Gd_2O_3-Nd_2O_3-ZrO_2-CeO_2体系的高温固相反应研究
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摘要
为研究Gd_2O_3-Nd_2O_3-ZrO_2-CeO_2四元氧化物体系的高温固相反应,以Gd_2O_3、Nd_2O_3、ZrO_2、CeO_2混合粉体为原材料,在1 673K和1 773K温度下煅烧24、48、72h,分别制备了系列样品,并对合成样品进行了XRD和SEM分析。结果表明,合成产物为具有缺陷萤石相且伴有少量烧绿石相的Gd2-xNdxZr2-xCexO7(0≤x≤2)晶体化合物。随着煅烧温度的升高和煅烧时间的延长,产物中立方烧绿石相的化合物增多,晶粒尺寸变大,且有少量未知相生成。进而探讨了锆基陶瓷固化多核素的潜在应用,并提出了未来研究的相关热点问题。
To investigate solid-solid reactions of Gd_2O_3-Nd_2O_3-ZrO_2-CeO_2 quaternary oxide system at high temperature conditions,using the mixed powders of Gd_2O_3,Nd_2O_3,ZrO_2 and CeO_2 as raw materials,a series of samples were prepared at the calcination temperature of 1 673 Kor 1 773 Kin duration time of 24,48 and 72 h,respectively.By analysis of XRD and SEM for the as-gained samples,the results indicate that Gd2-xNdxZr2-xCexO7(0≤x≤2)crystalline compounds are synthesized,which possess oxygen-deficient fluorite phase companying with minor pyrochlore phase.As the rising of calcination temperature and/or the extending of calcination time,more pyrochlore phase and larger grain size and minor unknown phase are observed in the as-synthesized samples.Finally,the potential applications of zircon-based ceramic waste forms loading multi-nuclide were discussed and the related hotspot issues in future werepresented as well.
To investigate solid-solid reactions of Gd_2O_3-Nd_2O_3-ZrO_2-CeO_2 quaternary oxide system at high temperature conditions,using the mixed powders of Gd_2O_3,Nd_2O_3,ZrO_2 and CeO_2 as raw materials,a series of samples were prepared at the calcination temperature of 1 673 Kor 1 773 Kin duration time of 24,48 and 72 h,respectively.By analysis of XRD and SEM for the as-gained samples,the results indicate that Gd2-xNdxZr2-xCexO7(0≤x≤2)crystalline compounds are synthesized,which possess oxygen-deficient fluorite phase companying with minor pyrochlore phase.As the rising of calcination temperature and/or the extending of calcination time,more pyrochlore phase and larger grain size and minor unknown phase are observed in the as-synthesized samples.Finally,the potential applications of zircon-based ceramic waste forms loading multi-nuclide were discussed and the related hotspot issues in future werepresented as well.
引文
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[4]WEBER W J,EWING R C,ANGELL C A,et al.Radiation defects in crystalline ceramics for the immobilization of high-level nuclear waste and plutonium disposal[J].J Mater Res,1998,13(6):1 434-1 484.
[5]WEBER W J,EWING R C.Plutonium immobilization and radiation effects[J].Science,2000,289:2 051-2 052.
[6]SICKAFUS K E,MINERVINI L,GRIMES R W,et al.Radiation tolerance of complex oxides[J].Science,2000,289:478-751.
[7]SICKAFUS K E,GRIMES R W,VALDEZ J A,et al.Radiation-induced amorphization resistance and radiation tolerance in structurally related oxides[J].Nature Materials,2007,6(3):217-223.
[8]李国武,邢晓琳,徐凯.烧绿石及碱硬锰矿型矿物晶体化学及其核废料固化基材研究进展[J].中国材料进展,2016,35(7):489-517.LI Guowu,XING Xiaolin,XU Kai.The crystal structure and chemistry of pyrochlore-and hollandite-type minerals and their applications as nuclear waste-forms[J].Materials China,2016,35(7):489-517(in Chinese).
[9]NSTREN C,JARDIN R,SOMER J,et al.Actinide incorporation in a zirconia based pyrochlore(Nd1.8An0.2)Zr2O7+x(An=Th,U,Np,Pu,Am)[J].J Solid State Chem,2009,182:1-7.
[10]SYKORA R E,RAISON P E,HAIRE R G.Self-irradiation induced structural changes in the transplutonium pyrochlores An2Zr2O7(An=Am,Cf)[J].J Solid State Chem,2005,178:578-583.
[11]LIAN J,YUDINTSEV S V,STEFANOVSKY S V,et al.Ion beam irradiation of U-,Th-and Ce-doped pyrochlores[J].J Alloys Comp,2007,444-445:429-433.
[12]EWING R C.The design and evaluation of nuclear-waste forms:Clues from mineralogy[J].Canad Miner,2001,39:697-715.
[13]YUNDINSEV S V,LUKINYKH A N,TOMILIN A A,et al.Alpha-decay induced amorphization of Cm-doped Gd2Ti2O7[J].J Nucl Mater,2009,385:200-203.
[14]MANDAL B P,GRAG N,SHARMA S M,et al.Solubility of ThO2in Gd2Zr2O7 pyrochlore:XRD,SEM and Raman spectroscopic studies[J].J Nucl Mater,2009,392:95-99.
[15]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 Jingyou,CHEN Xiaomou,PAN Sheqi,et al.Synthesis of Gd2Zr2O7pyrochlore with cubic structure at high pressure and high temperature conditions[J].Atomic Energy Science and Technology,2010,44(4):394-399(in Chinese).
[16]宁明杰,董发勤,张宝述,等.Gd2Zr2-xCexO7(0.0≤x≤2.0)的制备与表征[J].原子能科学技术,2013,47(2):202-205.NING Mingjie,DONG Faqin,ZHANG Baoshu,et al.Synthesis and characterization of Gd2Zr2-x CexO7(0.0≤x≤2.0)[J].Atomic Energy Science and Technology,2013,47(2):202-205(in Chinese).
[17]谢华,王烈林,江阔,等.烧绿石(La1-yNdy)2Zr2O7模拟固化241 Am的晶体结构稳定性研究[J].原子能科学技术,2013,47(5):724-729.XIE Hua,WANG Lielin,JIANG Kuo,et al.Stability study on crystal structure of(La1-yNdy)2Zr2O7pyrochlore simulated immobilizing 241 Am[J].Atomic Energy Science and Technology,2013,47(5):724-729(in Chinese).
[18]苏思瑾.模拟双核素放射性废物的钆锆烧绿石固化及稳定性研究[D].绵阳:西南科技大学,2015.
[19]樊龙.钆锆烧绿石晶格固化多核素的机理及稳定性研究[D].绵阳:西南科技大学,2016.