Crystallization and Phase-Transition Characteristics of Sol−Gel-Synthesized Zinc Titanates

The synthesis of a ZnO−TiO 2 nanocomposite usually results in the formation of one or more of three compounds—Zn 2 TiO 4, Zn 2 Ti 3 O 8, and ZnTiO 3 —along with other secondary impurity phases, such as rutile-TiO 2 or ZnO. Obtaining a phase-pure composite of either of these materials is one of the challenges in materials chemistry. For example, pure ZnTiO 3 cannot be synthesized under normal conditions, because the ZnTiO 3 phase readily transforms to Zn 2 TiO 4 and rutile. Zn 2 Ti 3 O 8 is reported as a metastable form of ZnTiO 3 . The Zn 2 TiO 4 form is usually synthesized via solid-state reaction at high temperatures (typically above 1000 °C). In the current study, the crystalline and phase-transformation behaviors of sol−gel-synthesized zinc titanates has been investigated systematically, with regard to various Zn:Ti precursor molar ratios. X-ray diffraction (XRD) has shown that, with excess titanium precursor, zinc metatitanate (ZnTiO 3 ) is the preferred zinc titanate phase formed at temperatures of 600−900 °C, with a direct transformation of zinc metatitanate to zinc orthotitanate (Zn 2 TiO 4 ) occurring at 1000 °C. However, synthesis involving titanium precursor in the presence of excess zinc precursor forms Zn 2 Ti 3 O 8 with a cubic defect spinel structure at temperatures of 700−900 °C, with a direct transformation to zinc orthotitanate occurring at 1000 °C. The current study also indicated that the percentage of zinc titanate phases can be controlled by varying the initial sol−gel reaction conditions. Spectroscopic investigations have been carried out to understand the effect of precursor (Zn(CH 3 COO) 2 ·2H 2 O and H 2 C 2 O 4 ) formulations on the crystallization and phase-transition behaviors of these composites. Fourier transform infrared and Raman spectroscopy have shown the presence of the oxalate form of zinc and titanium. However, neither of these techniques could reveal if the titanium oxalate chains exist separately from zinc oxalate chains or if they combine during the initial stages of preparation. Further powder XRD investigation proposed that two separate metal oxalate chains were formed during the synthesis. Previous reports indicate that the formation of Zn 2 TiO 4 and Zn 2 Ti 3 O 8 is limited by the presence of anatase and ZnTiO 3 only forms in the presence of rutile. Results from the present study confirm that, in a sol−gel synthesis, the formation of various forms of zinc titanates is influenced by the zinc oxide/titanium dioxide composition.