Thermal and structural properties of B2O3–H2O glasses

B2–2xO3–2xH2x glasses were prepared by quenching the melt contained in sealed tubes. The glass-forming range extends from x = 0 to 0.50 (equal to the stoichiometry of metaboric acid, HBO2). The glasses were characterized by differential scanning calorimetry and x-ray scattering. With increasing water content, the glass-transition temperature, Tg, decreases from 553 to 333 K. The specific heat of water-rich samples shows an unusual peak just above Tg. The origin of this peak, which is seen upon heating and cooling, has not been identified. Unlike the composition dependence of Tg, the x-ray structure factors depend for the most part linearly on the composition. In analogy with the crystalline layer compounds α-HBO2 and B(OH)3, the x-ray scattering data show evidence for layering in the medium-range order of water-rich glasses.