SrAl_2O_4：Eu~（2+），Dy~（3+）的高温固相法合成工艺研究
摘要
SrAl_2O_4: Eu~(2+), Dy~(3+)是20世纪90年代开发的新型功能材料。SrAl_2O_4: Eu~(2+), Dy~(3+)是以铝酸锶为基质,掺杂Eu、Dy作为激活剂的一种优质的铝酸盐体系夜光材料。这类夜光材料不含任何放射性元素,无毒无害。因其性能优越,成为近年来生产量最大,应用范围最广的夜光材料。但随着稀土铝酸锶夜光材料的应用领域的扩大,其性能已不能满足实际使用的要求。稀土铝酸锶夜光材料需改进的方面有:1.余辉衰减太快,衰减后期余辉亮度不够;2.颜色种类较少;3.需在保证夜光材料亮度的情况下,减小其粒径。所以需改进夜光材料的制备工艺,以此提高其各方面性能,使铝酸锶夜光材料更好地应用于各个领域。
夜光材料的发光性质在很大程度上取决于基质材料的组成和合成工艺条件,所以要提高SrAl_2O_4: Eu~(2+), Dy~(3+)的光学性能,关键在于合理选择原料和工艺条件。
首先,通过理论分析,比较了高温固相法、溶胶一凝胶法、微波热合成法、共沉淀法,燃烧合成法、喷雾干燥法等方法的优缺点,从环保、成本和制成品性能等方面考虑,初步选择高温固相法和微波热合成法作为实验方法。然后分别用高温固相法和微波热合成法试制SrAl_2O_4: Eu~(2+), Dy~(3+),并测试制成品性能,因高温固相法合成的材料光学性能远远高于微波热合成法制备的材料光学性能。决定选用高温固相法合成SrAl_2O_4: Eu~(2+), Dy~(3+)。
使用高温固相法合成夜光材料,对原料混合均匀性要求高,为此采用新的方法对原料进行预处理,改善了高温固相法原料混合不均的问题。
原料经过预处理后,采用高温固相法合成掺杂稀土的铝酸锶夜光材料,通过测试分析材料的晶相组成、激发光谱、发射光谱和余辉性能,研究了不同工艺条件对稀土铝酸锶夜光材料光学性能的影响。实验结果表明,预处理工序是制备材料的前提,新的预处理方法有效地改善了余辉性能;原料配比影响晶相组成和发光颜色;激活剂的种类和含量影响荧光光谱和余辉性能;烧结温度和助熔剂含量主要影响晶相组成和余辉性能。最后通过反复实验得到了较为理想的原料配比和较合理的工艺参数。
SrAl_2O_4: Eu~(2+), Dy~(3+) is a new functional material which was developed in the the 90’s of the 20th Century. SrAl_2O_4: Eu~(2+), Dy~(3+) is a kind of aluminate system luminous materials which doped Eu, Dy into strontium aluminate, it have high performance. Rare-earth strontium aluminate luminous materials is free from radioactivity, nontoxic and harmless. The properties of this kind of material is so good that it have the largest output and applied range in the past few years. The rare-earth strontium aluminate luminous materials should be improved from three contents: 1.Luminous intensity is not large enough; 2. The number of colour is little; 3. The grain size of materials should be minish without losing luminous intensity. As a result, It is necessary to improve the process in order to uprate the luminescent properties of the rare-earth strontium aluminate luminous materials which will be applied extensively in a lot of professions.
The luminance of luminous materials mostly depend on component element of host material and preparation technology conditions. The key of improving the luminescent properties is to choose right raw material and technological parameter properly.
Firstly compare relative merits of different methods such as solid phase reaction, sol-gel preparation, microwave synthesis coprecipitation method, Hydriding combustion synthesis, and spray drying process through theoretical analyzing. To consider in the fields of environmental protection, prime cost and the luminance properpties of materials, preliminary choose solid phase reaction and microwave synthesis. Secondly trial-produce SrAl_2O_4: Eu~(2+), Dy~(3+) by solid phase reaction and microwave synthesis, test the luminance properpties of products. The luminance properpties of products made by solid phase reaction is further better than which made by microwave synthesis, so we decide to produe SrAl_2O_4: Eu~(2+), Dy~(3+) by solid phase reaction.
Because of the important of uniformity of raw material when produce materials by solid phase reaction, we pretreated raw materisls in new ways, improve the uniformity effectively. Raw material was pretreated in new ways, then the rare-earth strontium aluminate luminous materials were produced by solid phase reaction method. The phase composition, excitation spectrum, emission spectrum and phosphorescence properties of luminous material were tested. To study influence of process conditions on luminescent properties of the rare-earth strontium aluminate luminous materials. The experimental results indicate that the pre-processing is premise of the synthesis of luminous material, new pre-processing improve luminescent properties of the rare-earth strontium aluminate luminous materials effectively, raw material ratio effect on phase composition and luminescent color, the sintering temperature and flux content effect on phase composition and luminescent properties. The species and contents of activating agent effect on excitation spectrum, emission spectrum and phosphorescence properties. The best component proportion of luminous materials were found after lots of trial and error, good technology has been gotten through many experimentations.
夜光材料的发光性质在很大程度上取决于基质材料的组成和合成工艺条件,所以要提高SrAl_2O_4: Eu~(2+), Dy~(3+)的光学性能,关键在于合理选择原料和工艺条件。
首先,通过理论分析,比较了高温固相法、溶胶一凝胶法、微波热合成法、共沉淀法,燃烧合成法、喷雾干燥法等方法的优缺点,从环保、成本和制成品性能等方面考虑,初步选择高温固相法和微波热合成法作为实验方法。然后分别用高温固相法和微波热合成法试制SrAl_2O_4: Eu~(2+), Dy~(3+),并测试制成品性能,因高温固相法合成的材料光学性能远远高于微波热合成法制备的材料光学性能。决定选用高温固相法合成SrAl_2O_4: Eu~(2+), Dy~(3+)。
使用高温固相法合成夜光材料,对原料混合均匀性要求高,为此采用新的方法对原料进行预处理,改善了高温固相法原料混合不均的问题。
原料经过预处理后,采用高温固相法合成掺杂稀土的铝酸锶夜光材料,通过测试分析材料的晶相组成、激发光谱、发射光谱和余辉性能,研究了不同工艺条件对稀土铝酸锶夜光材料光学性能的影响。实验结果表明,预处理工序是制备材料的前提,新的预处理方法有效地改善了余辉性能;原料配比影响晶相组成和发光颜色;激活剂的种类和含量影响荧光光谱和余辉性能;烧结温度和助熔剂含量主要影响晶相组成和余辉性能。最后通过反复实验得到了较为理想的原料配比和较合理的工艺参数。
SrAl_2O_4: Eu~(2+), Dy~(3+) is a new functional material which was developed in the the 90’s of the 20th Century. SrAl_2O_4: Eu~(2+), Dy~(3+) is a kind of aluminate system luminous materials which doped Eu, Dy into strontium aluminate, it have high performance. Rare-earth strontium aluminate luminous materials is free from radioactivity, nontoxic and harmless. The properties of this kind of material is so good that it have the largest output and applied range in the past few years. The rare-earth strontium aluminate luminous materials should be improved from three contents: 1.Luminous intensity is not large enough; 2. The number of colour is little; 3. The grain size of materials should be minish without losing luminous intensity. As a result, It is necessary to improve the process in order to uprate the luminescent properties of the rare-earth strontium aluminate luminous materials which will be applied extensively in a lot of professions.
The luminance of luminous materials mostly depend on component element of host material and preparation technology conditions. The key of improving the luminescent properties is to choose right raw material and technological parameter properly.
Firstly compare relative merits of different methods such as solid phase reaction, sol-gel preparation, microwave synthesis coprecipitation method, Hydriding combustion synthesis, and spray drying process through theoretical analyzing. To consider in the fields of environmental protection, prime cost and the luminance properpties of materials, preliminary choose solid phase reaction and microwave synthesis. Secondly trial-produce SrAl_2O_4: Eu~(2+), Dy~(3+) by solid phase reaction and microwave synthesis, test the luminance properpties of products. The luminance properpties of products made by solid phase reaction is further better than which made by microwave synthesis, so we decide to produe SrAl_2O_4: Eu~(2+), Dy~(3+) by solid phase reaction.
Because of the important of uniformity of raw material when produce materials by solid phase reaction, we pretreated raw materisls in new ways, improve the uniformity effectively. Raw material was pretreated in new ways, then the rare-earth strontium aluminate luminous materials were produced by solid phase reaction method. The phase composition, excitation spectrum, emission spectrum and phosphorescence properties of luminous material were tested. To study influence of process conditions on luminescent properties of the rare-earth strontium aluminate luminous materials. The experimental results indicate that the pre-processing is premise of the synthesis of luminous material, new pre-processing improve luminescent properties of the rare-earth strontium aluminate luminous materials effectively, raw material ratio effect on phase composition and luminescent color, the sintering temperature and flux content effect on phase composition and luminescent properties. The species and contents of activating agent effect on excitation spectrum, emission spectrum and phosphorescence properties. The best component proportion of luminous materials were found after lots of trial and error, good technology has been gotten through many experimentations.
引文
1.肖志国.蓄光型发光材料及其制品[M].北京:化学工业出版社. 2002:36.
2.葛明桥,虞国炜.彩色与彩色光稀土夜光纤维及其制造方法:中国专利,1584138 [P].2005—02—23.
3.李晓微,金为群.稀土发光材料的研究与展望[J].中国材料科技与设备,2006,2:20—22.
4.郑子樵,李红英.稀土功能材料[M].北京:化学化工出版社.173—174.
5. Palilla F.C, Luvine AX,Tomkus MR.Fluorescent properties of alkaline earth aluminates of the type MA1204 activated by divalent europium[J].J.Electro.Chem.Soc,1968,115(6):642—644
6.唐明道,李长宽,高志武,等. Sr2AlO4∶Eu的发光特性研究[J].发光学报,1995,16(l):51—56.
7.宋庆梅,陈暨耀,吴中亚.掺镁的铝酸锶铕磷光体的发光特性[J]. .复旦学报(自然科学版),1995,34(l):103—106.
8. MATSUZAWAT, AOKI Y, TAKEUCHI N, et al. A new phos-phorescent phosphor with high brightness, SrAl_2O_4∶Eu~(2+), Dy~(3+)[J]. J. Electrochem. Soc., 1996. 143(8): 2670-2673
9. Z.C.Wu,J.X.Shi,J.Wang, et al. Synthesis and luminescent properties of SrAl_2O_4∶Eu~(2+) green-emitting phosphor for white LEDs[J]. J.Materials letters.2006, 3(38): 3499—3501.
10. Chengkang Chang,Dali Mao,Jianfeng Shen,et al. Preparation of long persistent SrO·Al2O3 ceramics and their luminescent properties[J].Journal of Alloys and Compounds. 2003 (348) :224—230.
11.金钦汉等.微波化学[M].科学出版社.1999:94.
12.赵菊梅,郭雪峰,徐燕娜等.稀土铝酸锶夜光纤维发光性质的研究[J].纺织学报,2008,29(11):1—5.
13.孙家跃,杜海燕.固体发光材料[M].北京:化学化工出版社.2003:5—6.
14.张瑞军,张玉奇,刘小蕊等.稀土蓝色长余辉发光材料的研究进展[J].中国陶瓷工业,2006,13(4):37—40.
15.白木子荫.稀土发光材料的发光原理与应用[J].稀土,2002,26(6):48—51.
16.张瑞俭,宋桂玲.发光体MA12O4:Eu~(2+),RE3+的长余辉机理[J]光电子技术2003,23(1),30—34.
17.李群,滕晓明,庄卫东等.稀土长余辉发光材料的研究现状和发展趋势[J].稀土,2005,26(4):62—67.
18.林元华,张中太,张枫等.长余辉光致发光玻璃的制备及其性能的研究[J].材料科学与工艺,2000,8(1):1—6.
19. Xu, Ming-Xia; Guo, Qing-Jie; Qin, Yu-Xing.Preparation of long afterglow photoluminescent material SrAl_2O_4: Eu~(2+), Dy~(3+) and its luminescent property Transactions of Tianjin University.2004,9(10): 201—205
20. Qiu Guanming,Chen Yongjie,Geng Xiujuan, et al. Synthesis of Long Aferglow Phosphors MAl_2O_4:Eu~(2+),Dy~(3+) (M=Ca,Sr,Ba) by Microemulsion Method and Their Luminescent Properties[J]. Journal OF RARE EARTHS.2005, 10(23): 629—632.
21.吕兴栋,舒万艮,黄可龙. SrO/Al2O3比率对Sr2AlO4∶Eu,Dy发光性能的影响[J].发光学报.2004.12(6):674—677.
22. Peng mingying,Da Ning,Qiao Yanbo,et al. Investigation on Valence-Change Behavior of Europium Ions in Eu-Doped Aluminate and Silicate Phosphors[J]. Journal OF RARE EARTHS.2006, 9(8): 749—753.
23.刘光华.稀土材料学[M].北京:化学化工出版社.2007:200—201.
24. Xixian Luo, Wanghe Cao and Zhiguo Xiao. Investigation on the distribution of rare earth ions in strontium aluminate phosphors[J]. Journal of Alloys and Compounds, 2006, 10(3):250—255.
25.张平,徐明霞,沈毅等.Eu~(2+)对纳米SrAl_2O_4:Eu,Dy发光性能的影响[J].中国稀土学报,2005.12(23):12—15.
26. LU Xingddong, SHU Wangen.Roles of crystal defects in persistent luminescence of Eu~(2+),Dy~(3+)co-doped strontium aluminate based phosphors[J].RARE METALS,2007,8(26): 305—310
27.何大伟,崔兴龙.稀土氧化钕对铝酸盐长余辉发光材料性能的影响[J].中国稀土学报,2001(12) : 599—601.
28.吕兴栋,舒万艮,黄可龙,周文华.掺杂B3+在SrAl_2O_4∶Eu, Dy中的作用及其机制研究. 2004.6(3):313—317.
29.李金龙,郝虎在,黄平等.硼掺杂对SrA12O4:Eu,Dy长余辉发光材料合成温度及性能的影响[J].太原理工大学学报,2007,39(2):105—107.
30.许晓.超长余辉发光材料的制备及其性能表征[D]:[硕士学位论文].南京:华东师范大学化学系,2008
31.耿杰,吴召平,陈玮等. SrAl_2O_4:Eu~(2+),Dy~(3+)发光粉体的长余辉特性研究[J].无机材料学报,2003.3(18):480—484
32.张玉军,尹衍升. Eu~(2+),Dy~(3+)共激活铝酸锶发光材料长余辉发光机理探讨[J].人工晶体学报,2004.2 (33):67—70
33.赵淑金,林元华,张中太等. Eu~(2+)离子在Sr2Al6O11基磷光体中发光行为的研究[J].无机材料学报,2003.1(18):225—228
34. Jiang, Hongyi; Xu, Bo. Preparation of silicate long afterglow photo-luminescent materials by high temperature solid-state reaction[J]. Journal of the Chinese Ceramic Society.2006, 9(36):1154—1157
35. Yang, Zhi-Ping; Liu, Zhen; Zhu, Sheng-Chao.The luminescent character of long-afterglow material SrAl_2O_4:Eu~(2+), Dy~(3+)[J]. Proceedings of SPIE - The International Society for Optical Engineering. 2002(4918):413—417
2.葛明桥,虞国炜.彩色与彩色光稀土夜光纤维及其制造方法:中国专利,1584138 [P].2005—02—23.
3.李晓微,金为群.稀土发光材料的研究与展望[J].中国材料科技与设备,2006,2:20—22.
4.郑子樵,李红英.稀土功能材料[M].北京:化学化工出版社.173—174.
5. Palilla F.C, Luvine AX,Tomkus MR.Fluorescent properties of alkaline earth aluminates of the type MA1204 activated by divalent europium[J].J.Electro.Chem.Soc,1968,115(6):642—644
6.唐明道,李长宽,高志武,等. Sr2AlO4∶Eu的发光特性研究[J].发光学报,1995,16(l):51—56.
7.宋庆梅,陈暨耀,吴中亚.掺镁的铝酸锶铕磷光体的发光特性[J]. .复旦学报(自然科学版),1995,34(l):103—106.
8. MATSUZAWAT, AOKI Y, TAKEUCHI N, et al. A new phos-phorescent phosphor with high brightness, SrAl_2O_4∶Eu~(2+), Dy~(3+)[J]. J. Electrochem. Soc., 1996. 143(8): 2670-2673
9. Z.C.Wu,J.X.Shi,J.Wang, et al. Synthesis and luminescent properties of SrAl_2O_4∶Eu~(2+) green-emitting phosphor for white LEDs[J]. J.Materials letters.2006, 3(38): 3499—3501.
10. Chengkang Chang,Dali Mao,Jianfeng Shen,et al. Preparation of long persistent SrO·Al2O3 ceramics and their luminescent properties[J].Journal of Alloys and Compounds. 2003 (348) :224—230.
11.金钦汉等.微波化学[M].科学出版社.1999:94.
12.赵菊梅,郭雪峰,徐燕娜等.稀土铝酸锶夜光纤维发光性质的研究[J].纺织学报,2008,29(11):1—5.
13.孙家跃,杜海燕.固体发光材料[M].北京:化学化工出版社.2003:5—6.
14.张瑞军,张玉奇,刘小蕊等.稀土蓝色长余辉发光材料的研究进展[J].中国陶瓷工业,2006,13(4):37—40.
15.白木子荫.稀土发光材料的发光原理与应用[J].稀土,2002,26(6):48—51.
16.张瑞俭,宋桂玲.发光体MA12O4:Eu~(2+),RE3+的长余辉机理[J]光电子技术2003,23(1),30—34.
17.李群,滕晓明,庄卫东等.稀土长余辉发光材料的研究现状和发展趋势[J].稀土,2005,26(4):62—67.
18.林元华,张中太,张枫等.长余辉光致发光玻璃的制备及其性能的研究[J].材料科学与工艺,2000,8(1):1—6.
19. Xu, Ming-Xia; Guo, Qing-Jie; Qin, Yu-Xing.Preparation of long afterglow photoluminescent material SrAl_2O_4: Eu~(2+), Dy~(3+) and its luminescent property Transactions of Tianjin University.2004,9(10): 201—205
20. Qiu Guanming,Chen Yongjie,Geng Xiujuan, et al. Synthesis of Long Aferglow Phosphors MAl_2O_4:Eu~(2+),Dy~(3+) (M=Ca,Sr,Ba) by Microemulsion Method and Their Luminescent Properties[J]. Journal OF RARE EARTHS.2005, 10(23): 629—632.
21.吕兴栋,舒万艮,黄可龙. SrO/Al2O3比率对Sr2AlO4∶Eu,Dy发光性能的影响[J].发光学报.2004.12(6):674—677.
22. Peng mingying,Da Ning,Qiao Yanbo,et al. Investigation on Valence-Change Behavior of Europium Ions in Eu-Doped Aluminate and Silicate Phosphors[J]. Journal OF RARE EARTHS.2006, 9(8): 749—753.
23.刘光华.稀土材料学[M].北京:化学化工出版社.2007:200—201.
24. Xixian Luo, Wanghe Cao and Zhiguo Xiao. Investigation on the distribution of rare earth ions in strontium aluminate phosphors[J]. Journal of Alloys and Compounds, 2006, 10(3):250—255.
25.张平,徐明霞,沈毅等.Eu~(2+)对纳米SrAl_2O_4:Eu,Dy发光性能的影响[J].中国稀土学报,2005.12(23):12—15.
26. LU Xingddong, SHU Wangen.Roles of crystal defects in persistent luminescence of Eu~(2+),Dy~(3+)co-doped strontium aluminate based phosphors[J].RARE METALS,2007,8(26): 305—310
27.何大伟,崔兴龙.稀土氧化钕对铝酸盐长余辉发光材料性能的影响[J].中国稀土学报,2001(12) : 599—601.
28.吕兴栋,舒万艮,黄可龙,周文华.掺杂B3+在SrAl_2O_4∶Eu, Dy中的作用及其机制研究. 2004.6(3):313—317.
29.李金龙,郝虎在,黄平等.硼掺杂对SrA12O4:Eu,Dy长余辉发光材料合成温度及性能的影响[J].太原理工大学学报,2007,39(2):105—107.
30.许晓.超长余辉发光材料的制备及其性能表征[D]:[硕士学位论文].南京:华东师范大学化学系,2008
31.耿杰,吴召平,陈玮等. SrAl_2O_4:Eu~(2+),Dy~(3+)发光粉体的长余辉特性研究[J].无机材料学报,2003.3(18):480—484
32.张玉军,尹衍升. Eu~(2+),Dy~(3+)共激活铝酸锶发光材料长余辉发光机理探讨[J].人工晶体学报,2004.2 (33):67—70
33.赵淑金,林元华,张中太等. Eu~(2+)离子在Sr2Al6O11基磷光体中发光行为的研究[J].无机材料学报,2003.1(18):225—228
34. Jiang, Hongyi; Xu, Bo. Preparation of silicate long afterglow photo-luminescent materials by high temperature solid-state reaction[J]. Journal of the Chinese Ceramic Society.2006, 9(36):1154—1157
35. Yang, Zhi-Ping; Liu, Zhen; Zhu, Sheng-Chao.The luminescent character of long-afterglow material SrAl_2O_4:Eu~(2+), Dy~(3+)[J]. Proceedings of SPIE - The International Society for Optical Engineering. 2002(4918):413—417