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

Lithium zinc silicate glasses of composition (mol%): 17.5Li2O–(72−x)SiO2–xZnO−5.1Na2O−1.3P2O5−4.1B2O3, 5.5⩽x⩽17.7, were prepared by conventional melt-quenched technique and converted to glass-ceramic by controlled crystallization process. 29Si and 31P MAS-NMR was used to characterize the structure of both glass and glass-ceramic samples. Despite the complex glass composition, Q2, Q3 and Q4 sites are identified from 29Si MAS-NMR, which relative intensities are found to vary with the ZnO content, indicating a network depolymerization by ZnO. Moreover, well separated Q3 and Q4 resonances for low ZnO content indicates the occurrence of phase separation. From 31P MAS-NMR, it is seen that phosphorus is mainly present in the form of ortho-(Q0) and pyro-phosphate (Q1) 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 (Li2Si2O5), lithium zinc ortho-silicate (Li3Zn0.5SiO4), tridymite (SiO2) and cristobalite (SiO2) were identified as major silicate crystalline phases. Using 29Si MAS-NMR, quantification of these silicate crystalline phases is carried out and correlated with the ZnO content in the glass-ceramics samples. In addition, 31P spectra unambiguously revealed the presence of crystalline Li3PO4 and (Na,Li)3PO4 in the glass-ceramics.

29Si and 31P MAS-NMR analyses were carried out on multi-component Li2O–SiO2–ZnO–Na2O–P2O5–B2O3 glasses and glass-ceramics developed for sealing application. Structural data are reported, including phase separation process and quantification of amorphous and crystalline phases.Figure optionsDownload as PowerPoint slide