Melting and premelting of silicates: Raman spectroscopy and X-ray diffraction of Li2SiO3 and Na2SiO3

The isostructural lithium (Li₂SiO₃) and sodium (Na₂SiO₃) metasilicates have been investigated from room temperature up to the melting point by single-crystal Raman spectroscopy and energy-dispersive X-ray powder diffraction. The unit-cell parameters and Raman frequencies of Li₂SiO₃ vary regularly with temperature up to the melting point, which is consistent with the lack of premelting effects in calorimetric measurements. In contrast, Na₂SiO₃ undergoes a transition at about 850 K from orthorhombic Cmc 2₁ symmetry, to a lower symmetry (possibly Pmc 2₁), and shows near 1200 K changes in the Raman spectra that correlate well with the premelting effects as determined from calorimetry observations. In both compounds, a high alkali mobility likely sets in several hundreds of degrees below the melting point. Premelting in Na₂SiO₃ is associated with extensive deformation of the silicate chains as evidenced near the melting point by similarities in the Raman spectra of the crystalline and liquid phases.