稀有金属
稀有金屬
희유금속
CHINESE JOURNAL OF RARE METALS
2009年
6期
779-784
,共6页
李晴宇%杜继红%奚正平%李争显%杨升红
李晴宇%杜繼紅%奚正平%李爭顯%楊升紅
리청우%두계홍%해정평%리쟁현%양승홍
熔盐电解%ZrO_2与TiO_2混合物%制备%钛锆合金%反应历程
鎔鹽電解%ZrO_2與TiO_2混閤物%製備%鈦鋯閤金%反應歷程
용염전해%ZrO_2여TiO_2혼합물%제비%태고합금%반응역정
electrolysis in molten calcium chloride%ZrO_2 and TiO_2 mixture%preparation%TiZr alloy%reaction mechanism
采用熔盐电解法由ZrO_2与TiO_2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 ℃, CaCl_2熔盐中以烧结的ZrO_2与TiO_2混合氧化物为阴极,石墨棒为阳极, 3.1 V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ZrO_2先生成CaZrO_3, 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, TiO_2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ZrO_2, TiO_2先形成CaZr_mTi_nO_x, 然后直接脱氧还原为TiZr.
採用鎔鹽電解法由ZrO_2與TiO_2混閤氧化物(Ti, Zr原子比為1∶ 1)一步製備齣瞭TiZr閤金, 併探討瞭反應機製. 溫度為900 ℃, CaCl_2鎔鹽中以燒結的ZrO_2與TiO_2混閤氧化物為陰極,石墨棒為暘極, 3.1 V恆電壓電解, 製備齣瞭鈦鋯閤金. 結果錶明, 所得產物的組分與投料比例一緻, 鈦、鋯為無限互溶的固溶體, 電解反應是由外嚮內進行的. 其閤金化歷程為: 部分ZrO_2先生成CaZrO_3, 然後繼續脫氧還原為鋯的低價氧化物直至還原為金屬鋯, 一旦有金屬鋯生成, TiO_2在金屬鋯上直接電解還原形成鈦的低價氧化物, 直至生成金屬鈦後與鋯形成固溶體; 其餘ZrO_2, TiO_2先形成CaZr_mTi_nO_x, 然後直接脫氧還原為TiZr.
채용용염전해법유ZrO_2여TiO_2혼합양화물(Ti, Zr원자비위1∶ 1)일보제비출료TiZr합금, 병탐토료반응궤제. 온도위900 ℃, CaCl_2용염중이소결적ZrO_2여TiO_2혼합양화물위음겁,석묵봉위양겁, 3.1 V항전압전해, 제비출료태고합금. 결과표명, 소득산물적조분여투료비례일치, 태、고위무한호용적고용체, 전해반응시유외향내진행적. 기합금화역정위: 부분ZrO_2선생성CaZrO_3, 연후계속탈양환원위고적저개양화물직지환원위금속고, 일단유금속고생성, TiO_2재금속고상직접전해환원형성태적저개양화물, 직지생성금속태후여고형성고용체; 기여ZrO_2, TiO_2선형성CaZr_mTi_nO_x, 연후직접탈양환원위TiZr.
Direct preparation of TiZr alloy from ZrO_2, TiO_2 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 ZrO_2, TiO_2 oxide mixture as the cathode, was performed in molten salt of CaCl_2 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 pre-determined ratio, and Ti-Zr alloy produced a solid solution with complete miscibility in the entire range of composition. There were two kinds of mechanism in the process of electrolysis: part of ZrO_2 was transformed to CaZrO_3 firstly, then CaZrO_3 was reduced to Zr, once Zr metal occured, TiO_2 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 ZrO_2 and TiO_2 oxide mixture formed CaZr_mTi_nO_x firstly, then formed TiZr alloy directly.