聚噻吩基导电油墨的制备及其印刷适性研究
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摘要
聚噻吩及其衍生物具有高导电性、环保性、热稳定性等优点,将其制备成导电油墨,在印刷电子和智能包装等领域中极具应用前景。本文以聚(3,4-乙撑二氧噻吩)(PEDOT)、导电炭黑(CB)以及羧甲基纤维素钠(CMC)为主体,采用原位聚合法制备了PEDOT-CB/CMC导电油墨。系统地研究了连接料、辅助添加剂及烧结温度等对油墨黏度、附着力、分散性和导电性能的影响;并借助于丝网印刷技术对油墨的印刷适性进行了研究。结果表明,导电油墨具备良好的分散性和附着力;印品经烧结处理后,其电阻值明显下降并随墨条长度、宽度的增加呈现规律性变化。另外,导电油墨在纸、塑料、棉布等不同基材上均能满足丝网印刷的要求。
Polythiophene and its derivatives have the advantages in high electrical conductivity, environmental protection, and thermal stability. It can be prepared into conductive ink, which has great application prospects in the fields of printed electronics and smart packaging. PEDOT-CB/CMC conductive ink was prepared by in-situ polymerization. The effects of binders, auxiliary additives and sintering temperature on ink viscosity, adhesion, dispersibility and electrical conductivity were systematically studied. The printability of the ink was also studied by means of screen-printing technology. The results showed that the conductive ink had good dispersibility and adhesion properties. After the heat treatment of the printed product, the resistance value decreased significantly, while the resistance value would change regularly with the increase in the length and width of the printed product. In addition, the ink could meet the requirements of screen-printing on different substrates such as paper, plastic and cotton.
Polythiophene and its derivatives have the advantages in high electrical conductivity, environmental protection, and thermal stability. It can be prepared into conductive ink, which has great application prospects in the fields of printed electronics and smart packaging. PEDOT-CB/CMC conductive ink was prepared by in-situ polymerization. The effects of binders, auxiliary additives and sintering temperature on ink viscosity, adhesion, dispersibility and electrical conductivity were systematically studied. The printability of the ink was also studied by means of screen-printing technology. The results showed that the conductive ink had good dispersibility and adhesion properties. After the heat treatment of the printed product, the resistance value decreased significantly, while the resistance value would change regularly with the increase in the length and width of the printed product. In addition, the ink could meet the requirements of screen-printing on different substrates such as paper, plastic and cotton.
引文
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[27]HAN Y Q,SHEN M X,WU Y,et al.Preparation and Electrochemical Performances of PEDOT/sulfonic Acid-Functionalized Graphene Composite Hydrogel[J].Synthetic Metals,2013,172:21-27.
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[29]宋继中,贺英,朱棣,等.柔性光电器件发光层用ZnO微纳阵列/聚合物复合材料[J].物理化学学报,2011,27(5):1207-1213.SONG Jizhong,HE Ying,ZHU Di,et al.Polymer/ZnO Micro-Nano Array Composites for Light-Emitting Layer of Flexible Optoelectronic Devices[J].Acta Physico-Chimica Sinica,2011,27(5):1207-1213.
[30]WOLFART F,HRYNIEWICZ B M,GóES M S,et al.Conducting Polymers Revisited:Applications in Energy,Electrochromism and Molecular Recognition[J].Journal of Solid State Electrochemistry,2017,21(9):2489-2515.
[2]BALDE M,JACQUEMOUD-COLLET F,VENAA,et al.Wet Microelectronic Technologies on Paper Substrate for Flexible Electronic Applications[J].Sensors and Actuators A:Physical,2016,240:118-125.
[3]STAAKE T,THIESSE F,FLEISCH E.Extending the EPC Network:The Potential of RFID in AntiCounterfeiting[C]//Proceedings of the 2005 ACMSymposium on Applied Computing.Santa Fe:Association for Computing Machinery,2005:1607-1612.
[4]BIBI F,GUILLAUME C,GONTARD N,et al.AReview:RFID Technology Having Sensing Aptitudes for Food Industry and Their Contribution to Tracking and Monitoring of Food Products[J].Trends in Food Science and Technology,2017,62:91-103.
[5]YAN J M,GUO Z P,GAO H L,et al.Security System of CNC Machine Tools Based on Artificial Intelligence[J].Applied Mechanics and Materials,2012,271/272:488-492.
[6]李路海,莫黎昕,冉军,等.导电油墨及其应用技术进展[J].影像科学与光化学,2014,32(4):393-401.LI Luhai,MO Lixin,RAN Jun,et al.Conductive Ink and Its Application Technology Progress[J].Imaging Science and Photochemistry,2014,32(4):393-401.
[7]SHIRAKAWA H,IKEDA S.Infrared Spectra of Poly(acetylene)[J].Polymer Journal,1971,2(2):231-244.
[8]潘光华,李云,李彬胜,等.导电油墨在包装防伪印刷中的应用研究[J].包装工程,2012(17):130-132.PAN Guanghua,LI Yun,LI Binsheng,et al.Application Research on Electrically Conductive Ink for Anti-Counterfeit Package Printin[J].Packaging Engineering,2012(17):130-132.
[9]CHIANG C K,DRUY M A,GAU S C,et al.Synthesis of Highly Conducting Films of Derivatives of Polyacetylene,(CH)x[J].Journal of the American Chemical Society,1978,100(3):1013-1015.
[10]马秀峰,李飞.导电油墨技术及其研究方向[J].中国印刷与包装研究,2010,2(6):9-14.MA Xiufeng,LI Fei.Conductive Ink Technology and Research Direction[J].China Printing and Packaging Study,2010,2(6):9-14.
[11]钱俊,苏亚兰,周奕华,等.纳米铜导电油墨的制备及其应用[J].包装学报,2014(4):39-43.QIAN Jun,SU Yalan,ZHOU Yihua,et al.Preparation and Application Research of Nano-Copper Conductive Ink[J].Packaging Journal,2014(4):39-43.
[12]石高全,李春,梁映秋.高性能导电高分子材料[J].大学化学,1998,13(1):1-5.SHI Gaoquan,LI Chun,LIANG Yingqiu.High Performance Conductive Polymer Material[J].University Chemistry,1998,13(1):1-5.
[13]SHIRAKAWA H.The Discovery of Polyacetylene Film:The Dawning of an Era of Conducting Polymers(Nobel Lecture)[J].Angewandte Chemie International Edition,2001,40(14):2574-2580.
[14]WANG H,YIN L,PU X,et al.Facile Charge Carrier Adjustment for Improving Thermopower of Doped Polyaniline[J].Polymer,2013,54(3):1136-1140.
[15]XU K L,GAO C Y,CHEN G M,et al.Direct Evidence for Effect of Molecular Orientation on Thermoelectric Performance of Organic Polymer Materials by Infrared Dichroism[J].Organic Electronics,2016,31:41-47.
[16]LIU D,ZHANG L,LI M K,et al.Magnetic Fe3O4-PS-Polyacetylene Composite Microspheres Showing Chirality Derived from Helical Substituted Polyacetylene[J].Macromolecular Rapid Communications,2012,33(8):672-677.
[17]ZHU H F,LIU C C,SONG H J,et al.Thermoelectric Performance of Poly(3-hexylthiophene)Films Doped by Iodine Vapor with Promising High Seebeck Coefficient[J].Electronic Materials Letters,2014,10(2):427-431.
[18]GU H B,TADAKAMALLA S,HUANG Y D,et al.Polyaniline Stabilized Magnetite Nanoparticle Reinforced Epoxy Nanocomposites[J].ACS Applied Materials and Interfaces,2012,4(10):5613-5624.
[19]GUO J,ZHANG X,GU H B,et al.Reinforced Magnetic Epoxy Nanocomposites with Conductive Polypyrrole Nanocoating on Nanomagnetite as a Coupling Agent[J].RSC Advances,2014,4(69):36560-36572.
[20]DANG X D,INTELMANN C M,RAMMELT U,et al.Electrochemical Copolymerization of Pyrrole and2,2-Bithiophene and Semiconducting Characterization of the Resulting Copolymer Films by Electrochemical Impedance Spectroscopy and Photoelectrochemistry[J].Journal of Solid State Electrochemistry,2004,8(10):727-734..
[21]SALATELLI E,ANGIOLINI L,BRAZZI A,et al.Synthesis,Characterization and Electrochemical Properties of New Functional Polythiophenes[J].Synthetic Metals,2010,160(23/24):2681-2686.
[22]GURUNATHAN K,MURUGAN A V,MARIMUTHUR,et al.Electrochemically Synthesised Conducting Polymeric Materials for Applications Towards Technology in Electronics,Optoelectronics and Energy Storage Devices[J].Materials Chemistry and Physics,1999,61(3):173-191.
[23]卢小伟,梁祐慈,钟云飞,等.基于石墨烯的导电油墨配方优化设计[J].包装学报,2017,9(3):89-94.LU Xiaowei,LIANG Youci,ZHONG Yunfei,et al.Optimized Formulation Design of Graphene-Based Conductive Ink[J].Packaging Journal,2017,9(3):89-94.
[24]CINTI S,NEAGU D,CARBONE M,et al.Novel Carbon Black-Cobalt Phthalocyanine Nanocomposite as Sensing Platform to Detect Organophosphorus Pollutants at Screen-Printed Electrode[J].Electrochimica Acta,2016,188:574-581.
[25]陈挺.基于纳米聚3,4-乙撑二氧噻吩的导电复合材料制备及其在印刷电子中的应用[D].广州:华南理工大学,2018.CHEN Ting.Preparation of Conductive Composites Based on Nano-Poly(3,4-Ethylenedioxythiophene)and Its Application in Printed Electronics[D].Guangzhou:South China University of Technology,2018.
[26]王正祥,李运华,邓琪,等.UV固化水性聚氨酯基油墨的制备[J].包装学报,2016,8(1):20-24,58.WANG Zhengxiang,LI Yunhua,DENG Qi,et al.The Preparation of Ink Based on UV-Curable Waterborne Polyurethane[J].Packaging Journal,2016,8(1):20-24,58.
[27]HAN Y Q,SHEN M X,WU Y,et al.Preparation and Electrochemical Performances of PEDOT/sulfonic Acid-Functionalized Graphene Composite Hydrogel[J].Synthetic Metals,2013,172:21-27.
[28]HAN M G,FOULGER S H.Preparation of Poly(3,4-ethylenedioxythiophene)(PEDOT)Coated Silica CoreShell Particles and PEDOT Hollow Particles[J].Chemical Communications,2004(19):2154-2155.
[29]宋继中,贺英,朱棣,等.柔性光电器件发光层用ZnO微纳阵列/聚合物复合材料[J].物理化学学报,2011,27(5):1207-1213.SONG Jizhong,HE Ying,ZHU Di,et al.Polymer/ZnO Micro-Nano Array Composites for Light-Emitting Layer of Flexible Optoelectronic Devices[J].Acta Physico-Chimica Sinica,2011,27(5):1207-1213.
[30]WOLFART F,HRYNIEWICZ B M,GóES M S,et al.Conducting Polymers Revisited:Applications in Energy,Electrochromism and Molecular Recognition[J].Journal of Solid State Electrochemistry,2017,21(9):2489-2515.