Low‐Temperature Electrochemical Synthesis of ZrO ₂ Films on Zirconium Substrates: Deposition of Thick Amorphous Films and <i>in situ</i> Crystallization on Zirconium Anode

Abstract

The feasibility of synthesizing crystalline ZrO 2 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 Zr 4+ , 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 ZrO 2 .