不同晶核剂对硼硅酸盐钙钛锆石固化体析晶行为及化学稳定性的影响
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摘要
通过"一步法"热处理制备含24%(质量分数)模拟核废物的硼硅酸盐钙钛锆石固化体,从析晶动力学角度出发,利用Kinssinger法研究不同晶核剂(Fe_2O_3、Cr_2O_3、P_2O_5、CaF_2)作用下固化体的析晶行为及其对化学稳定性的影响。实验结果表明,Cr_2O_3的引入促进了板状CaZrTi_2O_7晶体的析出,析晶活化能E由218kJ/mol降至128kJ/mol,并使残留在玻璃基体中的模拟核素进入所析出的晶相,而其他晶核剂对析晶无明显影响。MCC-1标准测试法结果显示,Cr_2O_3作为晶核剂时,模拟核素Ce元素抗浸出性能最为优异,化学稳定性最佳,7d后归一化元素浸出率小于10~(-7) g·m~(-2)·d~(-1)。
The zirconolite-based borosilicate glass-ceramics containing 24 wt% simulated nuclear waste was prepared by the"one-step"thermal treatment,from the perspective of crystallization kinetics,the action of the solidified bodies' crystallization behavior and the effect of chemical stability under different nucleation agent(Fe_2O_3,Cr_2O_3,P_2 O_5,CaF_2)were investigated.As a result,the addition of Cr_2O_3 has led to the precipitation of tabular CaZrTi_2 O_7 crystals and the energy Eof crystallization activation decreased from 218 kJ/mol to 128 kJ/mol,and promoting the simulated nuclide remaining in the glass matrix to fuse into the precipitated crystal phase,yet other nucleation agents did not produce obvious effect.The MCC-1 experiment of glass-ceramics showed that the excellent leaching resistance and chemical stability under the impact of Cr_2O_3,and the normalized leaching rate of Ce below 10~(-7) g·m~(-2)·d~(-1) after 7 d.
The zirconolite-based borosilicate glass-ceramics containing 24 wt% simulated nuclear waste was prepared by the"one-step"thermal treatment,from the perspective of crystallization kinetics,the action of the solidified bodies' crystallization behavior and the effect of chemical stability under different nucleation agent(Fe_2O_3,Cr_2O_3,P_2 O_5,CaF_2)were investigated.As a result,the addition of Cr_2O_3 has led to the precipitation of tabular CaZrTi_2 O_7 crystals and the energy Eof crystallization activation decreased from 218 kJ/mol to 128 kJ/mol,and promoting the simulated nuclide remaining in the glass matrix to fuse into the precipitated crystal phase,yet other nucleation agents did not produce obvious effect.The MCC-1 experiment of glass-ceramics showed that the excellent leaching resistance and chemical stability under the impact of Cr_2O_3,and the normalized leaching rate of Ce below 10~(-7) g·m~(-2)·d~(-1) after 7 d.
引文
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3 卢喜瑞.钆锆烧绿石固化锕系核素机理及稳定性[M].北京:科学出版社,2016.
4 Zhang Y,Gregg D J,Kong L,et al.Zirconolite glass-ceramics for plutonium immobilization:The effects of processing redox conditions on charge compensation and durability[J].Journal of Nuclear Materials,2017,490:238.
5 Vance E R,Ball C J,Day R A,et al.Actinide and rare earth incorporation into zirconolite[J].Journal of Alloys&Compounds,1994,213-214(1):406.
6 Wu L,Li Y,Teng Y,et al.Preparation and characterization of borosilicate glass-ceramics containing zirconolite and titanite crystalline phases[J].Journal of Non-Crystalline Solids,2013,380(5):123.
7 Lin J S,Shen P.Fabrication of CaO-ZrO2-TiO2-Al2O3-B2O3-SiO2glasses and glass-ceramics[J].Journal of Non-Crystalline Solids,1996,204(2):135.
8 何峰.微晶玻璃的制备与应用[M].北京:化学工业出版社,2017.
9 Loiseau P,Caurant D,Majerus O,et al.Fillet.craystallization study of(TiO2,ZrO2)-rich SiO2-Al2O3-CaO glass-PartⅠpreparation and characterization of ziconolite-based glass-ceramics[J].Journal of Meterials Science,2003,38(4):843.
10 Bansal N P,Doremus R H,Bruce A J,et al.Kinetics of crystallization of ZrF4-BaF2-LaF3 glass by differential scanning calorimetrys[J].Journal of the American Ceramic Society,1983,66(4):233.
11 Kuang J Z.Effect of cooling-heating on crystallization kinetics of CaO-Al2O3-SiO2system glass[J].Transactions of Materials and Heat Treatment,2012,3(1):37.
12 Chu H R,Ruan J S,Zhang Y.Research progress of chemical durability assessment methods for high level radiation glass[J].Shandong Chemical Industry,2017,46(16):65(in Chinese).褚浩然,阮佳晟,张禹.高放玻璃固化体化学耐久性评估方法研究进展[J].山东化工,2017,46(16):65.
13 Neilson R M J,Nicolaras H,Lai J,et al.Leachability of solidified.Low-level radioactive waste forms[J].Transactions of the American Nuclear Society,1978,30(11):97.
14 Lv C X.The study of crystallization process of ZrO2[D].Lanzhou:Lanzhou University of Technology,2010(in Chinese).吕彩霞.氧化锆晶化过程的研究[D].兰州:兰州理工大学,2010.
15 Li P,Ding X G,Yang H,et al.Crystallization and leaching resistance performance of zirconolite-based glass-ceramics[J].Journal of Silicate,2012,40(2):324(in Chinese).李鹏,丁新更,杨辉,等.钙钛锆石玻璃陶瓷体的晶化和抗浸出性能[J].硅酸盐学报,2012,40(2):324.
16 Kong L,Wei T,Zhang Y,et al.Phase evolution and microstructure analysis of CaZrTi2O7,zirconolite in glass[J].Ceramics International,2018,44:6285.
17 Li P.The structure control and properties of simulated radionuclide cerium ions doped glass/glass-ceramics matrix[D].Hangzhou:Zhejiang University,2013(in Chinese).李鹏.掺杂模拟核素铈离子的玻璃/玻璃陶瓷固化体的结构控制与性能研究[D].杭州:浙江大学,2013.