Hydrothermal synthesis of sodium bismuth titanate and titanate nanofibers

A hydrothermal processing method was developed for the synthesis of sodium bismuth titanate powders and thin films from suitable precursors at 150°C. Oxide precursors were best suited for preparing pure phase materials. The sodium bismuth titanate powders consisted of cube shaped crystals. A modified solution-reprecitation model involving partial dissolution of the precursors was proposed to explain the growth of these particles. The thin films were prepared on strontium titanate (100) substrate. A sample holder was specially designed and fabricated to secure the substrates in the reaction vessel. The result was a relatively smooth film of thickness ≤550 nm. The films were essentially single crystalline and had strong epitaxial relationship with the substrate. Titanate nanofibers (NaxH yTinO2n+1° zH2O) were known to form under similar hydrothermal conditions as sodium bismuth titanate powders. Detail research revealed that the pure hydroxide and oxide precursors tend to form sodium bismuth titanate powders or thin films. Titanate nanofibers were the predominant product when any other ions or organics were present in the precursor. Much faster reaction kinetics for the formation of nanofibers was observed when certain organic compounds were added deliberately with the precursors. Accordingly, a hydrothermal process was developed for converting the precursors to titanate nanofibers in a significantly shorter time than reported in the literature. A thin film consisting of vertically aligned nanofibers was prepared on titanium substrate at 150°C in as little as 30 minutes. Complete conversion of starting precursors to free standing nanofibers was achieved in ∼8 hours at 150°C. The as-prepared nanofibers were some form of sodium titanate. They were converted to hydrogen titanate by ion exchange. Differential Scanning calorimetric experiments were performed to understand the thermal evolution of the fibers. The hydrogen titanate fibers underwent structural modifications even at temperatures less than 100°C. Research was done to understand the structure of these hydrogen titanate nanofibers with the aid of HRTEM, simulation of HRTEM images and x-ray diffraction. Initial results revealed that the fibers observed under the microscope had either a lepidocrocite type structure or an anatase type structure.