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The morphological and structural properties of sodium silicate (Na 2 O-SiO 2 ) glasses were analyzed using atomic force microscopy (AFM) and light scattering following thermal treatments. AFM observations indicated that the glass surface microstructure evolves during the phase separation mechanisms from continuous interpenetrating phases in the spinodal decomposition process to separated droplets embedded in a continuous matrix for the nucleation/growth one. Raman mapping gave evidence of a phase separation through the nucleation/growth process with formation of silica-rich clusters characterized by higher polymerization degree as separate droplets. The variations in inhomogeneities versus temperature investigated by Brillouin are exponential for spinodal decomposition and linear in the case of nucleation/growth mechanism. Nuclear magnetic resonance spectroscopy was used to investigate the spatial distribution of the various Q n species present in thermally treated glasses and allows determining fractal dimension between two and three.

Novel statistical analysis and machine learning algorithms are proposed for the deconvolution and interpretation of Raman spectra of silicate glasses in the Na 2 O-CaO-SiO 2 system. Raman spectra are acquired along diffusion profiles of three pairs of glasses centered around an average composition of 69.9 wt.% SiO 2 , 12.7 wt.% CaO, 16.8 wt.% Na 2 O. The shape changes of the Raman spectra across the compositional domain are analyzed using a combination of principal component analysis (PCA) and sparse non-negative matrix factorization (NMF). This procedure yields components accounting for the observed changes, as well as their mixing proportions, without any direct prior assumption as to their actual shape, number or position. These methods are applied separately to the Q band (wavenumbers in the range 850-1400 cm −1), the main band (200-850 cm −1) and to the whole spectra (200-1400 cm −1). Compositional profiles obtained by Electron Probe Micro-Analysis (EPMA) are then used to relate spectral components to structural entities. Spectral components extracted from a Q band analysis and a complete spectral analysis show significant similarities both in terms of shape of the components and their mixing proportions. This result implies a link between Q n species and the shift of the medium-range network features in the main band of the Raman spectra. To illustrate the possibilities of the method, a linear regression model is used to relate the proportions of spectral components derived from the Raman spectra to chemical composition. This model can be used to determine the composition of different glasses inside the investigated compositional domain with reasonable accuracy.