钆锆烧绿石的高温固相法制备及工艺影响研究
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摘要
为获得高温固相法制备钆锆烧绿石的最佳工艺条件,弄清制备工艺对钆锆烧绿石物相纯度等的影响,研究以Gd2O3和ZrO2粉体为原料,综合考虑成型压力(0~15 MPa)、烧结温度(1 350~1 500℃)及保温时间(12~72h)对烧结效果的影响,设计L16(45)正交实验开展钆锆烧绿石的制备工作。借助粉末X射线衍射仪(XRD)及拉曼散射光谱仪(Raman)对所制备样品的物相及分子结构进行分析,利用扫描电子显微镜(SEM)对样品的显微形貌进行观察。结果表明:所考虑工艺参数中对钆锆烧绿石烧结效果的影响大小依次为烧结温度、成型压力和保温时间;钆锆烧绿石的最佳制备条件为成型压力15 MPa,1 500℃保温72h。同时,探讨了制备工艺对烧结效果的影响机理。
In order to study the influence of preparation process on the phase purity and to optimize the process,Gd_2Zr_2O_7 pyrochlore was fabricated by the high temperature solid-phase method,using Gd_2O_3 and ZrO_2 as raw materials.Sintering parameters,such as temperature(1 350~1 500℃),holding time(12~72 h)and molding pressure(0~15 MPa)were comprehensively considered.The optimal process for the fabrication of Gd_2Zr_2O_7 pyrochlore was selected by L16(45)orthogonal experiment.XRD,Raman,SEM were exploited to characterize the phase and microstructure of the synthetic samples.The results shows that sintering temperature,shaping pressure and holding time influence the final effect in turn,and the best process conditions were obtained as sintering at 1 500℃for 72 hwith the molding pressure of15 MPa.In addition,the influence mechanism of preparation process on sintering was analyzed.
In order to study the influence of preparation process on the phase purity and to optimize the process,Gd_2Zr_2O_7 pyrochlore was fabricated by the high temperature solid-phase method,using Gd_2O_3 and ZrO_2 as raw materials.Sintering parameters,such as temperature(1 350~1 500℃),holding time(12~72 h)and molding pressure(0~15 MPa)were comprehensively considered.The optimal process for the fabrication of Gd_2Zr_2O_7 pyrochlore was selected by L16(45)orthogonal experiment.XRD,Raman,SEM were exploited to characterize the phase and microstructure of the synthetic samples.The results shows that sintering temperature,shaping pressure and holding time influence the final effect in turn,and the best process conditions were obtained as sintering at 1 500℃for 72 hwith the molding pressure of15 MPa.In addition,the influence mechanism of preparation process on sintering was analyzed.
引文
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[15]Fan L,Shu X,Ding Y,et al.Fabrication and Phase Transition of Gd2Zr2O7Ceramics Immobilized Various Simulated Radionuclides[J].Journal of Nuclear Materials,2015,456:467-470.
[16]Belin R C,Valenza P J,Reason P E,et al.Synthesis Andrietveld Structure Refinement of Americium Pyrochlore Am2Zr2O7[J].Journal of Alloys and Compounds,2008,448(1/2):321-324.
[17]刘燕炜,徐强,潘伟,等.固相反应Gd2Zr2O7陶瓷的形成机理研究[J].稀有金属材料与工程,2005,34(增刊1):584-586.Liu Y,Xu Q,Pan W,et al.Study of the Formation Mechanism of Gd2Zr2O7Ceramic by Solid State Reaction[J].Rare Metal Materials and Engineering,2005,34(Z1):584-586.
[18]唐敬友,陈晓谋,潘社奇,等.立方烧绿石Gd2Zr2O7的高温高压合成[J].原子能科学技术,2010,44(4):394-399.Tang J,Chen X,Pan S,et al.Synthesis of Gd2Zr2O7Pyrochiore with Cubic Structure at High Pressure and High Temperature Conditions[J].Atomic Energy Science and Technology,2010,44(4):394-399.
[19]毛雪丽,唐敬友,易发成,等.Gd2Zr2O7烧绿石的高温高压快速合成[J].西南科技大学学报,2011,26(2):5-9.Mao X,Tang J,Yi F,et al.Rapid Synthesis of Isometric Pyrochlore Gd2-xNdxZr2O7at High Pressure and High Temperature[J].Journal of Southwest University of Science and Technology,2011,26(2):5-9.
[20]李权,马伟民,马雷,等.共沉淀法制备纳米粒子[J].人工晶体学报,2013,42:72-77.Li Q,Ma W,Ma L,et al.Preparation of Gd2Zr2O7Nanoparticles by Coprecipitation Method[J].Journal of Synthetic Crystals,2013,42:72-77.
[21]Durand A M,Klavins P,Corruccini L R.Heat Capacity of the Frustrated Magnetic Pyrochlores Gd2Zr2O7and Gd2Hf2O7[J].Journal of Physics:Condensed Matter,2008,20(23):235208.
[22]Urban S,Dolcet P,M9ller M,et al.Synthesis and Full Characterization of the Phase-pure Pyrochlore Ce2Zr2O7and theκ-Ce2Zr2O8Phases[J].Applied Catalysis B:Environmental,2016,197:23-34.
[23]宁明杰,董发勤,张宝述,等.钆锆烧绿石粉体的高温固相制备工艺[J].中国粉体技术,2012,18:37-39.Ning M,Dong F,Zhang B,et al.Preparation of Pyrochlore Gd2Zr2O7 Powders by High Temperature Solid State Reaction[J].China Powder Science and Technology,2012,18:37-39.
[24]Lu X,Ding Y,Dan H,et al.Rapid Synthesis of Single Phase Gd2Zr2O7 Pyrochlore Waste Forms by Microwave Sintering[J].Ceramics International,2014,40(8):13191-13194.
[25]Lu Xirui,Dong Faqin,Song Gongbao,et al.Phase and Structure in the System Gd2-xEuxZr2O7(0.0≤x≤2.0)[J].Journal of Wuhan University of Technology-Mater.Sci.Ed.2014(1):1-4.
[26]樊龙,苏思瑾,卢喜瑞,等.微波烧结法制备钆锆烧绿石工艺研究[J].世界核地质科学,2014,31(增刊1):398-401.Fan L,Su S,Lu X,et al.Study on the Preparation of Pyrochlore Gd2Zr2O7by Microwave Sintering[J].World Nuclear Geoscience,2014,31(Z 1):398-401.
[27]Shu X,Fan L,Lu X,et al.Structure and Performance Evolution of the System(Gd1-xNdx)2(Zr1-yCey)2O7(0≤x,y≤1.0)[J].Journal of the European Ceramic Society,2015,35(11):3095-3102.
[28]Uehara T,Koto K,Kanamaru F,et al.Stability and Antiphase Domain Structure of the Pyrochlore Solid Solution in the ZrO2-Gd2O3System[J].Solid State Ionics,1987,23(1-2):137-143.
[29]Lee Y H,Sheu H S,Deng J P,et al.Preparation and Fluorite–pyrochlore Phase Transformation in Gd2Zr2O7[J].Journal of Alloys&Compounds,2009,487(1-2):595-598.
[30]Jang B K,Kim S,Oh Y S,et al.Influence of La2O3 Addition on Thermophysical Properties of ZrO2-4mol%Y2O3Ceramics Fabricated by Spark Plasma Sintering[J].Journal-Ceramic Society Japan,2011,119(1396):929-932.
[31]Zhou L,Huang Z,Qi J,et al.Thermal-driven Fluorite-pyrochlore-fluorite Phase Transitions of Gd2Zr2O7Ceramics Probed in Large Range of Sintering Temperature[J].Metallurgical and Materials Transactions A,2016,47(1):623-630.
[32]Zhang F X,Lang M,Ewing R C.Atomic Disorder in Gd2Zr2O7 Pyrochlore[J].Applied Physics Letters,2015,106(19):191902.
[2]B考夫曼.核燃料循环中放射性废物的处理和处置[M].汤宝龙,译.北京:原子能出版社,1981:209-218.
[3]Deokattey S,Bhanumurthy K,Wattal P K.High Level Waste Management in Asia:R&D Perspectives[J].Progress in Nuclear Energy,2013:62:37.
[4]Ringwood A E.Immobilisation of High Level Nuclear Reactor Wastes in SYNROC[J].Nature,1979,278:219-223.
[5]Ewing R C.Nuclear Waste Forms for Actinides[J].Proceedings of the National Academy of Sciences,1999,96:3432-3439.
[6]Hatch L P.Ultimate Disposal of Radioactive Wastes[J].American Science,1953,41:410-421.
[7]周冠南.烧绿石固化高放废物的研究进展[J].材料导报,2006,20(9):38-41.Zhou G.The Progress in Research Pyrochlore Immobilization of High Radioactive Waste[J].Materials Review,2006,20(9):38-41.
[8]Ewing R C,Weber W J,Lian J.Nuclear Waste Disposal-pyrochlore(A2B2O7):Nuclear Waste Form for the Immobilization of Plutonium and“Minor”Actinides[J].Journal of Applied Physics,2004,95(11):5949-5971.
[9]Fan L,Shu X,Lu X,et al.Phase Structure and Aqueous Stability of TRPO Waste Incorporation Into Gd2Zr2O7Pyrochlore[J].Ceramics International,2015,41(9):11741-11747.
[10]Lu X,Ding Y,Dan H,et al.High Capacity Immobilization of TRPO Waste by Gd2Zr2O7Pyrochlore[J].Materials Letters,2014,136:1-3.
[11]Díaz-Guillén J A,DuráO J,Díaz-Guillén M R,et al.Thermo Physical Properties of Gd2Zr2O7 Powders Prepared by Mechanical Milling:Effect of Homovalent Gd3+Substitution[J].Journal of Alloys and Compounds,2015,649:1145-1150.
[12]Wang J W,Zhang F X,Lian J,et al.Energetics and Concentration of Defects in Gd2Ti2O7and Gd2Zr2O7Pyrochlore Under High Press[J].Acta Materialia,2011,59:1607-1618.
[13]Bouattour S,Ferreira D P,Hamdi A,et al.Spectroscopic Studies of Mixed Pyrochlore-oxide(Y/Gd)2Ti2O7Samples Prepared Via Sol–gel and Solid-state Methodologies and Calcined at Different Temperatures[J].Materials Chemistry and Physics,2013,138(2):507-513.
[14]Moreno K J,Fuentes A F,Maczka M,et al.Structural Manipulation of Pyrochlores:Thermal Evolution of Metastable Gd2(Ti1-yZry)2O7 Powders Prepared by Mechanical Milling[J].Journal of Solid State Chemistry,2006,179(12):3805-3813.
[15]Fan L,Shu X,Ding Y,et al.Fabrication and Phase Transition of Gd2Zr2O7Ceramics Immobilized Various Simulated Radionuclides[J].Journal of Nuclear Materials,2015,456:467-470.
[16]Belin R C,Valenza P J,Reason P E,et al.Synthesis Andrietveld Structure Refinement of Americium Pyrochlore Am2Zr2O7[J].Journal of Alloys and Compounds,2008,448(1/2):321-324.
[17]刘燕炜,徐强,潘伟,等.固相反应Gd2Zr2O7陶瓷的形成机理研究[J].稀有金属材料与工程,2005,34(增刊1):584-586.Liu Y,Xu Q,Pan W,et al.Study of the Formation Mechanism of Gd2Zr2O7Ceramic by Solid State Reaction[J].Rare Metal Materials and Engineering,2005,34(Z1):584-586.
[18]唐敬友,陈晓谋,潘社奇,等.立方烧绿石Gd2Zr2O7的高温高压合成[J].原子能科学技术,2010,44(4):394-399.Tang J,Chen X,Pan S,et al.Synthesis of Gd2Zr2O7Pyrochiore with Cubic Structure at High Pressure and High Temperature Conditions[J].Atomic Energy Science and Technology,2010,44(4):394-399.
[19]毛雪丽,唐敬友,易发成,等.Gd2Zr2O7烧绿石的高温高压快速合成[J].西南科技大学学报,2011,26(2):5-9.Mao X,Tang J,Yi F,et al.Rapid Synthesis of Isometric Pyrochlore Gd2-xNdxZr2O7at High Pressure and High Temperature[J].Journal of Southwest University of Science and Technology,2011,26(2):5-9.
[20]李权,马伟民,马雷,等.共沉淀法制备纳米粒子[J].人工晶体学报,2013,42:72-77.Li Q,Ma W,Ma L,et al.Preparation of Gd2Zr2O7Nanoparticles by Coprecipitation Method[J].Journal of Synthetic Crystals,2013,42:72-77.
[21]Durand A M,Klavins P,Corruccini L R.Heat Capacity of the Frustrated Magnetic Pyrochlores Gd2Zr2O7and Gd2Hf2O7[J].Journal of Physics:Condensed Matter,2008,20(23):235208.
[22]Urban S,Dolcet P,M9ller M,et al.Synthesis and Full Characterization of the Phase-pure Pyrochlore Ce2Zr2O7and theκ-Ce2Zr2O8Phases[J].Applied Catalysis B:Environmental,2016,197:23-34.
[23]宁明杰,董发勤,张宝述,等.钆锆烧绿石粉体的高温固相制备工艺[J].中国粉体技术,2012,18:37-39.Ning M,Dong F,Zhang B,et al.Preparation of Pyrochlore Gd2Zr2O7 Powders by High Temperature Solid State Reaction[J].China Powder Science and Technology,2012,18:37-39.
[24]Lu X,Ding Y,Dan H,et al.Rapid Synthesis of Single Phase Gd2Zr2O7 Pyrochlore Waste Forms by Microwave Sintering[J].Ceramics International,2014,40(8):13191-13194.
[25]Lu Xirui,Dong Faqin,Song Gongbao,et al.Phase and Structure in the System Gd2-xEuxZr2O7(0.0≤x≤2.0)[J].Journal of Wuhan University of Technology-Mater.Sci.Ed.2014(1):1-4.
[26]樊龙,苏思瑾,卢喜瑞,等.微波烧结法制备钆锆烧绿石工艺研究[J].世界核地质科学,2014,31(增刊1):398-401.Fan L,Su S,Lu X,et al.Study on the Preparation of Pyrochlore Gd2Zr2O7by Microwave Sintering[J].World Nuclear Geoscience,2014,31(Z 1):398-401.
[27]Shu X,Fan L,Lu X,et al.Structure and Performance Evolution of the System(Gd1-xNdx)2(Zr1-yCey)2O7(0≤x,y≤1.0)[J].Journal of the European Ceramic Society,2015,35(11):3095-3102.
[28]Uehara T,Koto K,Kanamaru F,et al.Stability and Antiphase Domain Structure of the Pyrochlore Solid Solution in the ZrO2-Gd2O3System[J].Solid State Ionics,1987,23(1-2):137-143.
[29]Lee Y H,Sheu H S,Deng J P,et al.Preparation and Fluorite–pyrochlore Phase Transformation in Gd2Zr2O7[J].Journal of Alloys&Compounds,2009,487(1-2):595-598.
[30]Jang B K,Kim S,Oh Y S,et al.Influence of La2O3 Addition on Thermophysical Properties of ZrO2-4mol%Y2O3Ceramics Fabricated by Spark Plasma Sintering[J].Journal-Ceramic Society Japan,2011,119(1396):929-932.
[31]Zhou L,Huang Z,Qi J,et al.Thermal-driven Fluorite-pyrochlore-fluorite Phase Transitions of Gd2Zr2O7Ceramics Probed in Large Range of Sintering Temperature[J].Metallurgical and Materials Transactions A,2016,47(1):623-630.
[32]Zhang F X,Lang M,Ewing R C.Atomic Disorder in Gd2Zr2O7 Pyrochlore[J].Applied Physics Letters,2015,106(19):191902.