Structure and dissolution of silicophosphate glass

Abstract

P₂O₅–SiO₂–Na₂O–CaO glasses are promising therapeutic ion-releasing materials. Herein, we investigated the state of silicon (Si) in P₂O₅–SiO₂–Na₂O–CaO glass using a model with a composition of 55.0P₂O₅–21.3SiO₂–23.7Na₂O (mol%), incorporating a six-fold-coordinated silicon structure (^[6]Si). The model was constructed using a classical molecular dynamics method and relaxed using the first-principles method. Further, we experimentally prepared glasses, substituting Na₂O for CaO, to investigate the dissolution of glass with varying ^[6]Si and PO₄ tetrahedra (Q_Pⁿ) distributions (n = number of bridging oxygens (BOs) to neighboring tetrahedra). ^[6]Si in the glass model preferentially coordinated with Q_P³. When Si was surrounded by phosphate groups, phosphorus (P) induced the formation of ^[6]Si by elongating the Si–O distance, and ^[6]Si acted like a glass network former (NWF). Na⁺ coordinated with ^[6]Si–O–P bonds via electrostatic interactions with BO. ³¹P and ²⁹Si magic-angle-spinning-nuclear-magnetic-resonance spectra of three experimental glass samples with the compositions of 55.0P₂O₅–21.3SiO₂–xCaO–(23.7 − x)Na₂O (mol%, x = 0, 12.4, and 23.7) showed that Q_P³ and ^[6]Si increased with increasing Na₂O. When each glass powder was immersed in a tris-HCl buffer solution at 37 °C, the dissolution of NWF ions and network modifier (NWM) ions increased almost monotonically with time for all samples, indicating that the solubility of the samples was suppressed by the coexistence of CaO and Na₂O, attributed to the delocalization of the electron distribution of P in the ^[6]Si-coordinated Q_P³ units compared to that in the P- or ^[4]Si-coordinated Q_P³ units, which reduces hydrolysis.