMS). The 23 Na spectra were acquired at 132.225 MHz using a 1-ms p/10 pulse for solution with a recycle delay of 1 s, the spectra referenced to 1 M aqueous NaCl. Fourier transform infrared spectroscopy was carried out on samples suspended in KBr discs using a Perkin-Elmer 2000 FTIR spectrometer. 3. Results and discussion 3.1. Thermal behaviour of the unlled geopolymer matrix The thermal analysis curves of geopolymer Na-PSS1 are shown in Fig. 1, which also contains a typical dilatometer trace for this sample. The TG curve (Fig. 1A) indicates that the sample dried at 65 8C retains about 15% water, of which 12% is lost below about 230 8C; the remainder is either more tightly bound or less able to diffuse to the

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Fig. 1. Thermal analysis curves of sample Na-PSS1: (A) TG curve, heating rate 20 8C min1 in nitrogen (20 ml min1); (B) dilatometer curve, heating rate 1 8C min1 in ambient atmosphere; (C) DSC curve, heating rate 10 8C min1 in nitrogen (20 ml min1).

surface, and continues to evolve gradually up to about 500 8C. The DSC curve (Fig. 1C) indicates that this endothermic water evolution has an associated energy of 0.24 kJ g1. The dilatometer curve (Fig. 1B) shows that the water loss is associated with a small degree of shrinkage, but between about 250 and 800 8C the polymer is essentially dimensionally stable. Above 800 8C, further shrinkage occurs due to densication and/or volume changes occurring within the sample bulk as a result of crystallisation. This shrinkage is not due to melting, or viscous creep, since it

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Fig. 2. Typical X-ray powder diffractograms of Na-PSS1 heated for 1 h at the indicated temperatures. Key: q, quartz (PDF no. 33-1161); m, mullite (PDF no. 15-776); c, corundum (a-alumina; PDF no. 10-173).

ceases abruptly at 880 8C and the sample again becomes dimensionally stable up to the temperature limit of the experiment (1000 8C). This nal dimensional stability is retained on cooling and in further thermal cycling. The sample begins to melt at about 1300 8C. A selection of typical powder XRD traces of cured geopolymer Na-PSS1 heated to various temperatures is shown in Fig. 2. The cured and dried polymer (Fig. 2A) is X-ray amorphous, displaying a typical background feature on which is superimposed the sharp major reection of the quartz impurity present in the original kaolinite. Between 400 and 1100 8C the polymer remains X-ray amorphous, but the quartz peak becomes much less distinct, possibly reecting a degree of dissolution under the alkaline conditions prevailing within the polymer. By 1200 8C, weak diffraction lines corresponding to mullite (Al6Si2O13) are superimposed on the broad amorphous background feature (Fig. 2C). These become sharper at

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Fig. 3. Typical 11.7 T MAS NMR spectra of Na-PSS1 heated for 1 h at the indicated temperatures. (AC) (D) 29 Si spectrum; (EG) 23 Na spectra. Asterisks denote spinning side bands.

27

Al spectra;

1300 8C, at which temperature evidence of corundum (a-Al2O3) also appears (Fig. 2D), but the persistence of a signicant amorphous hump at 1300 8C indicates the stability of the polymer to these temperatures. Typical 27 Al, 29 Si and 23 Na MAS NMR spectra of heated Na-PSS1 samples are shown in Fig. 3. The 27 Al spectrum of cured and dried Na-PSS1 (Fig. 3A) shows a major resonance at 56 ppm, indicating that the greater part of the aluminium is in tetrahedral coordination. The small, broad octahedral resonance at about 5 ppm is also typical of these polymers and may betray the presence of a small amount of unreacted metakaolinite [1]. The aluminium environment in Na-PSS1 is extraordinarily stable, being maintained unchanged up to at least 1100 8C. Even at 12001300 8C, the aluminium atoms in this polymer remain in essentially the same tetrahedral sites, with small

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changes being conned to the octahedral aluminium sites. At 1200 8C, a small octahedral feature at about 13 ppm has become detectable (Fig. 3B), evolving into the characteristic resonance of corundum by 1300 8C (Fig. 3C). The small amount of mullite detected by XRD in these high-temperature samples is not evident in the 27 Al spectra, probably being masked by the much stronger tetrahedral and octahedral signatures of the polymer and corundum, respectively. Since the high-temperature changes are conned to the spectral features probably arising from unreacted starting material rather than the polymer, the small amount of mullite and corundum formed could arise from this impurity rather than the polymer, which may itself be thermally stable up to and beyond its softening point. The thermal stability of the polymer is conrmed by the 29 Si spectra of the heated samples (Fig. 3D), which remains essentially unchanged over the whole temperature range. The silicon component of the small amount of mullite formed at higher temperatures would be expected at about 86 ppm, but this will be masked by the broadness of the polymer resonance centred at about 93 ppm. The 23 Na spectra of this polymer show the greatest changes on heating, as would be expected from the proposed polymer structure [1] in which hydrated sodium ions are located in cavities in the crosslinked polymeric chains. The 23 Na spectrum of hydrated Na in these cavities (Fig. 3E) has a chemical shift of 5.5 to 7 ppm, similar to the shift of hydrated Na in hydrothermally-altered glass [4] and Na-hectorite [5]. As the hydration water is removed by heating, the 23 Na resonance moves progressively upeld to 14 ppm at 800 8C (Fig. 3F), settling down at 19 ppm at 11001300 8C (Fig. 3G). This nal chemical shift value is typical of unhydrated sodium aluminosilicate glass and rhyolite glass [6] as would be expected for the proposed glass-like structure of the polymer, providing further conrmation of the stability of this structure up to high temperatures. A selection of FTIR spectra of Na-PSS1 heated to various temperatures is shown in Fig. 4. The spectrum of the unheated polymer (Fig. 4A) contains absorption bands at about 3450 and 1650 cm1 resulting from hydration water, a strong SiO stretching vibration at about 1088 cm1 and an SiO bending vibration at about 450 cm1. The bands between 600800 cm1 are due to AlOSi vibrations [7,8]. The absence of a band at 1460 cm1 indicates that sodium carbonate species are not present in this sample [9]. Heating the geopolymer to 1000 8C (Fig. 4B) produces a marked decrease in the water bands to a constant level consistent with adventitious water in the sample disks and the spectrometer system. Apart from this obvious change in the sample hydration on heating >1000 8C, small changes also occur in the AlSiO region, especially the development of the broad mullite band at about 850 cm1, consistent with the XRD results. In summary, all the results indicate that the removal of hydration water from a well-cured Na-PSS1 polymer brings about no signicant change to the structure. Furthermore, the structure displays a high degree of thermal stability at higher temperatures, retaining its X-ray amorphous character and the atomic environment of its constituent Al, Si and Na components. The small amounts of crystalline mullite and corundum which appear >1000 8C probably result from solid-state transformations in the traces of unreacted metakaolinite starting material, and do not necessarily denote a signicant breakdown of the polymer. 3.2. Thermal stability of other polymer compositions A selection of XRD traces of Na-PSS2 and Na-PSS7 heated to 11001200 8C are shown in Fig. 5.

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Fig. 4. FTIR spectra of Na-PSS1 and Na-PSS7, unheated and heated for 1 h at the indicated temperatures.

Neither of these compositions hardened properly on curing or drying, due to incomplete reaction between the components resulting in a high concentration of residual sodium silicate. On drying, the sodium in these samples has been found to migrate to the surface of the body, where it undergoes atmospheric carbonation [1]. The XRD traces of both these unheated polymers are similar to that of unheated Na-PSS1. The amorphous nature of the XRD traces persists in Na-PSS2 to 1100 8C (Fig. 5A), at which temperature a small amount of crystalline nepheline (NaAlSiO4) appears (PDF no. 35-424) in addition to the major reection of mullite (PDF no. 15-776). The appearance of nepheline in this sample is transitory, since by 1200 8C mullite is the only crystalline phase with diffraction lines superimposed on the broad amorphous baseline feature (Fig. 5B). The onset of melting occurred in this sample at a similar temperature to Na-PSS1 (1300 8C), at which temperature the diffraction lines of corundum had also appeared, as in Na-PSS1 heated to 1300 8C (Fig. 2D). Thus, the thermal behaviour

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Fig. 5. X-ray powder diffractograms of Na-PSS2 and Na-PSS7 heated for 1 h at the indicated temperatures.

of these two samples of the same composition is identical except for the brief appearance of a small amount of nepheline at 1100 8C. The formation of the latter reects the availability of some uncombined surface sodium, which in turn results from incomplete polymerisation due to the additional water in sample Na-PSS2 [1]. By contrast with Na-PSS1, the FTIR spectrum of unheated Na-PSS2 contains a band at 1450 cm1 arising from the presence of sodium carbonate species which disappears on heating at 1000 8C; in all other respects the FTIR spectra of these two polymers heated at 1000 1300 8C are identical. By contrast, the XRD trace of Na-PSS7, which is richer in Na and Si than the other two formulations, shows at 800 8C the presence of nepheline (Fig. 5C), which remains to the onset of melting at 1100 8C. The lower melting temperature of this sample and its crystallisation product are explicable in terms of the composition of this sample. The FTIR spectrum of unheated Na-PSS7 (Fig. 4E) contains a strong carbonate band at 1450 cm1, arising from the carbonation of a high concentration of unreacted Na. By 1000 8C these species have thermally decomposed, releasing the Na to form

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nepheline and giving a simpler spectrum in the AlO region consisting of a single peak at about 750 cm1 (Fig. 4F). The 29 Si and 27 Al MAS NMR spectra of this material heated at 1100 8C are identical with the spectra of Na-PSS1 (Fig. 3), except for the absence of the 27 Al corundum peak at 13 ppm. The 23 Na spectrum contains a single resonance at 16.5 ppm, slightly downeld of the resonance in Na-PSS1 (19 ppm). This indicates that the Na environment of the amorphous component of heated polymer Na-PSS1 is not the same as that of nepheline. 3.3. Thermal behaviour of Na-PSS1 composites The compressive strengths and densities of the cured geopolymer composites containing 10 vol.% of various inorganic ller powders are shown in Table 1 and their thermal expansion curves are shown in Fig. 6. These data suggest that the properties of the composites represent a combination of the properties of the geopolymer matrix and the inorganic ller. The at portion in the thermal expansion curves of all the composites up to about 800 8C (Fig. 6) indicates a useful working temperature range similar to that of the unlled geopolymer. The compressive strength of all the composites is less than the best strength value obtained for the unlled polymer matrix, this strength reduction being the most signicant in the composites containing alumina and b-sialon, both of which are unreactive at ambient temperatures and unlikely either to sinter or to bond to any degree with the matrix. These llers, therefore, reduce the overall strength by diluting the geopolymer without contributing any signicant strength of their own. Possible interactions between the inorganic ller and the geopolymer matrix were investigated by Xray powder diffraction and solid-state 27 Al, 29 Si and 23 Na MAS NMR of samples heated for 1 hr at temperatures between 10001300 8C. A common feature of all the heated composites was the absence of change in the XRD, 27 Al and 29 Si NMR up to 1000 8C apart from thermally-induced changes in some of the llers at this temperature. The geopolymer remains stable, however, and apparently does not react with any of the llers. A change in the 23 Na peak position from about 3 to 18 ppm was observed in all the heated composites and is typical of the unlled geopolymer matrix. Above 1000 8C, the crushed brick ller undergoes thermal reactions to form quartz mullite at 1200 8C and quartz corundum at 1300 8C, the latter showing its characteristic 27 Al NMR signature at 13 ppm. Thermal reaction of the powdered stone ller above 1000 8C results in the replacement of the

Table 1 Properties of cured composites of Na-PSS1 geopolymer with inorganic llers Filler Crushed brick Powdered stone Kaolinite Titanomagnetite ironsand Corundum b-Sialon Unfilled Composite density (g ml1) 1.65 1.62 1.62 2.06 1.90 1.72 1.40 Composite compressive strength (MPa) 19 26 30 21 8 15 54

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Fig. 6. Dilatometer curves for Na-PSS1 geopolymer composites, containing 10 vol.% of various inorganic llers. Heating rate 1 8C min1 in ambient atmosphere.

phlogopite and albite components with quartz corundum at 1300 8C, while the kaolinite ller undergoes a progressive change to mullite above 1000 8C (with some corundum also formed at 1300 8C). Thermal reaction of the magnetite ironsand to hematite has occurred by 1000 8C, the XRD pattern being superimposed on the unchanged amorphous trace of the geopolymer (the presence of the iron in these samples rendered NMR spectroscopy impracticable). The alumina-lled composite remained unchanged up to 1000 8C, beyond which temperature a small amount of mullite also appeared, as in the unlled polymer. The geopolymer-b-sialon composite was also unchanged up to 1000 8C, but above this temperature a small amount of mullite forms; the persistence of the b-sialon at 1200 8C suggests that this is likely to originate from the geopolymer rather than from oxidation of the sialon, at least below 1300 8C. The presence of a signicant amount of b-sialon even at 1300 8C indicates that the geopolymer matrix provides substantial protection from oxidation, since this b-sialon progressively oxidises in air to mullite silica above 1000 8C [10]. Some of the geopolymer composites, e.g. those with higher sialon contents, showed signs of microcracking after demolding. This defect could be cured by the addition to the mixture of small amounts of glycerol (5 vol.%), which acts as a plasticiser [11], increasing the exibility of the composite and reducing the tendency to crack during drying. The addition of small amounts of glycerol for this purpose does not appear to adversely affect the physical or thermal properties of the composite.

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To summarise, these results indicate that Na-PSS1 geopolymer composites with a variety of inorganic llers ranging from waste mining and demolition materials to high-technology ceramics are thermally stable up to high temperatures. Even though the ller itself may undergo thermal reactions, these are not necessarily detrimental, and may even contribute to the strength of the composite by processes akin to reaction bonding. 4. Conclusions 1. Sodium polysialate polymers of suitable composition for optimum curing are remarkably thermally stable. On heating they irreversibly lose their hydration water (approximately 15 wt.%) in an endothermic reaction at 100200 8C, which is accompanied by a small degree of shrinkage. Further irreversible shrinkage occurs at about 800 8C, whereupon the polymer becomes dimensionally stable. 2. The X-ray amorphous character of the well-cured polymer is retained on heating up to the onset of melting at about 1300 8C. Small traces of mullite and corundum (a-alumina), which appear at 1200 1300 8C, are suggested to arise from the presence of a small amount of unreacted metakaolinite starting material. The extreme stability of this material is conrmed by FTIR spectroscopy and 27 Al, 29 Si and 23 Na MAS NMR spectroscopy, which, apart from the 23 Na NMR, shows little change throughout the heating range. The 23 Na spectra show that the Na environment is sensitive to the loss of hydration water, changing on heating from typically hydrated sites to sites more typical of unhydrated aluminosilicate and rhyolite glass. 3. A more poorly-curing polymer formulation containing more water shows evidence of the presence of unbound Na which migrates to the surface on drying and reacts on heating at 1100 8C with some of the unpolymerised starting material to form a small amount of nepheline (NaAlSiO4). At higher temperatures, mullite and corundum are formed in this material. Another poorly-curing polymer formulation containing a higher Na and Si content was found to form well-crystallised nepheline at 8001100 8C, prior to the onset of melting at about 1100 8C. 4. Composites consisting of a matrix of well-cured polysialate containing a variety of granular inorganic llers exhibit the good thermal behavior of the unlled geopolymer, with little detectable reaction occurring between the ller and matrix up to and in some cases beyond 1000 8C. The chemical components of a properly curing geopolymer formulation are locked into the glass-like structure, which is maintained at high temperatures even in the presence of inorganic llers, extending the range of possible applications for such materials. The geopolymer matrix also appears to protect non-oxide llers such as sialon from oxidation. 5. Microcracking during drying of geopolymer composites can be minimised by the addition of a small amount of glycerol, which acts as a plasticiser. Acknowledgements We are indebted to M.E. Bowden for assistance with the dilatometry and to R.L. Frost for the FTIR spectroscopy. VFFB is grateful to CAPES and FAPERJ for nancial support. KJDM is indebted to the Royal Society of New Zealand for a James Cook Research Fellowship under which part of this work was carried out.

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