Potentiostatic electrolysis of fluoride melts with zirconium oxide additives

Currently, the demand for zirconium-based alloys and materials is growing significantly due to their high thermal and corrosion resistance combined with mechanical strength. Existing technologies for producing zirconium and its alloys are complicated by the high temperature of the process, or labor intensity and multi-stage nature, which significantly increases the cost of the target material up to the loss of profitability of the process. Electrochemical synthesis of zirconium and its alloys in fluoride-based melts, using zirconium oxides as the main metal-containing consumable component, seems more profitable. In this work, a series of electrolysis tests were carried out to deposit Al-Zr alloy at a potential of 1.6 V on graphite and molybdenum cathodes. According to the previously obtained results, in the presence of ZrO₂ in the KF-AlF₃-Al₂O₃ melt, a plateau and a discharge peak of electroactive ions appear on the cathode branch of the voltammograms at potentials of -1.4 and -1.7 V, ZrI and ZrII, respectively. Similar responses appear on tungsten at potentials of -1.3 and -1.6 V, respectively, and in the potential region of -1.9 V there is a clear peak (Al) of electroreduction of aluminum ions. As a result of electrolysis, it was found that the graphite anode was consumed, and a fairly well-bonded deposit was formed on the cathode. Part of the cathode deposit was mechanically separated from the cathode for analysis of its chemical and phase composition. Based on the results of X-ray phase analysis, it was found that the cathode deposit mainly consists of Al₃Zr and aluminum compounds with molybdenum impurities, with the composition Al₁₂Mo, which is consistent with known ideas about the formation of intermetallic compounds during the interaction of aluminum with other metals. Electrolysis of the melt on the graphite cathode was carried out under similar conditions. Based on a microphotograph of the cathode cross section, it was found that during electrolysis, a layer of deposit containing both zirconium and aluminum was formed at the electrode-electrolyte phase boundary.