Preparation of NASIglasses by Sol-Gel Process

솔-젤법에 의한 NASIglass의 제조

  • 김희주 (경상대학교 무기재료공학과) ;
  • 강은태 (경상대학교 무기재료공학과) ;
  • 김종옥 (배재대학교 무기재료공학과)
  • Published : 1995.12.01

Abstract

Nasigels of composition Na0.75Zr2PSi2O12 and Na3Zr2PSi2O12 have been synthesized by the sol-gel technique using metal alkoxide precursors. The monolithic dry gels of Na0.75Zr2PSi2O12 with no crack have been prepared by the control of the shrinkage rte, but gels of Na3Zr2PSi2O12 were impossible to prepare without cracking. The gels treated up to 80$0^{\circ}C$ led to the formtion of glass but the glasses were converted to the crystalline phases at above this temperature. Crystaline phases precipitated from the Na0.75Zr2PSi2O12 glass were NASICON-like phase, Na2Si2O5, and free Zirconia. Phase that precipitated from the Na3Zr2PSi2O12 was only rhombohedral NASICON. For Na0.75Zr2PSi2O12 gels, framework of PO4 tetrahedra and SiO4(PO4) tetrahedra formed at low temperature but changed to that of SiO4 and SiO4(PO4) tetrahedras as it were crystallized. In the case of Na3Zr2PSi2O12 gel, framework of isolated PO4 and SiO4 tetrahedras formed at low temperature but changed to SiO4(PO4) tetrahedra framework which usually formed in the NASICON crystal after crystallization at high temperature. The gels treated up to 80$0^{\circ}C$ contained the residual water. The ionic conduction was attributed to the motion of proton and Na+ ion at low (up to 150~20$0^{\circ}C$) and high temperatures, respectively. As the temperature of heat treatment increased, ionic conductivity gradaully increased with the extent of precipitation of crystalline phase.

Keywords

References

  1. Superionic Solids and Solid Electrolytes Recent Trends Nasicon Materials G. Collin;J.P. Boilot;A.L. Laskar(ed.);S.Chandra(ed.)
  2. Mat. Res. Bull. v.14 Phase Transformation in $N_{1+x}Si_xZr_2P_{1-x}O_{12}$ J.P. Boilot;J.P. Salanie;G. Desplanches;D. Le Potier
  3. Solid State Jonics v.3/4 Fabrication and Characterization of Nasicon Electrolytes R.S. Gordon;G.R. Miller;B.J. McEntire;E.D. Beck;J.R. Rasmussen
  4. Solid State Ionics v.9/10 Nasiglas: A new Vitreous Electrolyte S. Susman;C.J. Delbecq;J.A. McMillan
  5. 일본요업협회지 v.97 no.10 Ionic Conductivity of Na₂O-ZrO₂-P₂-SiO₂System Glass Certamic S. Morimoto
  6. Solid State Ionics International Conference on Advanced Materials-ICAM91 Super-Conducting Glass in the System Na₂O-ZrO₂-S₁O₂-P₂$O_5$ J.W. Hoj;J. Engell
  7. Solid State Ionics v.9/10 Formation of Superionic Gels and Glasses by Low Temperature Chemical Polymerization J.P. Boilot;Colomban;N. Blanchard
  8. Solid State Ionics v.18/19 NASICON:Amorphous to Crystalline Compounds J.P. Boilot;Colomban;G. Collin
  9. J. Mat. Sci v.16 Conversion of Monolithic Gels to Glasses in a Multicomponent Silicate Glass System C.J. Brinker;S.P. Mukherjee
  10. J. Solid State Ionics v.21 Orientational Disorder, Glass/Crystal Transition and Superionic Conductivity in NASICON Colomban
  11. J. Mat. Sci v.13 Synthesis of Glasses by Hot-Pressing of Gels M. Decottingnies;J. Phalippou;J. Zarzycki
  12. J. Non-Cryst Solids v.20 Vibrational Spectra of Vapor-Deposited Binary Phosphosilicate Glasses J. Wong
  13. J. Non-Cryst. Solids v.40 An Infrared Study of Crystallization in Sodium-Disilicate Glasses Containing Iron Oxides J.W. Park;H. Chen
  14. Phy. Chem. Glasses v.26 no.3 The Vibrational Spectra of Glasses in the Na₂O-SiO₂-P₂$O_5$ System with a 1:1 SiO₂:P₂$O_5 $ Molar Ratio I.N. Chakraborty;R.A. Condrate Snr.
  15. J. Mat. Sci. v.23 The Infrared and Raman Spectra of ZrO₂-SiO₂Glasses Prepared by a Sol-Gel Process S.W. Lee;R.A. Condrate Sr
  16. Mat. Res. Bull. v.11 Crystal Structures and Crystal Chemistry in the System Na₁-xZr₂SixP₃-x$O_{12}$ H. Y-P. Hong