针对高放废液硼硅酸盐玻璃固化体易析出辉石晶相的问题,本文采用P_(2)O_(5)部分替代硼硅酸盐基础玻璃配方中的MgO和CaO,研究了P_(2)O_(5)掺量(质量分数为0~8%)对玻璃固化体析晶和抗浸出性能的影响。结果表明,当P_(2)O_(5)掺量为0~3%时,...针对高放废液硼硅酸盐玻璃固化体易析出辉石晶相的问题,本文采用P_(2)O_(5)部分替代硼硅酸盐基础玻璃配方中的MgO和CaO,研究了P_(2)O_(5)掺量(质量分数为0~8%)对玻璃固化体析晶和抗浸出性能的影响。结果表明,当P_(2)O_(5)掺量为0~3%时,样品为无定形态,在850℃热处理6 h后,P_(2)O_(5)掺量为0~2%的样品主要析出辉石晶相,而P_(2)O_(5)掺量为3%的样品析出了少量硅酸钙晶相,辉石晶相基本消失;当P_(2)O_(5)掺量高于3%时,样品析出球形Na_(3)Ca_(6)(PO_(4))_(5)晶体,且析晶度随P_(2)O_(5)掺量的增加而升高。29 Si MAS NMR和^(11)B MAS NMR分析表明,随着P_(2)O_(5)掺量的增加,玻璃网络结构中Q^(3)、Q^(4)和BO_(3)结构单元含量逐渐增加。静态浸泡法(MCC-1)试验结果表明,样品的抗浸出性能随P_(2)O_(5)掺量的增加而逐渐提高,其中P_(2)O_(5)掺量为3%的样品浸泡28 d后,Si、B、Na和Cs元素的归一化浸出率分别为0.508、0.468、0.533、0.280 g/(m^(2)·d)。展开更多
The vacuum ultraviolet (VUV) spectroscopic properties of praseodymium (Pr3+, 1at%) doped LaF3 nanocrystals/glass at room temperature and 20 K are reported. Two types of Pr3+ ions, those in LaF3 nanocrystals and those ...The vacuum ultraviolet (VUV) spectroscopic properties of praseodymium (Pr3+, 1at%) doped LaF3 nanocrystals/glass at room temperature and 20 K are reported. Two types of Pr3+ ions, those in LaF3 nanocrystals and those in the glass host, were excited to 4f 5d band by VUV using synchrotron radiation as an excitation source, and emissions of 1S0 → 1D2 (336 nm), 1S0 → 1I6 (397 nm ) of Pr3+ in the nanocrystals and emissions of 4f 5d → 3HJ, 3FJ of Pr3+ in the glass appeared at the same time. But unlike in the bulk sample crystals, emission of 3P0 → 3HJ, 3FJ as the second step of the quantum splitting (QS) of Pr3+ in the LaF3 nanocrystals was not observed at room temperature, which could be explained that Pr3+ ions in the glass absorbed the energy of 3P0 → 3H4 of Pr3+ in the nanocrystals. Two types of excitation spectra monitoring different emissions were also measured, so it could be observed that the lowest energy of 4f 5d band of Pr3+ in the nanocrystals was about 53 500 cm-1 (186 nm) and in the glass about 33 800 cm-1(295 nm), respectively. These emission and excitation spectra were contrasted to those of bulk sample crystals LaF3∶Pr3+.展开更多
文摘针对高放废液硼硅酸盐玻璃固化体易析出辉石晶相的问题,本文采用P_(2)O_(5)部分替代硼硅酸盐基础玻璃配方中的MgO和CaO,研究了P_(2)O_(5)掺量(质量分数为0~8%)对玻璃固化体析晶和抗浸出性能的影响。结果表明,当P_(2)O_(5)掺量为0~3%时,样品为无定形态,在850℃热处理6 h后,P_(2)O_(5)掺量为0~2%的样品主要析出辉石晶相,而P_(2)O_(5)掺量为3%的样品析出了少量硅酸钙晶相,辉石晶相基本消失;当P_(2)O_(5)掺量高于3%时,样品析出球形Na_(3)Ca_(6)(PO_(4))_(5)晶体,且析晶度随P_(2)O_(5)掺量的增加而升高。29 Si MAS NMR和^(11)B MAS NMR分析表明,随着P_(2)O_(5)掺量的增加,玻璃网络结构中Q^(3)、Q^(4)和BO_(3)结构单元含量逐渐增加。静态浸泡法(MCC-1)试验结果表明,样品的抗浸出性能随P_(2)O_(5)掺量的增加而逐渐提高,其中P_(2)O_(5)掺量为3%的样品浸泡28 d后,Si、B、Na和Cs元素的归一化浸出率分别为0.508、0.468、0.533、0.280 g/(m^(2)·d)。
文摘The vacuum ultraviolet (VUV) spectroscopic properties of praseodymium (Pr3+, 1at%) doped LaF3 nanocrystals/glass at room temperature and 20 K are reported. Two types of Pr3+ ions, those in LaF3 nanocrystals and those in the glass host, were excited to 4f 5d band by VUV using synchrotron radiation as an excitation source, and emissions of 1S0 → 1D2 (336 nm), 1S0 → 1I6 (397 nm ) of Pr3+ in the nanocrystals and emissions of 4f 5d → 3HJ, 3FJ of Pr3+ in the glass appeared at the same time. But unlike in the bulk sample crystals, emission of 3P0 → 3HJ, 3FJ as the second step of the quantum splitting (QS) of Pr3+ in the LaF3 nanocrystals was not observed at room temperature, which could be explained that Pr3+ ions in the glass absorbed the energy of 3P0 → 3H4 of Pr3+ in the nanocrystals. Two types of excitation spectra monitoring different emissions were also measured, so it could be observed that the lowest energy of 4f 5d band of Pr3+ in the nanocrystals was about 53 500 cm-1 (186 nm) and in the glass about 33 800 cm-1(295 nm), respectively. These emission and excitation spectra were contrasted to those of bulk sample crystals LaF3∶Pr3+.
