Abstract
One-part geopolymers were synthesized from two different silica materials (a silica-rich residue from chlorosilane production and a commercial microsilica) and sodium aluminate at three different SiO2/Al2O3 ratios and a nominal water/solids ratio of 0.5. The degree of reaction of the silica in the cured geopolymers (i.e. the fraction of silica dissolved to form aluminosilicates and minor products) was determined using two different methods: chemical attack with HCl to dissolve the reaction products and evaluation of peak areas of 29Si MAS NMR spectra. It was found that the degree of reaction of the silica decreases with increasing the silica content of the starting mix, and that it is almost constant after 1 day of curing and almost independent from the kind of starting silica. From the results of the NMR-based method, the mean SiO2/Al2O3 ratio of the reaction products (aluminosilicates and minor products) can be estimated to be ca. 2.0, nearly independent of the starting composition of the geopolymers. The dissolution method is biased, but of sufficient precision to be useful for following changes of the degree of reaction. Major crystalline phases in the cured geopolymers are zeolite A and/or hydrosodalite. Depending on the starting composition, the relative amounts of these zeolites vary; additionally, sodalite (only for the residue from chlorosilane production with >1 wt% Cl−), faujasite, and zeolite EMT can appear in the geopolymers. The 29Si and 27Al MAS NMR results indicate mainly Si(4Al) and Al(4Si) sites, in line with the presence of zeolite A, hydrosodalite, sodalite, and geopolymeric gel of comparatively low SiO2/Al2O3 ratio.
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References
Herr R (2004) Geopolymere - eine neue mineralische Baustoff-Generation für den Brandschutz von Ingenieurbauwerken. IEMB Info 2004/7. Institut für Erhaltung und Modernisierung von Bauwerken e.V., Berlin
Bell J, Gordon M, Kriven W (2005) Use of geopolymeric cements as a refractory adhesive for metal and ceramic joins. Ceram Eng Sci Proc 26(3):407–413
Krivenko PV, Kovalchuk GY (2007) Directed synthesis of alkaline aluminosilicate minerals in a geocement matrix. J Mater Sci 42:2944–2952. doi:10.1007/s10853-006-0528-3
Krivenko PV, Pushkavera YK, Sukhanevich MV, Guziy SG (2009) Fireproof coatings on the basis of alkaline aluminum silicate systems. Ceram Eng Sci Proc 29(10):129–142
Temuujin J, Minjigmaa A, Rickard W, Lee M, Williams I, van Riessen A (2010) Fly ash based geopolymer thin coatings on metal substrates and its thermal evaluation. J Hazard Mater 180:748–752
Montes C, Allouche EN (2012) Evaluation of the potential of geopolymer mortar in the rehabilitation of buried infrastructure. Struct Infrastruct Eng 8:89–98
Duxson P, Provis JL, Lukey GC, van Deventer JSJ (2007) The role of inorganic polymer technology in the development of ‘green concrete’. Cem Concr Res 37:1590–1597
Duxson P, Fernández-Jiménez A, Provis JL, Lukey GC, Palomo A, van Deventer JSJ (2007) Geopolymer technology: the current state of the art. J Mater Sci 42:2917–2933. doi:10.1007/s10853-006-0637-z
Provis JL, van Deventer JSJ (eds) (2014) Alkali activated materials: state-of-the-art-report, RILEM TC 224-AAM. Springer, Dordrecht
Hajimohammadi A, Provis JL, van Deventer JSJ (2008) One-part geopolymer mixes from geothermal silica and sodium aluminate. Ind Eng Chem Res 47:9396–9405
Duxson P, Provis JL (2008) Designing precursors for geopolymer cements. J Am Ceram Soc 91:3864–3869
Koloušek D, Brus J, Urbanova M, Andertova J, Hulinsky V, Vorel J (2007) Preparation, structure and hydrothermal stability of alternative (sodium silicate-free) geopolymers. J Mater Sci 42:9267–9275. doi:10.1007/s10853-007-1910-5
Hajimohammadi A, Provis JL, van Deventer JSJ (2010) Effect of alumina release rate on the mechanism of geopolymer gel formation. Chem Mater 22:5199–5208
Feng D, Provis JL, van Deventer JSJ (2012) Thermal activation of albite for the synthesis of one-part mix geopolymers. J Am Ceram Soc 95:565–572
Brew DRM, MacKenzie KJD (2007) Geopolymer synthesis using silica fume and sodium aluminate. J Mater Sci 42:3990–3993. doi:10.1007/s10853-006-0376-1
Hajimohammadi A, Provis JL, van Deventer JSJ (2011) The effect of silica availability on the mechanism of geopolymerisation. Cem Concr Res 41:210–216
Gluth GJG, Lehmann C, Rübner K, Kühne H-C (2013) Geopolymerization of a silica residue from waste treatment of chlorosilane production. Mater Struct 46:1291–1298
Greiser S, Gluth GJG, Sturm P, Brouwers HJH, Jäger C (2014) 27Al-1H and 27Al-29Si double resonance NMR of one-part geopolymers. In: Non-Traditional Cement & Concrete V—Proceedings of the International Conference, Brno, Czech Republic, pp 91–94
Sturm P, Gluth GJG, Schmidt W, Astorg A, Kühne H-C, Brouwers HJH (2014) Rheological properties of microsilica and sodium aluminate based one-part geopolymers compared to ordinary Portland cement. In: Non-Traditional Cement & Concrete V—Proceedings of the International Conference, Brno, Czech Republic, pp 241–244
Sturm P, Gluth GJG, Lindemann M, Greiser S, Jäger C, Brouwers HJH (2014) Structural investigations on one-part geopolymers after different drying regimes. In: Proceedings of the 34th Annual Cement and Concrete Science Conference, and Workshop on Waste Cementation, Sheffield, United Kingdom, pp 37–40
Bennett AE, Rienstra CM, Auger M, Lakshmi KV, Griffin RG (1995) Heteronuclear decoupling in rotating solids. J Chem Phys 103:6951–6958
Massiot D, Fayon F, Capron M, King I, Le Calvé S, Alonso B, Durand J-O, Bujoli B, Gan Z, Hoatson G (2002) Modelling one- and two-dimensional solid-state NMR spectra. Magn Reson Chem 40:70–76
Fernández-Jiménez A, de la Torre AG, Palomo A, López-Olmo G, Alonso MM, Aranda MAG (2006) Quantitative determination of phases in the alkaline activation of fly ash. Part II: degree of reaction. Fuel 85:1960–1969
Zhang B, MacKenzie KJD, Brown IWM (2009) Crystalline phase formation in metakaolinite geopolymers activated with NaOH and sodium silicate. J Mater Sci 44:4668–4676. doi:10.1007/s10853-009-3715-1
Weitkamp J, Schumacher R, Weiß U (1992) Hydrothermalsynthese und Charakterisierung von Zeolith EMT. Chem Ing Tech 64:1109–1112
Provis JL, Lukey GC, van Deventer JSJ (2005) Do geopolymers actually contain nanocrystalline zeolites? A reexamination of existing results. Chem Mater 17:3075–3085
Engelhardt G, Michel D (1987) High-resolution solid-state NMR of silicates and zeolites. Wiley, Chichester
Lippmaa E, Mägi M, Samoson A, Tarmak M, Engelhardt G (1981) Investigation of the structure of zeolites by solid-state high-resolution 29Si NMR spectroscopy. J Am Chem Soc 103:4992–4996
Fletcher RA, MacKenzie KJD, Nicholson CL, Shimada S (2005) The composition range of aluminosilicate geopolymers. J Eur Ceram Soc 25:1471–1477
Engelhardt G, Felsche J, Sieger P (1992) The hydrosodalite system Na6+x [SiAlO4]6(OH) x ∙nH2O: formation, phase composition, and de- and rehydration studied by 1H, 23Na, and 29Si MAS–NMR spectroscopy in tandem with thermal analysis, X-ray diffraction, and IR spectroscopy. J Am Chem Soc 114:1173–1182
Brough AR, Dobson CM, Richardson IG, Groves GW (1995) A study of the pozzolanic reaction by solid-state 29Si nuclear magnetic resonance using selective isotopic enrichment. J Mater Sci 30:1671–1678. doi:10.1007/BF00351595
Sun G, Brough AR, Young JF (1999) 29Si NMR study of the hydration of Ca3SiO5 and β-Ca2SiO4 in the presence of silica fume. J Am Ceram Soc 82:3225–3230
Leemann A, Le Saout G, Winnefeld F, Rentsch D, Lothenbach B (2011) Alkali-silica reaction: the influence of calcium on silica dissolution and the formation of reaction products. J Am Ceram Soc 94:1243–1249
Fyfe CA, Gobbi GC, Hartman JS, Klinowski J, Thomas JM (1982) Solid-state magic-angle spinning aluminum-27 nuclear magnetic resonance studies of zeolites using a 400-MHz high-resolution spectrometer. J Phys Chem 86:1247–1250
Lippmaa E, Samoson A, Mägi M (1986) High-resolution 27Al NMR of aluminosilicates. J Am Chem Soc 108:1730–1735
Hartman RL, Fogler HS (2005) Reaction kinetics and mechanisms of zeolite dissolution in hydrochloric acid. Ind Eng Chem Res 44:7738–7745
Hartman RL, Fogler HS (2007) Understanding the dissolution of zeolites. Langmuir 23:5477–5484
Oh JE, Moon J, Mancio M, Clark SM, Monteiro PJM (2011) Bulk modulus of basic hydrosodalite, Na8[AlSiO4]6(OH)2·2H2O, a possible zeolitic precursor in coal-fly-ash-based geopolymers. Cem Concr Res 41:107–112
Felsche J, Luger S (1987) Phases and thermal decomposition characteristics of hydro-sodalites Na6+x [AlSiO4]6(OH) x ·nH2O. Thermochim Acta 118:35–55
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Sturm, P., Greiser, S., Gluth, G.J.G. et al. Degree of reaction and phase content of silica-based one-part geopolymers investigated using chemical and NMR spectroscopic methods. J Mater Sci 50, 6768–6778 (2015). https://doi.org/10.1007/s10853-015-9232-5
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DOI: https://doi.org/10.1007/s10853-015-9232-5