MAS-NMR study of lithium zinc silicate glasses and glass-ceramics with various ZnO content

Journal Article · Fri Feb 15 00:00:00 EST 2008 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2007.11.023· OSTI ID:21043887

Goswami, Madhumita ^[1]; Kothiyal, Govind P ^[2]; Montagne, Lionel ^[1]; Delevoye, Laurent ^[1]

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1. UCCS-Unite de Catalyse et Chimie du Solide, UMR CNRS 8181, Ecole Nationale Superieure de Chimie de Lille, Universite des Sciences et Technologies de Lille, BP 108, 59652 Villeneuve d'Ascq Cedex (France)
2. Technical Physics and Prototype Engineering Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India)

Lithium zinc silicate glasses of composition (mol%): 17.5Li{sub 2}O-(72-x)SiO{sub 2}-xZnO-5.1Na{sub 2}O-1.3P{sub 2}O{sub 5}-4.1B{sub 2}O{sub 3}, 5.5{<=}x{<=}17.7, were prepared by conventional melt-quenched technique and converted to glass-ceramic by controlled crystallization process. {sup 29}Si and {sup 31}P MAS-NMR was used to characterize the structure of both glass and glass-ceramic samples. Despite the complex glass composition, Q{sup 2}, Q{sup 3} and Q{sup 4} sites are identified from {sup 29}Si MAS-NMR, which relative intensities are found to vary with the ZnO content, indicating a network depolymerization by ZnO. Moreover, well separated Q{sup 3} and Q{sup 4} resonances for low ZnO content indicates the occurrence of phase separation. From {sup 31}P MAS-NMR, it is seen that phosphorus is mainly present in the form of ortho-(Q{sup 0}) and pyro-phosphate (Q{sup 1}) structural units and variation of ZnO content did not have much effect on these resonances, which provides an additional evidence for phase separation in the glass. On conversion to glass-ceramics, lithium disilicate (Li{sub 2}Si{sub 2}O{sub 5}), lithium zinc ortho-silicate (Li{sub 3}Zn{sub 0.5}SiO{sub 4}), tridymite (SiO{sub 2}) and cristobalite (SiO{sub 2}) were identified as major silicate crystalline phases. Using {sup 29}Si MAS-NMR, quantification of these silicate crystalline phases is carried out and correlated with the ZnO content in the glass-ceramics samples. In addition, {sup 31}P spectra unambiguously revealed the presence of crystalline Li{sub 3}PO{sub 4} and (Na,Li){sub 3}PO{sub 4} in the glass-ceramics. - Graphical abstract: {sup 29}Si and {sup 31}P MAS-NMR analyses were carried out on multi-component Li{sub 2}O-SiO{sub 2}-ZnO-Na{sub 2}O-P{sub 2}O{sub 5}-B{sub 2}O{sub 3} glasses and glass-ceramics developed for sealing application. Structural data are reported, including phase separation process and quantification of amorphous and crystalline phases.

• OSTI ID: 21043887
• Journal Information: Journal of Solid State Chemistry, Vol. 181, Issue 2; Other Information: DOI: 10.1016/j.jssc.2007.11.023; PII: S0022-4596(07)00494-X; Copyright (c) 2007 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BORON OXIDES
CERAMICS
CRISTOBALITE
CRYSTALLIZATION
DEPOLYMERIZATION
GLASS
LITHIUM OXIDES
LITHIUM PHOSPHATES
LITHIUM SILICATES
NUCLEAR MAGNETIC RESONANCE
PHOSPHORUS
PHOSPHORUS 31
PHOSPHORUS OXIDES
SEPARATION PROCESSES
SILICON 29
SILICON OXIDES
SODIUM OXIDES
SPECTRA
ZINC OXIDES
ZINC SILICATES