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Deciphering the structural origins of high sulfur solubility in vanadium-containing borosilicate glasses 1 1 Introduction 1 2 Experimental details 2 2.1 Synthesis of sulfur-free glasses 2 2.2 Synthesis of sulfur-containing glasses 2 2.3 Compositional analysis of glasses 3 2.4 Structural analysis of glasses 3 2.5 Density and thermal analysis 3 3 Results 4 3.1 Redox chemistry of vanadium in the investigated glasses 4 3.2 Impact of vanadium on the structure of glasses 5 3.2.1 Raman spectroscopy 5 3.2.2 11B, 27Al and 51V MAS NMR spectroscopy 6 3.2.3 Density, molar volume, and glass transition temperature 8 3.3 Sulfur solubility in glasses and its impact on glass structure and properties 8 3.3.1 Sulfur solubility in glasses 8 3.3.2 Impact of sulfur on the structure and properties of glasses 9 4 Discussion 10 4.1 Compositional dependence of redox chemistry of vanadium 10 4.2 Impact of vanadium redox on the glass structure 10 4.3 Impact of glass structure on SO42− solubility 11 5 Conclusion 11 Declaration of Competing Interest 12 Data availability 12 Acknowledgement 12 References 12
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