染料电子墨水电泳的原理研究
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摘要
电子纸,是具有普通纸质印刷物显示效果的超薄、柔软的电子显示器件,具有高反射率、宽视角、柔软便携、双稳态显示、耗电量低等特点。近年来,电子纸受到了广泛关注。电泳显示电子纸技术,是多种电子纸技术中发展最成熟,最接近产业化的技术之一。
传统的电泳显示电子纸器件是基于分散体系中的带电颜料颗粒在电场下发生电泳移动完成显示的。文献记载的电泳显示电子纸原理器件所采用的电泳显示颗粒集中在无机颜料颗粒如二氧化钛、二氧化硅、有机颜料,如PY14,PY12这两大类上。但是颜料电泳的最大缺点就是体系稳定性差。电泳显示过程中,由于比重大,颜料颗粒很容易絮凝,沉降破坏显示。能否找到一种新的电泳显色材料代替颜料是设计本课题的出发点,在此基础上研究染料电泳体系的电泳原理是本文的最终目的。
本文通过实验测试了几类染料电泳电子墨水的组成与性能关系,通过金相显微镜拍摄的照片详细地描述了染料电泳过程,密度计记录了染料电泳前后的密度变化,集中测试了金属络合染料类和酸性染料类电子墨水的电化学性能,系统研究了染料在溶剂中的存在状态。此外,对染料电泳响应时间的影响因素,以及染料体系吸光度随时间的变化进行了系统的研究。
本文的研究证实了染料电泳显示,找到了几种电泳性能较好的染料电泳体系,通过测试证明了染料在溶剂中并不是以单个分子存在,而是以分子的聚集态形式存在。进而推测电泳显示电泳液中染料带电的原理。此外,确定了金属络合红Red04和酸性黑1染料在电泳过程中伴随着电化学反应的发生,生成了氧化偶氮苯。并且测试得到了四种染料电泳的响应时间,分析染料电泳速度较慢的原因。认为目前染料在电子纸中的应用具有一定的局限性。
Electronic paper technology has received a great deal of attention in recent years. Electronic paper is a paper—like display monitor which has many properties such as high reflection, wide visual angle, portability, flexibility and bistable. Electrophoresis image displays (EPID) is the most likely candidate in search for a display which has these properties.
Traditional EPIDs are thin, flexible reflective displays based on the movement of electrical charged pigment particles which are dispersed in a colored dielectric medium. Most of the reported prototype electronic papers are based on the electrophoresis of charged particles in colloidal suspension, which take the inorganic pigment titanium dioxide (TiO2) or silicon dioxide (SiO2) as particles. The dielectric medium such as tetrachloroethylene, isopar, xylene, are of high specific gravity to compatible with pigment particles. However, the pigment electrophoresis ink has a problem with suspension stability such as agglomeration, lateral migration and sedimentation because of the high density of pigment. Other materials which can substitute pigments as colored particles and the solvents which can disperse the colored particles well will be introduced later in this paper. Indeed, there are many papers referring to organic and inorganic pigment particle electrophoresis colloid, while less report is concerned about the electrophoresis of dye. In order to prepare a novel electronic ink, this study has been focused on the principle of electrophoresis of dye in different solvent or surfactant, and the relationship between the composition and electrophoresis properties of the electronic ink of dye.
Dozens of dye have been tested in this paper including dispersed dyes, acid dyes, solvent dyes, metal complex dye and etc. To compatible with dye, several kinds of solvents and charge control agents also have been tested including pyridine, ethanol, xylene, Tetrachlorethylene, diethylamine, aniline, PIBI. Dyes were dissolved or dispersed in the solvents with certain surfactant and the electrophoresis performance of the solvent was observed in electrophoresis display prototype which was composed by 2 pieces of parallel ITO glass.
The process of dye electrophoresis was described by photos of Metallurgical Microscopy; the density change of dye system before and after electrophoresis was recorded by X-Rite, in these ways we generally know the phenomenon of dye electrophoresis.
The electrochemistry reaction of the dye, solvent and electrode was determined by electrochemistry station. It can be found that the system consisting of conductive medium is instable in electrophoresis. Electrode, electrophoresis media and dyes would be suffered electrochemical damage under the supplied voltage. Most of the dye in polarity medium would decompose during electrophoresis if the applied voltage is higher than certain value.
And we also study the state of dye in the solvent. It was confirmed that the dye was not existed individually in the solvent, but was gathered together. Because dye particles of electronic ink was smaller than pigment of Electronic ink, so it was solved that pigment in the solvent were easily gathered. And luckily it was showed that it was clear and easily distinguishable before and after the dye system electrophoresis.
Additionally, we tested the dye electrophoresis response time through UV-Vis spectrophotometer, and studied the factors of influencing dye electrophoresis response time, including the voltage, the concentration of dye system and structure of dye. And the UV-visible absorption change of a fixed point with time was also systematically studied.
It was insufficient that the best electrophoresis performance is the dye solution of weak polar system in the present, when the voltage greater than a certain value, the system will happen electrochemical reaction, leading to dye decomposition.
传统的电泳显示电子纸器件是基于分散体系中的带电颜料颗粒在电场下发生电泳移动完成显示的。文献记载的电泳显示电子纸原理器件所采用的电泳显示颗粒集中在无机颜料颗粒如二氧化钛、二氧化硅、有机颜料,如PY14,PY12这两大类上。但是颜料电泳的最大缺点就是体系稳定性差。电泳显示过程中,由于比重大,颜料颗粒很容易絮凝,沉降破坏显示。能否找到一种新的电泳显色材料代替颜料是设计本课题的出发点,在此基础上研究染料电泳体系的电泳原理是本文的最终目的。
本文通过实验测试了几类染料电泳电子墨水的组成与性能关系,通过金相显微镜拍摄的照片详细地描述了染料电泳过程,密度计记录了染料电泳前后的密度变化,集中测试了金属络合染料类和酸性染料类电子墨水的电化学性能,系统研究了染料在溶剂中的存在状态。此外,对染料电泳响应时间的影响因素,以及染料体系吸光度随时间的变化进行了系统的研究。
本文的研究证实了染料电泳显示,找到了几种电泳性能较好的染料电泳体系,通过测试证明了染料在溶剂中并不是以单个分子存在,而是以分子的聚集态形式存在。进而推测电泳显示电泳液中染料带电的原理。此外,确定了金属络合红Red04和酸性黑1染料在电泳过程中伴随着电化学反应的发生,生成了氧化偶氮苯。并且测试得到了四种染料电泳的响应时间,分析染料电泳速度较慢的原因。认为目前染料在电子纸中的应用具有一定的局限性。
Electronic paper technology has received a great deal of attention in recent years. Electronic paper is a paper—like display monitor which has many properties such as high reflection, wide visual angle, portability, flexibility and bistable. Electrophoresis image displays (EPID) is the most likely candidate in search for a display which has these properties.
Traditional EPIDs are thin, flexible reflective displays based on the movement of electrical charged pigment particles which are dispersed in a colored dielectric medium. Most of the reported prototype electronic papers are based on the electrophoresis of charged particles in colloidal suspension, which take the inorganic pigment titanium dioxide (TiO2) or silicon dioxide (SiO2) as particles. The dielectric medium such as tetrachloroethylene, isopar, xylene, are of high specific gravity to compatible with pigment particles. However, the pigment electrophoresis ink has a problem with suspension stability such as agglomeration, lateral migration and sedimentation because of the high density of pigment. Other materials which can substitute pigments as colored particles and the solvents which can disperse the colored particles well will be introduced later in this paper. Indeed, there are many papers referring to organic and inorganic pigment particle electrophoresis colloid, while less report is concerned about the electrophoresis of dye. In order to prepare a novel electronic ink, this study has been focused on the principle of electrophoresis of dye in different solvent or surfactant, and the relationship between the composition and electrophoresis properties of the electronic ink of dye.
Dozens of dye have been tested in this paper including dispersed dyes, acid dyes, solvent dyes, metal complex dye and etc. To compatible with dye, several kinds of solvents and charge control agents also have been tested including pyridine, ethanol, xylene, Tetrachlorethylene, diethylamine, aniline, PIBI. Dyes were dissolved or dispersed in the solvents with certain surfactant and the electrophoresis performance of the solvent was observed in electrophoresis display prototype which was composed by 2 pieces of parallel ITO glass.
The process of dye electrophoresis was described by photos of Metallurgical Microscopy; the density change of dye system before and after electrophoresis was recorded by X-Rite, in these ways we generally know the phenomenon of dye electrophoresis.
The electrochemistry reaction of the dye, solvent and electrode was determined by electrochemistry station. It can be found that the system consisting of conductive medium is instable in electrophoresis. Electrode, electrophoresis media and dyes would be suffered electrochemical damage under the supplied voltage. Most of the dye in polarity medium would decompose during electrophoresis if the applied voltage is higher than certain value.
And we also study the state of dye in the solvent. It was confirmed that the dye was not existed individually in the solvent, but was gathered together. Because dye particles of electronic ink was smaller than pigment of Electronic ink, so it was solved that pigment in the solvent were easily gathered. And luckily it was showed that it was clear and easily distinguishable before and after the dye system electrophoresis.
Additionally, we tested the dye electrophoresis response time through UV-Vis spectrophotometer, and studied the factors of influencing dye electrophoresis response time, including the voltage, the concentration of dye system and structure of dye. And the UV-visible absorption change of a fixed point with time was also systematically studied.
It was insufficient that the best electrophoresis performance is the dye solution of weak polar system in the present, when the voltage greater than a certain value, the system will happen electrochemical reaction, leading to dye decomposition.
引文
[1] Makoto, Omodani, LI Lu-hai( 李 路 海 译 ),Advanced Display( 现 代 显示)[J],2004.6:47～51;
[2] Young N D, Bunn B M, Wilks R W, et al. Thin film transistor and diode addressed AMLCDs on polymer substrates [J]. Journal of the Society for Information Display, 1997, 5 (3):2752281;
[3] Gustafsson G, Cao Y, Treacy GM, et al. Flexible light emitting diodes made from soluble conducting polymers [J]. Nature, 1992, 357 (6378):4772479;
[4] Chen Y, Au J, Kazlas P, et al. Flexible active matrix electronic ink display [J]. Nature, 2003,423136;
[5] Gelinck, Gerwin H, Huitema H, et al. Flexible active matrix displays and shift registers based on solution2processes organic transistors [J]. Nature Materials, 2004, 3 (2):1062110;
[6] Tom Bert, Herbert De Smet, Dielectrophoresis in electronic paper, Displays 24 (2003) 223～230;
[7] Tom Bert, Herbert De Smet, The microscopic physics of electronic paper revealed, Displays 24 (2003) 103～110;
[8] Albert J,Comiskey B,Jacobson J.[P].US:5961804.1999;
[9] Chul Am Kim., Meyoung Ju Joung, [J] Synthetic Metals 151 (2005) 181～185;
[10] Rong-Chang Liang,XiaoJia Wang.HongMei Zang [P].US:0082864.2006;
[11] Foris P L, Brown R W, Phillips P S. Capsule manufacture [P]. US4001140. 1977;
[12] Foris P L, Brown R W, Phillips P S. Capsule manufacture [P]. US4087376. 1978;
[13] Shcridon N K,Richley E A,Mikkelsen J C,et a1.[J].Pros SO c Inform Display.1999,18:141～144;
[14] N. K. Sheridon, Berkovitz, M. A. The gycricon-a twisting ball display[J]. Proc. Soc Information Display, 1977,18:289～293;
[15] N .K Sheridon E. A. Richley, J. C. Mikkelsen, D. Tsuda, R. Sprague. The Gyricon rotating ball display [J].Society for Information 1999, 18:141～144;
[16] Joseph M. Crowley, Morgan Hill,Edward A. Richley, Nicholas K. Sheridon. Method and apparatus for fabricating bichromal balls for a twisting ball display [P].US: 5262098, 1993-11-16;
[17] Edward A. Richley. Method and apparatus for fabricating very small two-color ballsfor a twisting ball display[P].US: 5900192, 1999-5-4;
[18] 应根裕,胡文波,邱勇等编著,平板显示技术,人民邮电出版社;
[19] ROBERT A H. FEENSTAR B J. Video-speed electronic paperbased on electroweting, [J].Nature.2003, 425: 383～385;
[20] 胡欢,吴建刚等,一种新型基于电润湿的受光反射型显示单元,[J] MEMS器件与技术, 1671～4776 (2006)04-0190-04;
[21] 裴广玲,王亭杰,杨毅,金涌,电泳显示微胶囊的制备和性能,物理化学学报,2005,21(4);430～434;
[22] 杨毅,王亭杰,裴广玲,金涌,一步法制备脲醛树脂微胶囊过程的研究,高等化学工程学报,2005年6月,第19卷,第3期,338～343;
[23] 杨毅, 王亭杰, 金涌,高分子材料在微胶囊电泳显示技术中的应用,高分子材料科学与工程,2005年9月,第21卷,第5期,1～4;
[24] 吴建刚,岳瑞峰,曾雪锋,刘理天,新型低驱动电压电子纸显示单元的研究,电子学报,2006年2月,第34卷,第2期,198～200;
[25] 荣宇, 吴刚, 陈红征, 汪茫,电子墨水微胶囊及电泳显示原型器件的制备,高等学校化学学报,2005年5月,第26卷,第5期,982～984;
[26] 丁明惠,张彦奇,唐芳琼等,脲醛预聚条件对电泳微胶囊形态的影响,过程工程学报,2006年2月,第6卷,第1期,51～57;
[27] 张延芬,滕枫,徐征,对电泳液中颜料粒子运动性能的研究,光谱学与光谱分析,2005 年2月,第25卷,第2期;
[28] 段晓霞,徐征,滕枫等,基于电泳技术的电子纸研究进展,液晶与显示,2004年10月,第19卷,第5期;
[29] 李路海,何君勇,张淑芬等,微胶囊制作技术及其在电子纸中的应用,功能材料,2004年,第4期(35)卷;
[30] 刘会刚, 朱勇, 商光辉等,电泳显示器的研究及进展,现代显示,第60期,64～67;
[31] 郭慧林,王建平,赵晓鹏,准均匀分散电子墨水微胶囊的制备研究,功能材料,2005年第4期(36)卷,622～624;
[32] 王建平,赵晓鹏,蓝色电子墨水微胶囊的制备及其电场响应行为,液晶与显示,2004年12月,第19卷,第6期,434～438;
[33] 王建平等,预聚体特性粘数与电子墨水微胶囊性能的关系,材料研究学学报,2005年4月,第19卷,第2期,147～151;
[34] 左朝阳,王建平等,微胶囊化电子墨水的研究现状及其应用,2006年5月,第2卷,第5期,18～21;
[35] Drew Myers, Surfaces, Interfaces and Colloids: Principles and Applications;
[36] 赵国玺,朱 瑶 著,表面活性剂作用原理,中国轻工业出版社;
[37] 杨新伟, 罗钰言, 肖刚编, 染料, 化学工业出版社;
[38] 钱国坻著.染料化学.上海:上海交通大学出版社.1988:12-14;
[39] 马淳安编著.有机电化学合成导论.北京:科学出版社.2002:90～101;
[40] 阿伦.J.巴德 拉里.R.福克纳[美], 邵元华,朱果逸,董献堆,张柏林译.电化学方法原理及应用.化学工业出版社,2006;
[41] LI Yu(黎昱), LIU Jianping(刘建平),YE Tongxiang(童叶翔),etc.[J]Acta Scientiarum Naturalium Universitatis Suntatseni(Natural Science) (自然科学版) 1997,36(2) : 131～132;
[42] Jhon A. Dean, Analytical Chemistry Handbook (分析化学手册, 常文保等校译), Science Press, Beijing.2003.2:6.30;
[43] 李路海,张淑芬,蒲嘉陵,杨锦宗,邹竞,胺对联苯胺黄颜料的电荷控制作用及其红外光谱分析, 光谱学与光谱分析,2005年10月,第25卷,第10期,1584～1587;
[44] 周春隆,穆振义,有机颜料结构、特性及其应用,化学工业出版社,2002,224;
[45]王铭. 新型电子墨水构成与性能关系的研究[D]. 北京:北京印刷学院,2007:50～52;
[2] Young N D, Bunn B M, Wilks R W, et al. Thin film transistor and diode addressed AMLCDs on polymer substrates [J]. Journal of the Society for Information Display, 1997, 5 (3):2752281;
[3] Gustafsson G, Cao Y, Treacy GM, et al. Flexible light emitting diodes made from soluble conducting polymers [J]. Nature, 1992, 357 (6378):4772479;
[4] Chen Y, Au J, Kazlas P, et al. Flexible active matrix electronic ink display [J]. Nature, 2003,423136;
[5] Gelinck, Gerwin H, Huitema H, et al. Flexible active matrix displays and shift registers based on solution2processes organic transistors [J]. Nature Materials, 2004, 3 (2):1062110;
[6] Tom Bert, Herbert De Smet, Dielectrophoresis in electronic paper, Displays 24 (2003) 223～230;
[7] Tom Bert, Herbert De Smet, The microscopic physics of electronic paper revealed, Displays 24 (2003) 103～110;
[8] Albert J,Comiskey B,Jacobson J.[P].US:5961804.1999;
[9] Chul Am Kim., Meyoung Ju Joung, [J] Synthetic Metals 151 (2005) 181～185;
[10] Rong-Chang Liang,XiaoJia Wang.HongMei Zang [P].US:0082864.2006;
[11] Foris P L, Brown R W, Phillips P S. Capsule manufacture [P]. US4001140. 1977;
[12] Foris P L, Brown R W, Phillips P S. Capsule manufacture [P]. US4087376. 1978;
[13] Shcridon N K,Richley E A,Mikkelsen J C,et a1.[J].Pros SO c Inform Display.1999,18:141～144;
[14] N. K. Sheridon, Berkovitz, M. A. The gycricon-a twisting ball display[J]. Proc. Soc Information Display, 1977,18:289～293;
[15] N .K Sheridon E. A. Richley, J. C. Mikkelsen, D. Tsuda, R. Sprague. The Gyricon rotating ball display [J].Society for Information 1999, 18:141～144;
[16] Joseph M. Crowley, Morgan Hill,Edward A. Richley, Nicholas K. Sheridon. Method and apparatus for fabricating bichromal balls for a twisting ball display [P].US: 5262098, 1993-11-16;
[17] Edward A. Richley. Method and apparatus for fabricating very small two-color ballsfor a twisting ball display[P].US: 5900192, 1999-5-4;
[18] 应根裕,胡文波,邱勇等编著,平板显示技术,人民邮电出版社;
[19] ROBERT A H. FEENSTAR B J. Video-speed electronic paperbased on electroweting, [J].Nature.2003, 425: 383～385;
[20] 胡欢,吴建刚等,一种新型基于电润湿的受光反射型显示单元,[J] MEMS器件与技术, 1671～4776 (2006)04-0190-04;
[21] 裴广玲,王亭杰,杨毅,金涌,电泳显示微胶囊的制备和性能,物理化学学报,2005,21(4);430～434;
[22] 杨毅,王亭杰,裴广玲,金涌,一步法制备脲醛树脂微胶囊过程的研究,高等化学工程学报,2005年6月,第19卷,第3期,338～343;
[23] 杨毅, 王亭杰, 金涌,高分子材料在微胶囊电泳显示技术中的应用,高分子材料科学与工程,2005年9月,第21卷,第5期,1～4;
[24] 吴建刚,岳瑞峰,曾雪锋,刘理天,新型低驱动电压电子纸显示单元的研究,电子学报,2006年2月,第34卷,第2期,198～200;
[25] 荣宇, 吴刚, 陈红征, 汪茫,电子墨水微胶囊及电泳显示原型器件的制备,高等学校化学学报,2005年5月,第26卷,第5期,982～984;
[26] 丁明惠,张彦奇,唐芳琼等,脲醛预聚条件对电泳微胶囊形态的影响,过程工程学报,2006年2月,第6卷,第1期,51～57;
[27] 张延芬,滕枫,徐征,对电泳液中颜料粒子运动性能的研究,光谱学与光谱分析,2005 年2月,第25卷,第2期;
[28] 段晓霞,徐征,滕枫等,基于电泳技术的电子纸研究进展,液晶与显示,2004年10月,第19卷,第5期;
[29] 李路海,何君勇,张淑芬等,微胶囊制作技术及其在电子纸中的应用,功能材料,2004年,第4期(35)卷;
[30] 刘会刚, 朱勇, 商光辉等,电泳显示器的研究及进展,现代显示,第60期,64～67;
[31] 郭慧林,王建平,赵晓鹏,准均匀分散电子墨水微胶囊的制备研究,功能材料,2005年第4期(36)卷,622～624;
[32] 王建平,赵晓鹏,蓝色电子墨水微胶囊的制备及其电场响应行为,液晶与显示,2004年12月,第19卷,第6期,434～438;
[33] 王建平等,预聚体特性粘数与电子墨水微胶囊性能的关系,材料研究学学报,2005年4月,第19卷,第2期,147～151;
[34] 左朝阳,王建平等,微胶囊化电子墨水的研究现状及其应用,2006年5月,第2卷,第5期,18～21;
[35] Drew Myers, Surfaces, Interfaces and Colloids: Principles and Applications;
[36] 赵国玺,朱 瑶 著,表面活性剂作用原理,中国轻工业出版社;
[37] 杨新伟, 罗钰言, 肖刚编, 染料, 化学工业出版社;
[38] 钱国坻著.染料化学.上海:上海交通大学出版社.1988:12-14;
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