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第3期 郝占忠等：RE2ONH亚2系合成稀土氟化物的反应规律 .277 (③)降低系统压力，可以降低各反应的起始温 tion Eu2Os-NHaF.Can J Chem.1977.55(14):2620 度和终止温度，有利于反应进行， [8]刘文生，云月厚，李国栋.干法氟化制备高纯金属镝的研究.稀 有金属，2003,27(1)：154 (4)生产上应采用“常压低温合成一真空高温分 [9]颜豪威.NHF2氟化制备稀土氟化物的化学原理及工艺探 解、脱铵”的工艺 讨.江西冶金，1995,15(6)：31 [IO]由芳田，王颖霞，林建华.NHF一LF体系的合成及荧光性 参考文献 质.无机化学学报，2002,18(1)：41 [1]Spedding F H,Croat JJ.Beaudry B J.Research and Develop- [11]童兆达。碳酸稀土转型制备氟化稀土，稀土，1987,18(1)： ment Report Is-1900.lowa:Ames Laboratory.1968 62 [2]徐光宪.稀土（中册），北京：冶金工业出版社，1995：26 [12]Gschneidner K A Jr.Eyring L R.Handbook on the Physics and [3]金卓仁·稀土氟化物在复合自润滑轴承中作用的研究，稀土， Chemistry of Rare Earth,Vol.1.New York:North-Holland 1996,17(5):57 Publishing Company.1978 []王亚车，刘前，索全伶，等.稀土氟化物的沉淀方法及组成研 [13]库巴谢夫斯基0，奥尔考克CB.冶金热化学.邱竹贤，译. 究.稀土，2000,21(1)：14 北京：冶金工业出版社，1985：326 [5]Krupa J C.Mayolet A.Queffelee M.Luminescence in fluoride [14]梁英教，车荫昌，无机物热力学数据手册.沈阳：东北大学 compounds excited in the VUV range.Ann Chim Sci Mater. 出版社，1993：172 1998,23(1):431 [15]天津化工研究院，无机盐工业手册（上册）北京：化工出版 [6]Popov AI.Knudson G E.Preparation and properties of the rare 社，1979：685 earth fluorides and ox fluorides.J Am Chem Soc,1954,76(15): [16们李文超·治金与材料物理化学.北京：冶金工业出版社， 3921 2001:22 [7]Rajeshwar K,Secco E A.Study of NH4EuF4 in solid state reac Principles of reactions in the synthesis of rare earth fluorides in RE2O3-NH4HF2 systems HAO Zhanzhong),ZHA NG Jianliang,WANG Bin2) 1)Metallurgical and Ecological Engineering School.University of Science and Technology Beijing.Beijing 100083.China 2)Baotou Teachers College,Baotou 014030.China ABSTRACI Rare earth fluorides were synthesized with RE2O3 and NH4HF2 under atmospheric pressure and vacuum in RE2O3 NH4HF2 systems,the reactions in the systems were studied,and a new mechanism for the synthesis of REF3 was proposed.Powder La203,Gd203 started to react with NH4HF2 at low temperature,and the products were RENH4F4(RE=La,Gd),NH4F,NH3 and H20.RENH4F4 was decomposed to REF3 and NH4F at high temperature,accompanied with the volatilization and decomposition of NH4F.The whole process could be divided into three steps of synthesis,decomposition and deammoniation.The initial and final tempera tures of the reactions were reduced under vacuum.The combination process of synthesis under atmospheric pres- sure at low temperature and decomposition and deammoniation under vacuum at high temperature should be ap- plied to the preparation of rare earth fluorides. KEY WORDS rare earth fluorides;NH4HF2;synthesis;reaction（3） 降低系统压力可以降低各反应的起始温 度和终止温度有利于反应进行． （4） 生产上应采用“常压低温合成－真空高温分 解、脱铵”的工艺． 参 考 文 献 ［1］ Spedding F HCroat J JBeaudry B J．Research and Development Report Is－1900．Iowa：Ames Laboratory1968 ［2］ 徐光宪．稀土（中册）．北京：冶金工业出版社1995：26 ［3］ 金卓仁．稀土氟化物在复合自润滑轴承中作用的研究．稀土 199617（5）：57 ［4］ 王亚军刘前索全伶等．稀土氟化物的沉淀方法及组成研 究．稀土200021（1）：14 ［5］ Krupa J CMayolet AQueffelec M．Luminescence in fluoride compounds excited in the VUV range．Ann Chim Sci Mater 199823（1）：431 ［6］ Popov A IKnudson G E．Preparation and properties of the rare earth fluorides and ox fluorides．J Am Chem Soc195476（15）： 3921 ［7］ Rajeshwar KSecco E A．Study of NH4EuF4in solid state reaction Eu2O3－NH4F．Can J Chem197755（14）：2620 ［8］ 刘文生云月厚李国栋．干法氟化制备高纯金属镝的研究．稀 有金属200327（1）：154 ［9］ 颜豪威．NH4HF2 氟化制备稀土氟化物的化学原理及工艺探 讨．江西冶金199515（6）：31 ［10］ 由芳田王颖霞林建华．NH4F－LnF 体系的合成及荧光性 质．无机化学学报200218（1）：41 ［11］ 童兆达．碳酸稀土转型制备氟化稀土稀土198718（1）： 62 ［12］ Gschneidner K A JrEyring L R．Handbook on the Physics and Chemistry of Rare EarthVol．1．New York：North-Holland Publishing Company1978 ［13］ 库巴谢夫斯基 O奥尔考克 C B．冶金热化学．邱竹贤译． 北京：冶金工业出版社1985：326 ［14］ 梁英教车荫昌．无机物热力学数据手册．沈阳：东北大学 出版社1993：172 ［15］ 天津化工研究院．无机盐工业手册（上册）．北京：化工出版 社1979：685 ［16］ 李文超．冶金与材料物理化学．北京：冶金工业出版社 2001：22 Principles of reactions in the synthesis of rare earth fluorides in RE2O3－NH4HF2 systems HAO Zhanz hong 12）ZHA NG Jianliang 1）WA NG Bin 12） 1） Metallurgical and Ecological Engineering SchoolUniversity of Science and Technology BeijingBeijing100083China 2） Baotou Teachers CollegeBaotou014030China ABSTRACT Rare earth fluorides were synthesized with RE2O3 and NH4HF2 under atmospheric pressure and vacuum in RE2O3－NH4HF2systemsthe reactions in the systems were studiedand a new mechanism for the synthesis of REF3 was proposed．Powder La2O3Gd2O3started to react with NH4HF2at low temperatureand the products were RENH4F4（RE＝LaGd）NH4FNH3 and H2O．RENH4F4 was decomposed to REF3 and NH4F at high temperatureaccompanied with the volatilization and decomposition of NH4F．The whole process could be divided into three steps of synthesisdecomposition and deammoniation．The initial and final temperatures of the reactions were reduced under vacuum．The combination process of synthesis under atmospheric pressure at low temperature and decomposition and deammoniation under vacuum at high temperature should be applied to the preparation of rare earth fluorides． KEY WORDS rare earth fluorides；NH4HF2；synthesis；reaction 第3期 郝占忠等： RE2O3－NH4HF2 系合成稀土氟化物的反应规律 ·277·