稀土离子掺杂ZnO-P_2O_5-SiO_2长余辉发光玻璃的研究
摘要
选择ZnO-P_2O_5-SiO_2作为长余辉发光的基质材料,Tb~(3+)作为激活剂,用高温熔融法和溶胶-凝胶法制备了ZnO-P_2O_5-SiO_2: Tb~(3+)长余辉发光玻璃。总结了长余辉发光玻璃的研究进展、应用前景及其面临的主要问题。
用高温熔融法制备长余辉玻璃,得出:在用254nm的紫外灯激发15min以后,有明亮的绿色长余辉发光现象,其余辉在黑暗中持续9h仍肉眼可辨。当SiO_2含量一定时,ZnO的含量越大玻璃的长余辉性能越好;Tb~(3+)掺杂浓度越大,玻璃的长余辉性能越好,掺杂浓度为5%时,长余辉性能最好;用2%的RO(RO=CaO、SrO、BaO)替代2%ZnO时,玻璃的长余辉性能以CaO、SrO、BaO的顺序依次减弱;同种物质替代时,替代浓度越小,玻璃的长余辉性能越好。
溶胶-凝胶法制备玻璃,系统考察了合成工艺条件对凝胶形成和玻璃形态的影响,结论如下:此玻璃的烧成温度为1200℃,比高温熔融法低200℃;柠檬酸/ZnO(摩尔比)、加水量、pH值和反应温度均对凝胶的形成和玻璃形态有影响,当加水量为75~125ml,pH=0.5~2,反应温度为70~90℃,柠檬酸/ZnO=1.5~2时,均可形成性能良好的凝胶和均质、透明的玻璃。
溶胶-凝胶法制备长余辉玻璃,系统考察合成工艺条件对玻璃长余辉性能的影响,结论如下:Tb~(3+)掺杂浓度、柠檬酸的加入量、加水量、pH值均对玻璃的长余辉性能有影响,当加水量为100ml,pH=1.5,柠檬酸/ZnO=1.5时,形成的玻璃余辉性能最好。与高温熔融法相比,玻璃的荧光和余辉性能都有所增强,这是由于溶胶-凝胶法制备的玻璃组分比较均匀,没有出现离子的偏析和淀析所致。
ZnO-P_2O_5-SiO_2 was selected to be host materials of long-lasting phosphorescence glasses and Tb~(3+) ions were doped in host materials. The long-lasting phosphorescence glasses with the composition (in mol %) of ZnO-P_2O_5-SiO_2: Tb~(3+) were prepared in a conventional melt-quenched method and sol-gel. The histories, applications and open questions of long-lasting phosphorescence glasses were generalized.
The long-lasting phosphorescence glasses were prepared by conventional melt-quenched method. The results showed as follows: A visible greenish light can be observed with naked eyes after the glasses were irradiated by 254nm light. It can last for up to 9h in the dark after removal of the activating light. The masses of SiO_2 were definite and the luminescent properties of the glasses became better with masses of ZnO increasing. The luminescent properties of glasses were affected by different concentrations of Tb~(3+). The luminescent properties of glasses were optimum when the concentrations of Tb~(3+) were up to 5%. The luminescent properties of glasses became worse and worse in the sequence of CaO, SrO, BaO when 2% of ZnO was replaced by 2% of RO (RO= CaO, SrO, BaO). The luminescent properties of glasses became worse with the contents of RO (RO= CaO, SrO, BaO) increasing.
The glasses were prepared by sol-gel. The effects of technological conditions on formation of gels and glasses were discussed. The results showed as follows: The calcination temperature of the glasses was 1200℃,which was lower by 200℃than that of conventional melt-quenched method. Formation of gels and glasses was affected by different ratios of citric acid and ZnO, solvents, pH values and heat treatment temperatures. The gels and glasses can be prepared on the conditions that solvents were 75~125ml, pH values were 0.5~2, heat treatment temperatures were 70~90℃, ratios of citric acid and ZnO were 1.5~2.
The long-lasting phosphorescence glasses were prepared by sol-gel. The effects of technological conditions on the properties of long-lasting phosphorescence glasses were discussed. The results were showed as follows: The properties of long-lasting phosphorescence glasses were affected by different concentrations of Tb~(3+), ratio of citric acid and ZnO, solvents and pH values. The optimum long-lasting phosphorescence glasses were prepared on the condition that the solvent was 100ml, the pH value was 1.5, the heat treatment temperature was 80℃and the ratio of citric acid and ZnO was 1.5. Compared with long-lasting phosphorescence glasses which were prepared by conventional melt-quenched method, the fluorescent and luminescent properties of long-lasting phosphorescence glasses which were prepared by sol-gel were better because of homogeneous compositions and no aliquation of metallic ions of the glasses.
用高温熔融法制备长余辉玻璃,得出:在用254nm的紫外灯激发15min以后,有明亮的绿色长余辉发光现象,其余辉在黑暗中持续9h仍肉眼可辨。当SiO_2含量一定时,ZnO的含量越大玻璃的长余辉性能越好;Tb~(3+)掺杂浓度越大,玻璃的长余辉性能越好,掺杂浓度为5%时,长余辉性能最好;用2%的RO(RO=CaO、SrO、BaO)替代2%ZnO时,玻璃的长余辉性能以CaO、SrO、BaO的顺序依次减弱;同种物质替代时,替代浓度越小,玻璃的长余辉性能越好。
溶胶-凝胶法制备玻璃,系统考察了合成工艺条件对凝胶形成和玻璃形态的影响,结论如下:此玻璃的烧成温度为1200℃,比高温熔融法低200℃;柠檬酸/ZnO(摩尔比)、加水量、pH值和反应温度均对凝胶的形成和玻璃形态有影响,当加水量为75~125ml,pH=0.5~2,反应温度为70~90℃,柠檬酸/ZnO=1.5~2时,均可形成性能良好的凝胶和均质、透明的玻璃。
溶胶-凝胶法制备长余辉玻璃,系统考察合成工艺条件对玻璃长余辉性能的影响,结论如下:Tb~(3+)掺杂浓度、柠檬酸的加入量、加水量、pH值均对玻璃的长余辉性能有影响,当加水量为100ml,pH=1.5,柠檬酸/ZnO=1.5时,形成的玻璃余辉性能最好。与高温熔融法相比,玻璃的荧光和余辉性能都有所增强,这是由于溶胶-凝胶法制备的玻璃组分比较均匀,没有出现离子的偏析和淀析所致。
ZnO-P_2O_5-SiO_2 was selected to be host materials of long-lasting phosphorescence glasses and Tb~(3+) ions were doped in host materials. The long-lasting phosphorescence glasses with the composition (in mol %) of ZnO-P_2O_5-SiO_2: Tb~(3+) were prepared in a conventional melt-quenched method and sol-gel. The histories, applications and open questions of long-lasting phosphorescence glasses were generalized.
The long-lasting phosphorescence glasses were prepared by conventional melt-quenched method. The results showed as follows: A visible greenish light can be observed with naked eyes after the glasses were irradiated by 254nm light. It can last for up to 9h in the dark after removal of the activating light. The masses of SiO_2 were definite and the luminescent properties of the glasses became better with masses of ZnO increasing. The luminescent properties of glasses were affected by different concentrations of Tb~(3+). The luminescent properties of glasses were optimum when the concentrations of Tb~(3+) were up to 5%. The luminescent properties of glasses became worse and worse in the sequence of CaO, SrO, BaO when 2% of ZnO was replaced by 2% of RO (RO= CaO, SrO, BaO). The luminescent properties of glasses became worse with the contents of RO (RO= CaO, SrO, BaO) increasing.
The glasses were prepared by sol-gel. The effects of technological conditions on formation of gels and glasses were discussed. The results showed as follows: The calcination temperature of the glasses was 1200℃,which was lower by 200℃than that of conventional melt-quenched method. Formation of gels and glasses was affected by different ratios of citric acid and ZnO, solvents, pH values and heat treatment temperatures. The gels and glasses can be prepared on the conditions that solvents were 75~125ml, pH values were 0.5~2, heat treatment temperatures were 70~90℃, ratios of citric acid and ZnO were 1.5~2.
The long-lasting phosphorescence glasses were prepared by sol-gel. The effects of technological conditions on the properties of long-lasting phosphorescence glasses were discussed. The results were showed as follows: The properties of long-lasting phosphorescence glasses were affected by different concentrations of Tb~(3+), ratio of citric acid and ZnO, solvents and pH values. The optimum long-lasting phosphorescence glasses were prepared on the condition that the solvent was 100ml, the pH value was 1.5, the heat treatment temperature was 80℃and the ratio of citric acid and ZnO was 1.5. Compared with long-lasting phosphorescence glasses which were prepared by conventional melt-quenched method, the fluorescent and luminescent properties of long-lasting phosphorescence glasses which were prepared by sol-gel were better because of homogeneous compositions and no aliquation of metallic ions of the glasses.
引文
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[4] LI C Y, WANG S B, YU Y N, et al. Long-lasting phosphorescence in Eu2+, Dy3+ co-doped strontium aluminoborate glass-ceramic [J]. Chin. J. Lumin. 2002, 23: 233-237 (in Chinese).
[5] KODAMA N, TAKAHASHI T, YAMAGA M, et al. Long-lasting phosphorescence in Ce3+ doped Ca2Al2SiO7 and CaYAl3O7 crystals [J]. Appl. Phys. Lett, 1999, 75: 1715-1717.
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[7] LIU Y L,DING H. Research development of long lasting phosphorescent materials [J]. Chin. J. Inorg. Chem. (无机化学学报), 2001, 17(2): 182-185 (in Chinese).
[8] ZHANG J Y, ZHANG L, WANG T M, et al. Progress in study long-lasting phosphorescent materials [J]. Mater. Rev, 2003, 17(4): 17-20.
[9]李成宇.发光玻璃的研究-稀土长余辉玻璃[D].长春:中国科学院长春应用化学研究所,2002:4-5.
[10]陆佩文.无机材料科学基础[M].武汉:武汉工业大学出版社,1996:98-103.
[11]赵建军,李成宇,王淑彬,等.铽激活碱土硼硅酸盐玻璃的长余辉发光性质[J].发光学报,2004,25(6):655-659.
[12]干福熹.光子学玻璃一特种玻璃的重要发展[J].硅酸盐学报,1999,27(3):330-336.
[13]米晓云,肖志义,张夕艳.稀土Eu、Dy掺杂长余辉发光玻璃的研究[J].长春理工大学学.报,2005:87-89.
[14]李国龙,谭镜明,吴勘.稀土长余辉涂料的发光性能研究[J].四川化工,2006,9(4):8-10.
[15]宋庆梅,黄镜斐,吴茂钧,等.铝酸锶铕的合成与发光的研究[J].发光学报,1991,12(2):144-149.
[16]司春雷.长余辉发光聚丙烯纤维的研究[J].辽宁化工,2003,32(1):22-23.
[17]张俊英,张林,王天民,等.长余辉发光玻璃的研究进展[J].材料导报,2003,17(4):17-20.
[18] MATSUZAWA T, AOKI Y, TAKEUCHI N, et al. A New Long Phosphorescent Phosphor with High Brightness, SrAl2O4: Eu2+, Dy3+ [J]. J. Electrochem. Soc., 143, 1996, 2670-2673.
[19] HUSSAIN N, REDDY Y P. Luminescence spectra of Eu3+-doped GeO2-PbO-Bi2O3 glasses [J]. Buddhudu Y. Mater Res Bull, 2001, 36: 1813-1816.
[20] MASAAKI Y, YOSHINORI Y, SHINOBU N. Long luminescent glass: Tb3+-activated ZnO-B2O3-SiO2 glass [J]. Journal of Non-Crystalline Solids 241(1998): 71-73.
[21] LIN Y. Preparation and properties of photoluminescent rare earth doped SrO-MgO-B2O3-SiO2 glass [J]. Mater Sci Eng, 2001, 86: 79.
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