journal article·2018-07Open access

Examination of alkali-activated material nanostructure during thermal treatment

Brant Walkley, Alireza Kashani, Marc-Antoine Sani, Tuan D. Ngo, Priyan Mendis

Journal of Materials Science· Volume 53· Issue 13

Abstract

The key nanostructural changes occurring in a series of alkali-activated materials (AAM) based on blends of slag and fly ash precursors during exposure to temperatures up to 1000 °C are investigated. The main reaction product in each AAM is a crosslinked sodium- and aluminium-substituted calcium silicate hydrate (C-(N)-A-S-H)-type gel. Increased alkali content promotes the formation of an additional sodium aluminosilicate hydrate (N-A-S-(H)) gel reaction product due to the structural limitations on Al substitution within the C-(N)-A-S-H gel. Heating each AAM to 1000 °C results in the crystallisation of the disordered gels and formation of sodalite, nepheline and wollastonite. Increased formation of N-A-S-(H) reduces binder structural water content after thermal treatment and correlates closely with previous observations of improved strength retention and reduced microcracking in these AAM after heating to 1000 °C. This provides new insight into thermally induced changes to gel atomic structure and thermal durability of C-(N)-A-S-H/N-A-S-H gel blends which are fundamental for the development of new fire-resistant construction materials.
Source: openalex_inverted_index · Quality: baseline

Research context

OpenAlex topics: Concrete and Cement Materials Research · Magnesium Oxide Properties and Applications · Fire effects on concrete materials

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (82)

Show source-provided references
1. Provis JL, Palomo A, Shi C (2015) Advances in understanding alkali-activated materials. Cem Concr Res 78A:110–12510.1016/j.cemconres.2015.04.013 ↗
2. Vickers L, van Riessen A, Rickard WDA (2014) Fire-resistant geopolymers: role of fibres and fillers to enhance thermal properties. Springer, Singapore
3. Barbosa VFF, MacKenzie KJD (2003) Thermal behaviour of inorganic geopolymers and composites derived from sodium polysialate. Mater Res Bull 38:319–33110.1016/S0025-5408(02)01022-X ↗
4. Zhao R, Sanjayan JG (2011) Geopolymer and Portland cement concretes in simulated fire. Mag Concr Res 63:163–17310.1680/macr.9.00110 ↗
5. Kong DL, Sanjayan JG (2010) Effect of elevated temperatures on geopolymer paste, mortar and concrete. Cem Concr Res 40:334–33910.1016/j.cemconres.2009.10.017 ↗
6. Kashani A, Ngo TD, Walkley B, Mendis P (2017) Thermal performance of calcium-rich alkali-activated materials: a microstructural and mechanical study. Constr Build Mater 153:225–23710.1016/j.conbuildmat.2017.07.119 ↗
7. Rivera OG, Long WR, Weiss CA Jr, Moser RD, Williams BA, Torres-Cancel K, Gore ER, Allison PG (2016) Effect of elevated temperature on alkali-activated geopolymeric binders compared to portland cement-based binders. Cem Concr Res 90:43–5110.1016/j.cemconres.2016.09.013 ↗
8. Mendes A, Sanjayan J, Collins F (2008) Phase transformations and mechanical strength of OPC/Slag pastes submitted to high temperatures. Mater Struct 41:345–35010.1617/s11527-007-9247-8 ↗
9. Hertz KD (2005) Concrete strength for fire safety design. Mag Concr Res 57:445–45310.1680/macr.2005.57.8.445 ↗
10. Schilling PJ, Butler LG, Roy A, Eaton HC (1994) 29Si and 27AI MAS-NMR of NaOH-activated blast-furnace slag. J Am Ceram Soc 77:2363–236810.1111/j.1151-2916.1994.tb04606.x ↗
11. Myers RJ, Bernal SA, San Nicolas R, Provis JL (2013) Generalized structural description of calcium-sodium aluminosilicate hydrate gels: the cross-linked substituted tobermorite model. Langmuir 29:5294–530610.1021/la4000473 ↗
12. Richardson IG (2008) The calcium silicate hydrates. Cem Concr Res 38:137–15810.1016/j.cemconres.2007.11.005 ↗
13. Provis JL, Lukey GC, van Deventer JSJ (2005) Do geopolymers actually contain nanocrystalline zeolites? A reexamination of existing results. Chem Mater 17:3075–308510.1021/cm050230i ↗
14. Bernal SA, Provis JL, Rose V, de Gutierrez RM (2011) Evolution of binder structure in sodium silicate-activated slag-metakaolin blends. Cem Concr Compos 33:46–5410.1016/j.cemconcomp.2010.09.004 ↗
15. Yip CK, Lukey GC, Provis JL, van Deventer JSJ (2008) Effect of calcium silicate sources on geopolymerisation. Cem Concr Res 38:554–56410.1016/j.cemconres.2007.11.001 ↗
16. Yip CK, Van Deventer JSJ (2003) Microanalysis of calcium silicate hydrate gel formed within a geopolymeric binder. J Mater Sci 38:3851–3860. https://doi.org/10.1023/A:102590490517610.1023/A:1025904905176 ↗
17. Walkley B, San Nicolas R, Sani M-A, Rees GJ, Hanna JV, van Deventer JSJ, Provis JL (2016) Phase evolution of C-(N)-A-S-H/N-A-S-H gel blends investigated via alkali-activation of synthetic calcium aluminosilicate precursors. Cem Concr Res 89:120–13510.1016/j.cemconres.2016.08.010 ↗
18. Bernal SA, Provis JL, Walkley B, San Nicolas R, Gehman JD, Brice DG, Kilcullen AR, Duxson P, van Deventer JSJ (2013) Gel nanostructure in alkali-activated binders based on slag and fly ash, and effects of accelerated carbonation. Cem Concr Res 53:127–14410.1016/j.cemconres.2013.06.007 ↗
19. Myers RJ, Bernal SA, Provis JL (2014) A thermodynamic model for C-(N-)A-S-H gel: CNASH_ss. Derivation and validation. Cem Concr Res 66:27–4710.1016/j.cemconres.2014.07.005 ↗
20. Bernal SA, Rodriguez ED, de Gutierrez RM, Gordillo M, Provis JL (2011) Mechanical and thermal characterisation of geopolymers based on silicate-activated metakaolin/slag blends. J Mater Sci 46:5477–5486. https://doi.org/10.1007/s10853-011-5490-z10.1007/s10853-011-5490-z ↗
21. Ismail I, Bernal SA, Provis JL, San Nicolas R, Hamdan S, van Deventer JSJ (2014) Modification of phase evolution in alkali-activated blast furnace slag by the incorporation of fly ash. Cem Concr Compos 45:125–13510.1016/j.cemconcomp.2013.09.006 ↗
22. Yip CK, Lukey GC, van Deventer JSJ (2005) The coexistence of geopolymeric gel and calcium silicate hydrate at the early stage of alkaline activation. Cem Concr Res 35:1688–169710.1016/j.cemconres.2004.10.042 ↗
23. Provis JL, Bernal SA (2014) Geopolymers and related alkali-activated materials. Annu Rev Mater Res 44:299–32710.1146/annurev-matsci-070813-113515 ↗
24. Gartner EM, Macphee DE (2011) A physico-chemical basis for novel cementitious binders. Cem Concr Res 41:736–74910.1016/j.cemconres.2011.03.006 ↗
25. García-Lodeiro I, Palomo A, Fernández-Jiménez A, Macphee DE (2011) Compatibility studies between N-A-S-H and C-A-S-H gels. Study in the ternary diagram Na2O–CaO–Al2O3–SiO2–H2O. Cem Concr Res 41:923–93110.1016/j.cemconres.2011.05.006 ↗
26. Ali F, Nadjai A, Talamona D (2004) Assessment of the susceptibility of normal and high strength concrete for explosive spalling. J Appl Fire Sci 13:79–8810.2190/CQCT-QTG2-9KT7-5YAU ↗
27. Ali F, O’Connor D, Abu-Tair A (2001) Explosive spalling of high-strength concrete columns in fire. Mag Concr Res 53:197–20410.1680/macr.2001.53.3.197 ↗
28. Kong DL, Sanjayan JG, Sagoe-Crentsil K (2007) Comparative performance of geopolymers made with metakaolin and fly ash after exposure to elevated temperatures. Cem Concr Res 37:1583–158910.1016/j.cemconres.2007.08.021 ↗
29. Kong DL, Sanjayan JG (2008) Damage behavior of geopolymer composites exposed to elevated temperatures. Cem Concr Compos 30:986–99110.1016/j.cemconcomp.2008.08.001 ↗
30. Kong DL, Sanjayan JG, Sagoe-Crentsil K (2008) Factors affecting the performance of metakaolin geopolymers exposed to elevated temperatures. J Mater Sci 43:824–831. https://doi.org/10.1007/s10853-007-2205-610.1007/s10853-007-2205-6 ↗
31. Walkley B, San Nicolas R, Sani MA, Gehman JD, van Deventer JS, Provis JL (2016) Phase evolution of Na2O-Al2O3-SiO2-H2O gels in synthetic aluminosilicate binders. Dalton Trans 45:5521–553510.1039/C5DT04878H ↗
32. Hajimohammadi A, Provis JL, van Deventer JSJ (2011) Time-resolved and spatially-resolved infrared spectroscopic observation of seeded nucleation controlling geopolymer gel formation. J Colloid Interface Sci 357:384–39210.1016/j.jcis.2011.02.045 ↗
33. Dai Z, Tran TT, Skibsted J (2014) Aluminum incorporation in the C-S–H phase of white portland cement-metakaolin blends studied by 27Al and 29Si MAS NMR spectroscopy. J Am Ceram Soc 97:2662–267110.1111/jace.13006 ↗
34. Girão AV, Richardson IG, Taylor R, Brydson RMD (2010) Composition, morphology and nanostructure of C–S–H in 70% white Portland cement–30% fly ash blends hydrated at 55 °C. Cem Concr Res 40:1350–135910.1016/j.cemconres.2010.03.012 ↗
35. Tailby J, MacKenzie KJD (2010) Structure and mechanical properties of aluminosilicate geopolymer composites with Portland cement and its constituent minerals. Cem Concr Res 40:787–79410.1016/j.cemconres.2009.12.003 ↗
36. Buchwald A, Hilbig H, Kaps C (2007) Alkali-activated metakaolin-slag blends—performance and structure in dependence of their composition. J Mater Sci 42:3024–3032. https://doi.org/10.1007/s10853-006-0525-610.1007/s10853-006-0525-6 ↗
37. Dombrowski K, Buchwald A, Weil M (2007) The influence of calcium content on the structure and thermal performance of fly ash based geopolymers. J Mater Sci 42:3033–3043. https://doi.org/10.1007/s10853-006-0532-710.1007/s10853-006-0532-7 ↗
38. van Deventer JSJ, San Nicolas R, Ismail I, Bernal SA, Brice DG, Provis JL (2014) Microstructure and durability of alkali-activated materials as key parameters for standardization. J Sustain Cem Based Mater 4:116–12810.1080/21650373.2014.979265 ↗
39. Ismail I, Bernal S, Provis J, Hamdan S, Deventer JJ (2013) Drying-induced changes in the structure of alkali-activated pastes. J Mater Sci 48:3566–3577. https://doi.org/10.1007/s10853-013-7152-910.1007/s10853-013-7152-9 ↗
40. Delaglio F, Grzesiek S, Vuister G, Zhu G, Pfeifer J, Bax A (1995) NMRPipe: a multidimensional spectral processing system based on UNIX pipes. J Biomol NMR 6:277–29310.1007/BF00197809 ↗
41. 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 40:70–7610.1002/mrc.984 ↗
42. Provis JL, Duxson P, Lukey GC, van Deventer JSJ (2005) Statistical thermodynamic model for Si/Al ordering in amorphous aluminosilicates. Chem Mater 17:2976–298610.1021/cm050219i ↗
43. Fernández-Jiménez A, Palomo A, Sobrados I, Sanz J (2006) The role played by the reactive alumina content in the alkaline activation of fly ashes. Microporous Mesoporous Mater 91:111–11910.1016/j.micromeso.2005.11.015 ↗
44. Lecomte I, Henrist C, Liégeois M, Maseri F, Rulmont A, Cloots R (2006) (Micro)-structural comparison between geopolymers, alkali-activated slag cement and Portland cement. J Eur Ceram Soc 26:3789–379710.1016/j.jeurceramsoc.2005.12.021 ↗
45. Criado M, Fernández-Jiménez A, Palomo A, Sobrados I, Sanz J (2008) Effect of the SiO2/Na2O ratio on the alkali activation of fly ash. Part II: 29Si MAS-NMR Survey. Microporous Mesoporous Mater 109:525–53410.1016/j.micromeso.2007.05.062 ↗
46. Fechtelkord M, Stief F, Buhl J-C (2001) Sodium cation dynamics in nitrate cancrinite: a low and high temperature 23Na and 1H MAS NMR study and high temperature Rietveld structure refinement. Am Miner 86:165–17510.2138/am-2001-0118 ↗
47. Lloyd RR, Provis JL, Deventer JSJ (2009) Microscopy and microanalysis of inorganic polymer cements. 2: the gel binder. J Mater Sci 44:620–631. https://doi.org/10.1007/s10853-008-3078-z10.1007/s10853-008-3078-z ↗
48. Duxson P, Lukey GC, van Deventer JSJ (2006) Evolution of gel structure during thermal processing of Na-geopolymer gels. Langmuir 22:8750–875710.1021/la0604026 ↗
49. Bakharev T (2006) Thermal behaviour of geopolymers prepared using class F fly ash and elevated temperature curing. Cem Concr Res 36:1134–114710.1016/j.cemconres.2006.03.022 ↗
50. Provis JL, Yong CZ, Duxson P, van Deventer JSJ (2009) Correlating mechanical and thermal properties of sodium silicate-fly ash geopolymers. Colloids Surf A 336:57–6310.1016/j.colsurfa.2008.11.019 ↗
51. Felsche J, Luger S (1987) Phases and thermal decomposition characteristics of hydro-sodalites Na6+x,[AlSiO4]6,(OH)x·nH2O. Thermochim Acta 118:35–5510.1016/0040-6031(87)80069-2 ↗
52. Mitsuda T, Taylor HFW (1978) Normal and anomalous tobermorites. Mineral Mag 42:229–23510.1180/minmag.1978.042.322.09 ↗
53. Kalousek GL (1952) Application of differential thermal analysis in a study of the system lime–silica–water. In: Third international symposium on the chemistry of cement, cement and concrete association, London
54. Myers RJ, L’Hôpital ÉM, Provis JL, Lothenbach B (2015) Effect of temperature and aluminium on calcium (alumino)silicate hydrate chemistry under equilibrium conditions. Cem Concr Res 68:83–9310.1016/j.cemconres.2014.10.015 ↗
55. Myers RJ, Bernal SA, Gehman JD, van Deventer JSJ, Provis JL (2015) The role of Al in cross-linking of alkali-activated slag cements. J Am Ceram Soc 98:996–100410.1111/jace.13360 ↗
56. Lloyd RR, Provis JL, van Deventer JSJ (2009) Microscopy and microanalysis of inorganic polymer cements. 1: remnant fly ash particles. J Mater Sci 44:608–619. https://doi.org/10.1007/s10853-008-3077-010.1007/s10853-008-3077-0 ↗
57. Fernández-Jiménez A, Palomo A (2005) Composition and microstructure of alkali activated fly ash binder: effect of the activator. Cem Concr Res 35:1984–199210.1016/j.cemconres.2005.03.003 ↗
58. Winnefeld F, Leemann A, Lucuk M, Svoboda P, Neuroth M (2010) Assessment of phase formation in alkali activated low and high calcium fly ashes in building materials. Constr Build Mater 24:1086–109310.1016/j.conbuildmat.2009.11.007 ↗
59. Bernal SA, San Nicolas R, Myers RJ, Mejía de Gutiérrez R, Puertas F, van Deventer JSJ, Provis JL (2014) MgO content of slag controls phase evolution and structural changes induced by accelerated carbonation in alkali-activated binders. Cem Concr Res 57:33–4310.1016/j.cemconres.2013.12.003 ↗
60. Wang S-D, Scrivener KL (2003) 29Si and 27Al NMR study of alkali-activated slag. Cem Concr Res 33:769–77410.1016/S0008-8846(02)01044-X ↗
61. Palomo A, Alonso S, Fernández-Jiménez A, Sobrados I, Sanz J (2004) Alkaline activation of fly ashes: NMR study of the reaction products. J Am Ceram Soc 87:1141–114510.1111/j.1551-2916.2004.01141.x ↗
62. Merwin LH, Sebald A, Rager H, Schneider H (1991) 29Si and 27Al MAS NMR spectroscopy of mullite. Phys Chem Miner 18:47–5210.1007/BF00199043 ↗
63. Kowalczyk G, Roberts JE (1994) Solid State 29Si NMR determination of crystalline silica in natural iron oxide pigments. Anal Chim Acta 286:25–3510.1016/0003-2670(94)80173-8 ↗
64. Myers S, Cygan R, Assink R, Boslough M (1998) 29Si MAS NMR relaxation study of shocked Coconino Sandstone from Meteor Crater, Arizona. Phys Chem Miner 25:313–31710.1007/s002690050120 ↗
65. Le Saoût G, Ben Haha M, Winnefeld F, Lothenbach B, Jantzen C (2011) Hydration degree of alkali-activated slags: a 29Si NMR study. J Am Ceram Soc 94:4541–454710.1111/j.1551-2916.2011.04828.x ↗
66. Bonk F, Schneider J, Cincotto MA, Panepucci HC (2003) Characterization by multinuclear high-resolution NMR of hydration products in activated blast-furnace slag pastes. J Am Ceram Soc 86:1712–171910.1111/j.1151-2916.2003.tb03545.x ↗
67. Lippmaa ASE, Mägi M (1986) High-resolution 27Al NMR of aluminosilicates. J Am Chem Soc 108:1730–173510.1021/ja00268a002 ↗
68. Moesgaard M, Keding R, Skibsted J, Yue Y (2010) Evidence of intermediate-range order heterogeneity in calcium aluminosilicate glasses. Chem Mater 22:4471–448310.1021/cm1011795 ↗
69. Murdoch JB, Stebbins JF, Carmichael ISE (1985) High-resolution 29Si NMR study of silicate and aluminosilicate glasses: the effect of network-modifying cations. Am Miner 70:370–382
70. Walkley B, San Nicolas R, Sani M-A, Gehman JD, van Deventer JSJ, Provis JL (2016) Synthesis of stoichiometrically controlled reactive aluminosilicate and calcium-aluminosilicate powders. Powder Technol 297:17–3310.1016/j.powtec.2016.04.006 ↗
71. Engelhardt G, Michel D (1987) High-resolution solid state NMR of silicates and zeolites. Wiley, Chichester
72. Duxson P, Provis JL, Lukey GC, Separovic F, van Deventer JSJ (2005) 29Si NMR study of structural ordering in aluminosilicate geopolymer gels. Langmuir 21:3028–303610.1021/la047336x ↗
73. Skibsted J, Jakobsen HJ, Hall C (1995) Quantification of calcium silicate phases in Portland cements by 29Si MAS NMR spectroscopy. J Chem Soc Faraday Trans 91:4423–443010.1039/ft9959104423 ↗
74. Lippmaa E, Mägi M, Tarmak M, Wieker W, Grimmer AR (1982) A high resolution 29Si NMR study of the hydration of tricalciumsilicate. Cem Concr Res 12:597–60210.1016/0008-8846(82)90020-5 ↗
75. Stebbins JF, Murdoch JB, Carmichael ISE, Pines A (1986) Defects and short-range order in nepheline group minerals: a silicon-29 nuclear magnetic resonance study. Phys Chem Miner 13:371–38110.1007/BF00309182 ↗
76. Lippmaa E, Maegi M, Samoson A, Engelhardt G, Grimmer AR (1980) Structural studies of silicates by solid-state high-resolution silicon-29 NMR. J Am Chem Soc 102:4889–489310.1021/ja00535a008 ↗
77. 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 114:1173–118210.1021/ja00030a008 ↗
78. Hansen MR, Jakobsen HJ, Skibsted J (2003) 29Si chemical shift anisotropies in calcium silicates from high-field 29Si MAS NMR spectroscopy. Inorg Chem 42:2368–237710.1021/ic020647f ↗
79. Viallis H, Faucon P, Petit JC, Nonat A (1999) Interaction between salts (NaCl, CsCl) and calcium silicate hydrates (C − S−H). J Phys Chem B 103:5212–521910.1021/jp983757+ ↗
80. Duxson P, Lukey GC, Separovic F, van Deventer JSJ (2005) Effect of alkali cations on aluminum incorporation in geopolymeric gels. Ind Eng Chem Res 44:832–83910.1021/ie0494216 ↗
81. Stebbins JF, Farnan I, Williams EH, Roux J (1989) Magic angle spinning NMR observation of sodium site exchange in nepheline at 500 °C. Phys Chem Miner 16:763–76610.1007/BF00209699 ↗
82. Buhl JC, Engelhardt G, Felsche J, Luger S, Foerster H (1988) 23Na MAS-NMR and 1H MAS-NMR studies in the hydro-sodalite system. Ber Bunsenges Phys Chem 92:176–18110.1002/bbpc.198800039 ↗