采用熔盐电解法由ZrO2与TiO2混合氧化物(Ti,Zr原子比为1:1)一步制备出了TiZr合金,并探讨了反应机制。温度为900℃,CaCl2熔盐中以烧结的ZrO2与TiO2混合氧化物为阴极,石墨棒为阳极,3.1V恒电压电解,制备出了钛锆合金。结果表明,所得产物的组分与投料比例一致,钛、锆为无限互溶的固溶体,电解反应是由外向内进行的。其合金化历程为:部分ZrO2先生成CaZrO2,然后继续脱氧还原为锆的低价氧化物直至还原为金属锆,一旦有金属锆生成,TiO2在金属锆上直接电解还原形成钛的低价氧化物,直至生成金属钛后与锆形成固溶体;其余ZrO2,TiO2先形成CaZrmTinOx,然后直接脱氧还原为TiZr。
Direct preparation of TiZr alloy from ZrO2, TiO2 oxide mixture by electrolysis in molten salt of calcium chloride and its reaction mechanism was investigated, constant voltage ( 3.1 V) electrolysis, with a graphite anode and ZrO2, TiO2 oxide mixture as the cathode, was performed in molten salt of CaC12 at 900 ℃ for 0.5, 1, 3, 5, 8 and 12 h, respectively. The result showed that the atomic ratio of Ti to Zr in the prepared alloy agreed well with the rio, and Ti-Zr alloy produced a complete miscibility in the entire tion. There were two kinds of pre-determined rasolid solution with range of composi- mechanism in the process of electrolysis : part of ZrO2 was transformed to CaZrO3 firstly, then CaZrO3 was reduced to Zr, once Zr metal occured, TiO2 was reduced to Ti metal on the Zr atoms. The two kinds of metal was dissolved in each other to form TiZr solid solution; The rest of ZrO2 and TiO2 oxide mixture formed CaZrmTinOx firstly, then formed TiZr alloy directly.