Effect of TiO2 on the optical, structural and crystallization behavior of barium borate glasses

• Barium borate glass with different TiO2-doping concentrations were prepared.
• UV–visible spectra were applied to indicate the states of TiO2 doped glass.
• FTIR was applied to study the building groups and the effect of titanium ions in the structure.
• XRD was applied to investigate the microstructure of the glass – ceramics.
• The influence of TiO2 on thermal expansion behavior was investigated.

Collective characterizations of prepared binary barium borate glass (50 mol % BaO – 50 mol % B2O3) together with samples containing increasing added TiO2 contents (5% → 30%) were carried out by optical and FT infrared absorption measurements. FT infrared and X-ray diffraction analysis were done for heat treated glass – ceramic derivatives prepared through two step regime process. Optical spectra of the glasses reveal the presence of titanium ions mainly in the tetravalent state imparting additional UV band beside strong UV absorption due to trace iron impurity. IR spectral studies indicate the presence of triangular and tetrahedral borate groups through the modification of BaO to some BO3 to BO4 groups beside the presence of titanium ions as interfering or overlapping TiO4 or BOTi groupings in the glassy network. Crystalline X-ray diffraction results indicate the separation of crystalline barium borate of the composition (2BaO.5 B2O3) as a main constituent together with some crystalline alkali titanates confirming the role of TiO2 of both as nucleating agent beside acting as structural forming through reaction with alkali oxides to form crystalline titanates. The optical band gap values reveal progressive decrease and increase of Urbach energy with TiO2 content and the same for the refractive index values and all these parameters are correlated with the proposed changes in the glass constitution with the introduction of TiO2. The additional thermal expansion measurements indicate the peculiar characteristic negative expansion up to 300 °C and after which an increase in the coefficient of thermal expansion is identified with the increase in temperature. The thermal parameters are also correlated with the modification of the glass structure by the introduction of titanium ions.