Controlling oxygen coordination and valence of network forming cations
T. Aoyagi, Shinji Kohara, T. Naito, Yohei Onodera, Motomune Kodama, Taigo Onodera, Daiko Takamatsu, Shuta Tahara, Osami Sakata, Tatsuya Miyake, Kentaro Suzuya, Koji Ohara, Takeshi Usuki, Yamato Hayashi, Hirotsugu Takizawa
Abstract
Abstract Understanding the structure-property relationship of glass material is still challenging due to a lack of periodicity in disordered materials. Here, we report the properties and atomic structure of vanadium phosphate glasses characterized by reverse Monte Carlo modelling based on neutron/synchrotron X-ray diffraction and EXAFS data, supplemented by Raman and NMR spectroscopy. In vanadium-rich glass, the water durability, thermal stability and hardness improve as the amount of P 2 O 5 increases, and the network former of the glass changes from VO x polyhedra to the interplay between VO x polyhedra and PO 4 tetrahedra. We find for the first time that the coordination number of oxygen atoms around a V 4+ is four, which is an unusually small coordination number, and plays an important role for water durability, thermal stability and hardness. Furthermore, we show that the similarity between glass and crystal beyond the nearest neighbour distance is important for glass properties. These results demonstrate that controlling the oxygen coordination and valence of the network-forming cation is necessary for designing the properties of glass.