Simplified chemical route for the synthesis of barium titanyl oxalate (BTO)

A simple chemical route is developed to obtain an important molecular precursor (leading to barium titanate powders), namely barium titanyl oxalate (BTO) with nearly theoretical yield. In this route, 0.1 M alcoholic solution of titanium tetrabutoxide is reacted with 0.1 M alcoholic solution of oxalic acid to form titanyl oxalate (TiOC₂O₄). This was further converted to soluble ammonium titanyl oxalate (ATO); (NH₄)₂TiO(C₂O₄)₂.H₂O by reacting with an equimolar aqueous solution of ammonium oxalate (pH 4.25). Instead of using available barium salts (halide/nitrate/acetate) solution, a modified barium precursor solution with controlled pH (=4.2) is prepared for carrying out cation-exchange reaction with ATO. For this purpose the modified Ba-precursor solution is freshly prepared by partial neutralization of a 0.1 M aqueous solution of barium hydroxide with controlled addition of dilute HNO₃ (1.1 M) solution. The pH of this solution is the same as that of the ATO solution. The exchange reaction between equimolar ATO and modified Ba-precursor solution precipitated barium titanyl oxalate (BTO) with a quantitative yield at room temperature. Submicron-sized, stoichiometric, pure BaTiO₃ powders were obtained by the controlled pyrolysis of BTO in air. The present communication deals with the detailed analysis of this simplified method in producing BTO/BT powders and their characterization employing various physicochemical techniques.