高性能硅酸盐长余辉发光材料的制备与应用
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摘要
随着长余辉发光材料研究的深入和使用范围的不断拓展,提高和改善现有材料的使用性能、开发性能更佳的新型长余辉发光材料一直是人们关注的焦点。Eu激活的铝酸盐和硅酸盐长余辉发光粉是目前性能最好的两种发光材料,两者相比,以硅酸盐为基质的发光材料不仅有良好的化学稳定性和热稳定性,而且二氧化硅原料价廉、易得,烧结温度比铝酸盐体系低100℃以上,与陶瓷、玻璃等的相容性好于其它长余辉材料,因而具有广阔的应用前景。
本文研究化学组成和制备方法等对Sr_2MgSi_2O_7:Eu,Dy长余辉材料发光性能的影响。探讨了Eu,Dy和助熔剂加入量与发光性能之间的关系,得到了性能良好的硅酸盐长余辉发光粉的配方。进而研究了烧成时间、烧成方式、原料成分、发光粉粒径等对余辉时间的影响,确定了制备高性能硅酸盐长余辉材料的工艺方法。使用高温固相法,以氢气为还原气体制备出了初始亮度高、余辉时间长的硅酸盐蓝色长余辉发光粉。粒度为120目的发光粉初始亮度可达3.5cd/m~2。
本文研究了透明锶釉成分对釉性能的影响,制备出了具有合适高温粘度和较高透明度的含锶熔块釉,烧成温度为1150—1200℃。将高温固相法制得的发光粉和熔块釉混合制成陶瓷发光釉,研究了硅酸盐长余辉发光粉在锶釉中的发光性能。用高温固相法制备的硅酸盐长余辉发光粉,可用于制备1150℃烧成的发光釉。烧成温度超过1200℃,发光釉失去余辉性能。
本文还使用溶胶—凝胶法结合燃烧自蔓延在较低温度快速制备出了硅酸盐长余辉发光粉,研究了改善其发光性能的途径。
Luminescent material has long been a hot research field because of its extensive application. As two of the high performance long after glow phosphors, Eu actived silicate phosphor, made by cheap and abundance raw material SiO_2, has more chemical and thermal stability, lower sintering temperature and better consistent to ceramics than aluminate phosphor. It is doomed to have wide application in the near future.This paper investigate the impact of composition of Sr_2MgSi_2O_7: Eu, Dy on its luminescent performance, study the relationship between content of Eu, Dy, B and afterglow capability, obtain a recipe used for high performance silicate phosphor. Factors influence afterglow time are also investigated, such as sintering time, sintering method, composition of raw material, diameter of phosphor powder. A blue silicate long afterglow powder is prepared by using solid reaction and H_2 reduced method. It has better initial luminance and longer afterglow time, The initial luminance is 3.5 cd/m~2 when the powder's diameter is 0.125 mm.The impact of composition on glaze performance are also investigated and a transparent frit with a sintering temperature of 1150-1200℃ was developed, which had suitable viscosity and excellent transparence. Prepare luminescent ceramic glaze by using this frit and silicate long afterglow powder to study the luminescent performance of phosphor in glaze. Silicate luminescence powder prepared by solid reaction method, can be used to produce luminescent ceramic glaze sintered at 1150℃. Glaze will lose its afterglow capability when the temperature exceed 1200℃.Combined sol-gel and combustion method, a new method to obtain silicate phosphor in lower temperature and shorter time has been developed. Measures used for improving the luminescent performance are also discussed.
本文研究化学组成和制备方法等对Sr_2MgSi_2O_7:Eu,Dy长余辉材料发光性能的影响。探讨了Eu,Dy和助熔剂加入量与发光性能之间的关系,得到了性能良好的硅酸盐长余辉发光粉的配方。进而研究了烧成时间、烧成方式、原料成分、发光粉粒径等对余辉时间的影响,确定了制备高性能硅酸盐长余辉材料的工艺方法。使用高温固相法,以氢气为还原气体制备出了初始亮度高、余辉时间长的硅酸盐蓝色长余辉发光粉。粒度为120目的发光粉初始亮度可达3.5cd/m~2。
本文研究了透明锶釉成分对釉性能的影响,制备出了具有合适高温粘度和较高透明度的含锶熔块釉,烧成温度为1150—1200℃。将高温固相法制得的发光粉和熔块釉混合制成陶瓷发光釉,研究了硅酸盐长余辉发光粉在锶釉中的发光性能。用高温固相法制备的硅酸盐长余辉发光粉,可用于制备1150℃烧成的发光釉。烧成温度超过1200℃,发光釉失去余辉性能。
本文还使用溶胶—凝胶法结合燃烧自蔓延在较低温度快速制备出了硅酸盐长余辉发光粉,研究了改善其发光性能的途径。
Luminescent material has long been a hot research field because of its extensive application. As two of the high performance long after glow phosphors, Eu actived silicate phosphor, made by cheap and abundance raw material SiO_2, has more chemical and thermal stability, lower sintering temperature and better consistent to ceramics than aluminate phosphor. It is doomed to have wide application in the near future.This paper investigate the impact of composition of Sr_2MgSi_2O_7: Eu, Dy on its luminescent performance, study the relationship between content of Eu, Dy, B and afterglow capability, obtain a recipe used for high performance silicate phosphor. Factors influence afterglow time are also investigated, such as sintering time, sintering method, composition of raw material, diameter of phosphor powder. A blue silicate long afterglow powder is prepared by using solid reaction and H_2 reduced method. It has better initial luminance and longer afterglow time, The initial luminance is 3.5 cd/m~2 when the powder's diameter is 0.125 mm.The impact of composition on glaze performance are also investigated and a transparent frit with a sintering temperature of 1150-1200℃ was developed, which had suitable viscosity and excellent transparence. Prepare luminescent ceramic glaze by using this frit and silicate long afterglow powder to study the luminescent performance of phosphor in glaze. Silicate luminescence powder prepared by solid reaction method, can be used to produce luminescent ceramic glaze sintered at 1150℃. Glaze will lose its afterglow capability when the temperature exceed 1200℃.Combined sol-gel and combustion method, a new method to obtain silicate phosphor in lower temperature and shorter time has been developed. Measures used for improving the luminescent performance are also discussed.
引文
[1] 孙家跃.固体发光材料.北京:化学工业出版社,2003.1-10
[2] W. Lehmann. Activators and co-activators in calcium sulfide phosphors. J. Lumin. [J] , 1972, 5(2): 87-107
[3] 杨志平,郭智.Y_20_2S:Eu~(3+),Mg~(2+),Ti~(4+)红色材料的制备和长余辉性能 发光学报[J].2004,25(2):183-187
[4] 李治霞,张玉奇.CaTiO_3:Pr~(3+)红色磷光体余辉性能的改进.重庆大学学报[J].2004,27(7):53-55
[5] 刘正伟,刘应亮.CaWO_4中Eu~(2+)的长余辉发光.无机化学学报[J].2004,20(12):1432-1436
[6] Jing Wang, Qiang Su, Shubin Wang. A novel red long phosphorescent(LLP) material β-Zn3(PO4)2: Mn~(2+), Sm~(3+). Material Research Bullitin 40(2005) 590-598
[7] 林元华,张中太等.掺杂稀土CaAl_2O_4基发光材料的制备及发光机制.材料工程,2001,8,29-35
[8] 施朝淑,戚泽明.长余辉(寿命)材料研究的最新进展.无机材料学报[J].2004,19(5):961-969
[9] Palilla FC, Albere AK, Tomkus, MR, Fluorescence properties of SrAl_2O_4: Eu~(2+) sputtered films with long phosphorescence, J Elextrchem Soc, 1968, 115(6), 642-645
[10] 宋庆梅,黄锦斐,吴茂钧.铝酸锶铕的合成与发光的研究.发光学报[J],1991,12(2):144-149
[11] 松尺隆嗣等.日本第248回荧光体同学会讲演预稿 1993,1:1
[12] 肖志国.蓄光型发光材料及其制品.北京:化学工业出版社,2002,191-209
[13] 李成宇,苏锵,邱建荣.稀土元素掺杂长余辉发光材料研究的最新进展[J].发光学报,2003,24(1):19-27
[14] 罗昔贤等.新型硅酸盐长余辉发光材料.发光学报[J],2003,24(2):165-170
[15] 肖志国.长余辉夜光材料[P].中国专利:CN1157312A,1997-08-20 [16]
[16] Barry. L. Equilibria and Eu~(2+) luminescence of subsolidus phase bounded by Ba_3MgSi_2O_8, Sr_3MgSi_2O_8, Ca_3MgSi_2O_8. J. Electrochem. Soc., 1968, 115(7): 733-738
[17] L. Jiang, C. Chang, D. Mao, et al. Luminescent properties of CaMgSi_2O_6-based phosphors co-doped with different rare earth ions. Journal of Alloys and Compounds. 377 (2004)211-215
[18] Yuanhua Lin, et al. Luminescent properties of a new long afterglow Eu~(2+) and Dy~(3+) activated Ca_3MgSi_2O_8 phosphor. Journal of the European Ceramic Society. 21 (2001) 683-685
[19] Qin Fei, et al. Luminescent properties of Sr_2MgSi_2O_7 and Ca_2MgSi_2O_7 long lasting phosphor activated by Eu~(2+), Dy~(3+). Journal of Alloys and Compounds 390(2005)133-137
[20] 乔彬,张中太,唐子龙.Eu~(2+),Mn~(2+)共激活碱土镁硅酸盐基红色荧光粉的发光性能.中国稀土学报[J].2003,21(2):192-195
[21] Xiao-Jun Wang, Dongdong Jia. Mn~(2+) actived green, yellow, and red long persistent phosphors. Journal of Luminescence 2003(102-103): 34-37
[22] Yingliang Liu, Bingfu Lei, Chunshan Shi. Luminescent Properties of a White Afterglow Phosphor CdSiO_3: Dy~(3+). Chem. Mater. 2005, 17, 2108-2113.
[23] Chengyu Li, Qiang Su, Shunbin Wang. Multi-color long-lasting phosphorescence in Mn~(2+-)doped ZnO-B_2O_3-SiO_2 glass-ceramics. Materials research Bulletin 37(2002) 1443-1449
[24] 余锡宾,吴虹.正硅酸乙酯的水解、缩合过程研究[J].无机材料学报,1996,11(4):703-707
[25] 姜洪义,陈伟.Sr_2MgSi_2O_7基新型长余辉发光材料的合成与性能[J].武汉理工大学学报,2003,25(11):5-7
[26] J. J. Kingsley. J. Solid State Chem, 1990, 25: 1305-1312
[27] T. Matsuzawa, Y. Aoki, et al. J. Electronchem. Soc. 143(1996)2670.
[28] Poort S H M, Meyerink A, Blasse G, Lifetime measurements in Eu~(2+) doped host lattices [J]. J. Phys. chem. Solids, 1997, 58(9): 1451-1456
[29] Jianrong Qiu, M. Kawasaki, K. Tanaka, et al. Phenomenon and mechanism of long-lasting phosphorescence in Eu~(2+-)doped aluminosilicate glasses[J]. J Phys Chem Solid, 1998, 59(9): 1521-1525
[30] 戚泽明,施朝淑等,Eu,Dy共掺杂长余辉发光材料中稀土离子价态的研究[J] 核技术 2005.28:21-23
[31] G. B. Zhang, Z. M. Qi, H. J. Zhou, et al. Photoluminescence of (Eu~(2+) Dy~(3+)) co-doped silicare long lasting phoshors. Journal of Electron Spectroscopy and Related Phenomena 144-147(2005)861-863
[32] 汪健,张来平.新型陶瓷颜料夜光粉.景德镇陶瓷[J],1990,(2):16
[33] 李万军,袁振明,易炳.荧光釉的研制及机理探讨.中国陶瓷[J],1991(4):20
[34] 张玉军,金全建,段军.发光陶瓷釉面砖的研制[J].材料科学与工程,2000,18(2):32
[35] 邱子凤.包膜发光粉在发光釉料中的应用.[硕士学位论文].山东:山东大学,2005
[36] 徐叙瑢,苏勉曾.发光学与发光材料.北京:化学工业出版社,2004
[37] 陈永杰,孙彦彬等.超长余辉发光材料的研究,稀土[J],2002.23(4):50-53
[38] P. Dorebos. Mechanism of Persistent Luminescence in Eu~(2+) and Dy~(3+) Codoped Aluminate and Silicate Compounds. Journal od The Electrochemical Society, 152(7)H107-H110(2005)
[39] 姜洪义,万红峰,陈伟.溶胶-凝胶法合成Sr_2MgSi_2O_7:Eu~(2+),Dy~(3+)长余辉发光材料[J].武汉理工大学学报,2003,25(11):5-7.
[40] 缪春燕,李东平.燃烧法快速合成新型蓝色硅酸盐长余辉材料[J].中国陶瓷.2003,39(6):27-29
[41] 洪兴华,李保国.溶胶-凝胶(Sol-Gel)方法的原理与应用[J].天津师范大学学报,2001,21(1):5-8
[42] 李峻峰.燃烧法合成铝酸盐稀土发光材料及其发光性的研究.[硕士学位论文].四川:成都理工大学.2005
[43] 刘康时等.陶瓷工艺原理.广州:华南理工大学出版社,1994
[44] 祝桂洪,周健儿,曹春娥.陶瓷釉配制基础.北京,轻工业出版社,1989.
[45] 万红峰.中高温发光陶瓷釉的研究.[硕士学位论文].武汉:武汉理工大学.2005
[46] 李建宇.稀土发光材料及其应用.北京:化学工业出版社.2003
[47] 素木洋一.釉及色料,(刘可栋,刘光耀,中译本).北京:中国建筑工业出版社,1979
[48] 俞康泰.现代陶瓷色釉料与装饰技术手册.武汉:武汉工业大学出版社,1999
[49] 李家驹.陶瓷工艺学.北京:中国轻工业出版社.2001.
[50] 吴绳愚 陶瓷计算—坯釉配方及其性能计算 轻工业出版社.1983.
[2] W. Lehmann. Activators and co-activators in calcium sulfide phosphors. J. Lumin. [J] , 1972, 5(2): 87-107
[3] 杨志平,郭智.Y_20_2S:Eu~(3+),Mg~(2+),Ti~(4+)红色材料的制备和长余辉性能 发光学报[J].2004,25(2):183-187
[4] 李治霞,张玉奇.CaTiO_3:Pr~(3+)红色磷光体余辉性能的改进.重庆大学学报[J].2004,27(7):53-55
[5] 刘正伟,刘应亮.CaWO_4中Eu~(2+)的长余辉发光.无机化学学报[J].2004,20(12):1432-1436
[6] Jing Wang, Qiang Su, Shubin Wang. A novel red long phosphorescent(LLP) material β-Zn3(PO4)2: Mn~(2+), Sm~(3+). Material Research Bullitin 40(2005) 590-598
[7] 林元华,张中太等.掺杂稀土CaAl_2O_4基发光材料的制备及发光机制.材料工程,2001,8,29-35
[8] 施朝淑,戚泽明.长余辉(寿命)材料研究的最新进展.无机材料学报[J].2004,19(5):961-969
[9] Palilla FC, Albere AK, Tomkus, MR, Fluorescence properties of SrAl_2O_4: Eu~(2+) sputtered films with long phosphorescence, J Elextrchem Soc, 1968, 115(6), 642-645
[10] 宋庆梅,黄锦斐,吴茂钧.铝酸锶铕的合成与发光的研究.发光学报[J],1991,12(2):144-149
[11] 松尺隆嗣等.日本第248回荧光体同学会讲演预稿 1993,1:1
[12] 肖志国.蓄光型发光材料及其制品.北京:化学工业出版社,2002,191-209
[13] 李成宇,苏锵,邱建荣.稀土元素掺杂长余辉发光材料研究的最新进展[J].发光学报,2003,24(1):19-27
[14] 罗昔贤等.新型硅酸盐长余辉发光材料.发光学报[J],2003,24(2):165-170
[15] 肖志国.长余辉夜光材料[P].中国专利:CN1157312A,1997-08-20 [16]
[16] Barry. L. Equilibria and Eu~(2+) luminescence of subsolidus phase bounded by Ba_3MgSi_2O_8, Sr_3MgSi_2O_8, Ca_3MgSi_2O_8. J. Electrochem. Soc., 1968, 115(7): 733-738
[17] L. Jiang, C. Chang, D. Mao, et al. Luminescent properties of CaMgSi_2O_6-based phosphors co-doped with different rare earth ions. Journal of Alloys and Compounds. 377 (2004)211-215
[18] Yuanhua Lin, et al. Luminescent properties of a new long afterglow Eu~(2+) and Dy~(3+) activated Ca_3MgSi_2O_8 phosphor. Journal of the European Ceramic Society. 21 (2001) 683-685
[19] Qin Fei, et al. Luminescent properties of Sr_2MgSi_2O_7 and Ca_2MgSi_2O_7 long lasting phosphor activated by Eu~(2+), Dy~(3+). Journal of Alloys and Compounds 390(2005)133-137
[20] 乔彬,张中太,唐子龙.Eu~(2+),Mn~(2+)共激活碱土镁硅酸盐基红色荧光粉的发光性能.中国稀土学报[J].2003,21(2):192-195
[21] Xiao-Jun Wang, Dongdong Jia. Mn~(2+) actived green, yellow, and red long persistent phosphors. Journal of Luminescence 2003(102-103): 34-37
[22] Yingliang Liu, Bingfu Lei, Chunshan Shi. Luminescent Properties of a White Afterglow Phosphor CdSiO_3: Dy~(3+). Chem. Mater. 2005, 17, 2108-2113.
[23] Chengyu Li, Qiang Su, Shunbin Wang. Multi-color long-lasting phosphorescence in Mn~(2+-)doped ZnO-B_2O_3-SiO_2 glass-ceramics. Materials research Bulletin 37(2002) 1443-1449
[24] 余锡宾,吴虹.正硅酸乙酯的水解、缩合过程研究[J].无机材料学报,1996,11(4):703-707
[25] 姜洪义,陈伟.Sr_2MgSi_2O_7基新型长余辉发光材料的合成与性能[J].武汉理工大学学报,2003,25(11):5-7
[26] J. J. Kingsley. J. Solid State Chem, 1990, 25: 1305-1312
[27] T. Matsuzawa, Y. Aoki, et al. J. Electronchem. Soc. 143(1996)2670.
[28] Poort S H M, Meyerink A, Blasse G, Lifetime measurements in Eu~(2+) doped host lattices [J]. J. Phys. chem. Solids, 1997, 58(9): 1451-1456
[29] Jianrong Qiu, M. Kawasaki, K. Tanaka, et al. Phenomenon and mechanism of long-lasting phosphorescence in Eu~(2+-)doped aluminosilicate glasses[J]. J Phys Chem Solid, 1998, 59(9): 1521-1525
[30] 戚泽明,施朝淑等,Eu,Dy共掺杂长余辉发光材料中稀土离子价态的研究[J] 核技术 2005.28:21-23
[31] G. B. Zhang, Z. M. Qi, H. J. Zhou, et al. Photoluminescence of (Eu~(2+) Dy~(3+)) co-doped silicare long lasting phoshors. Journal of Electron Spectroscopy and Related Phenomena 144-147(2005)861-863
[32] 汪健,张来平.新型陶瓷颜料夜光粉.景德镇陶瓷[J],1990,(2):16
[33] 李万军,袁振明,易炳.荧光釉的研制及机理探讨.中国陶瓷[J],1991(4):20
[34] 张玉军,金全建,段军.发光陶瓷釉面砖的研制[J].材料科学与工程,2000,18(2):32
[35] 邱子凤.包膜发光粉在发光釉料中的应用.[硕士学位论文].山东:山东大学,2005
[36] 徐叙瑢,苏勉曾.发光学与发光材料.北京:化学工业出版社,2004
[37] 陈永杰,孙彦彬等.超长余辉发光材料的研究,稀土[J],2002.23(4):50-53
[38] P. Dorebos. Mechanism of Persistent Luminescence in Eu~(2+) and Dy~(3+) Codoped Aluminate and Silicate Compounds. Journal od The Electrochemical Society, 152(7)H107-H110(2005)
[39] 姜洪义,万红峰,陈伟.溶胶-凝胶法合成Sr_2MgSi_2O_7:Eu~(2+),Dy~(3+)长余辉发光材料[J].武汉理工大学学报,2003,25(11):5-7.
[40] 缪春燕,李东平.燃烧法快速合成新型蓝色硅酸盐长余辉材料[J].中国陶瓷.2003,39(6):27-29
[41] 洪兴华,李保国.溶胶-凝胶(Sol-Gel)方法的原理与应用[J].天津师范大学学报,2001,21(1):5-8
[42] 李峻峰.燃烧法合成铝酸盐稀土发光材料及其发光性的研究.[硕士学位论文].四川:成都理工大学.2005
[43] 刘康时等.陶瓷工艺原理.广州:华南理工大学出版社,1994
[44] 祝桂洪,周健儿,曹春娥.陶瓷釉配制基础.北京,轻工业出版社,1989.
[45] 万红峰.中高温发光陶瓷釉的研究.[硕士学位论文].武汉:武汉理工大学.2005
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