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Physics and Chemistry of Minerals

, Volume 23, Issue 8, pp 526–534 | Cite as

Dynamics of Na in sodium aluminosilicate glasses and liquids

  • A. M. George
  • J. F. Stebbins
Original Paper

Abstract

23Na NMR measurements on Na2Si3O7, Na3AlSi6O15, and NaAlSi3O8 glasses from room temperature to 1200°C show that the dynamics and local structure of sodium in silicate/aluminosilicate glasses and melts vary with composition and temperature.

The peak positions decrease in frequency between room temperature and 200°C indicating that the Na sees a larger average site as temperature is increased. Between 200°–300° and 700°C, line widths, nutation frequencies and peak positions are consistent with motional averaging of quadrupolar satellites. Above 700°C there is little or no change in the peak positions with temperature. Chemical shifts of the materials at 1000°C (Na2Si3O7: 3.6; Na3AlSi6O15:-1.3; NaAlSi3O8:-6.4 ppm) indicate a slight change in the average Na coordination number from 6–7 for the silicate to 7–8 for the aluminosilicates.

Relaxation time (T1) measurements show a shift in the T1 minimum to higher temperature with the addition of aluminum to the system. This is indicative of Na motion being hindered in aluminosilicates relative to silicates. Comparison of the data to a model for spin-lattice relaxation involving a distribution of barrier heights to atomic hopping (Svare et al. 1993) yields average barrier heights consistent with this, as well as indicating differences in the number of neighboring sites and amount of disorder around Na sites in the three glasses. The slopes on the high temperature side of the relaxation curves yield apparent activation energies for diffusion of 70 kJ/mol, as has been previously seen for several other alkali silicate liquids.

Keywords

Barrier Height Aluminosilicate Apparent Activation Energy Relaxation Curve Temperature Side 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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References

  1. Bansal NP, Doremus RH (1986) Handbook of glass properties. Academic Press, OrlandoGoogle Scholar
  2. Engelhardt G, Michel D (1987) High-resolution solid-state NMR of silicates and zeolites. Wiley, New YorkGoogle Scholar
  3. Fiske PS, Stebbins JF (1994) The structural role of Mg in silicate liquids: A high-temperature 23Mg, 23Na, and 29Si NMR study. Am Mineral 79:848–861Google Scholar
  4. Fiske PS, Stebbins JF, Farnan I (1994) Bonding and dynamical phenomena in MgO: A high-temperature 17O and 25Mg NMR study. Phys Chem Minerals 20:587–593Google Scholar
  5. George AM, Stebbins JF (1995) High-temperature 23Na MAS NMR data for albite: comparison to chemical-shift models. Am Mineral 80:878–884Google Scholar
  6. Göbel E, Müller-Warmuth W, Olyschläger H, Dutz H (1979) 7Li NMR spectra, nuclear relaxation, and lithium ion motion in alkali silicate, borate, and phosphate glasses. J Mag Res 36:371–387Google Scholar
  7. Greaves GN (1985) EXAFS and the structure of glass. J Non-Cryst Sol 71:203–217Google Scholar
  8. Greaves GN (1992) Glass structure and ionic transport. In: Pye LD, Lacourse WC, Stevens HJ (eds) Physics of non-crystalline solids. Taylor & Francis, London, pp 453–459Google Scholar
  9. Greaves GN, Ngai KL (1995) Reconciling ionic-transport properties with atomic structure in oxide glasses. Phys Rev B 52:6368–6380Google Scholar
  10. Hendrickson JR, Bray PJ (1974) Nuclear magnetic resonance studies of 7Li ionic motion in alkali silicate and borate glasses. J Chem Phys 61:2754–2764Google Scholar
  11. Hsieh CH, Jain H, Miller AC, Kamitsos EI (1994) X-ray photoelectron spectroscopy of Al- and B-substituted sodium trisilicate glasses. J Non-Cryst Sol 168:247–257Google Scholar
  12. Hughes DG (1993) Non-exponential relaxation of I=3/2 nuclear spins in solids. J Phys Cond Matt 5:2025–2032Google Scholar
  13. Kamitsos EI, Kapoutsis JA, Jain H, Hsieh CH (1994) Vibrational study of the role of trivalent ions in sodium trisilicate glass. J Non-Cryst Sol 171:31–45Google Scholar
  14. Klonkowski A (1983) The structure of sodium aluminosilicate glass. Phys Chem Glasses 24:166–171Google Scholar
  15. Lacourse WA (1976) Structural influences on diffusion in glassthe mixed site effect. J Non-Cryst Sol 21:431–434Google Scholar
  16. Lam DJ, Paulikas AP, Veal BW (1980) X-ray photoemission spectroscopy studies of soda aluminosilicate glasses. J Non-Cryst Sol 42:41–47Google Scholar
  17. Liu SB, Pines A, Brandriss M, Stebbins JF (1987) Relaxation mechanisms and effects of motion in albite (NaAlSi3O8) liquid and glass: a high temperature NMR study. Phys Chem Minerals 15:155–162Google Scholar
  18. Liu SB, Stebbins JF, Schneider E, Pines A (1988) Diffusive motion in alkali silicate melts: An NMR study at high temperature. Geochim Cosmochim Acta 52:527–538Google Scholar
  19. Maekawa H (1993) NMR studies of the structure and dynamics of silicate melts. Ph.D. thesis, Hokkaido UniversityGoogle Scholar
  20. Marchi GD, Mazzoldi P, Miotello A (1988) Analysis of ionic conductivity in alkali and mixed-alkali aluminosilicate glasses. J Non-Cryst Sol 105:307–312Google Scholar
  21. Mazurin OV, Streltsina MV, Schvaiko-Svaikovskaya TP (eds) (1987) Handbook of glass data, ternary silicate glasses. Elsevier, New YorkGoogle Scholar
  22. McKeown DA, Waychunas GA, Brown GEJ (1985) EXAFS and XANES study of the local coordination environment of sodium in a series of silica-rich glasses and selected minerals within the Na2O-Al2O3-SiO2 system. J Non-Cryst Sol 74:325–348Google Scholar
  23. Merzbacher CI, White WB (1988) Structure of Na in aluminosilicate glasses: a far-infrared reflectance spectroscopic study. Am Mineral 73:189–1094Google Scholar
  24. Neil JM, Apps JA (1979) Solubility of albite in the aqueous phase at elevated temperatures. Lawrence Berkeley Laboratory, LBL #10349Google Scholar
  25. Newell RG, Feuston BP, Garofalini SH (1989) The structure of sodium trisilicate glass via molecular dynamics employing three-body potentials. J Mat Res 4:434–439Google Scholar
  26. Sen S, George AM, Stebbins JF (1996) Ionic conduction and mixed cation effect in silicate glasses and liquids: 23Na and 7Li NMR spin-lattice relaxation and a multiple-barrier model of percolation. J Non-Cryst Sol 197:53–64Google Scholar
  27. Stebbins JF (1991) Nuclear magnetic resonance at high temperature. Chem Rev 91:1353–1373Google Scholar
  28. Svare I, Borsa F, Torgeson DR, Martin SW (1993) Correlation functions for ionic motion from NMR relaxation and electric conductivity n the glassy fast-ion conductor (Li2S)0.56(SiS2)0.44. Phys Rev B 48:9336–9344Google Scholar
  29. Uchino T, Sakka T, Ogata Y, Iwasaki M (1992) A new model of ionic transport for single- and mixed-alkali oxides based on ab initio molecular orbital calculations. J Non-Cryst Sol 146:26–42Google Scholar
  30. Wakabayashi H (1989) The relationship between composition and electrical conductivity in glasses containing network forming trivalent cations. Phys Chem Glasses 30:51–54Google Scholar
  31. Xue X, Stebbins JF (1993) 23Na NMR chemical shifts and local Na coordination environments in silicate crystals, melts, and glasses. Phys Chem Minerals 20:297–307Google Scholar
  32. Youngman RE, Zwanziger JW (1994) Multiple boron sites in borate glass detected with dynamic angle spinning nuclear magnetic resonance. J Non-Cryst Sol 168:293–297Google Scholar
  33. Zirl DM, Garofalini SH (1990) Structure of sodium aluminosilicate glasses. J Am Ceram Soc 73:2848–2856Google Scholar

Copyright information

© Springer-Verlag 1996

Authors and Affiliations

  • A. M. George
    • 1
  • J. F. Stebbins
    • 1
  1. 1.Deparment of Geological and Environmental SciencesStanford UniversityStanfordUSA

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