Low-Temperature Electrochemical Synthesis of ZrO2 Films on Zirconium Substrates: Deposition of Thick Amorphous Films and in situ Crystallization on Zirconium Anode

The feasibility of synthesizing crystalline ZrO₂ films at low temperatures was evaluated using an electrochemical method. Anodization of zirconium-metal substrates in tetraethyl ammonium hydroxide (TEAOH) solutions under constant applied voltage conditions at ～25° and ～100°C was investigated. The chemistry and microstructure of the anodic oxide films deposited on the zirconium-metal substrates under the above conditions were characterized using X-ray diffractometry and scanning electron microscopy. The results indicated that, with sufficiently high applied voltages (in the range of 300 V) at pH ～9.5, the initial dissolution of the zirconium anode resulted in the local saturation of the electrolyte solution with Zr⁴⁺, forming Zr(OH)^?₅, which deposited electrophoretically on the anode as a thick, gelatinous film at 25°C. Similar treatments at 100°C resulted in an in situ crystallization of Zr(OH)₄ gel to monoclinic ZrO₂.