发表论文

 

♦ 2019

73. Jingjing Liu, Meng Li, Yifei Zhao, Xiao Zhang, Junyong Lu, Zhicheng Zhang *. "Manipulating H-bonds in Glassy Dipolar Polymers as a New Strategy for High Energy Storage Capacitors with High Pulse Discharged Efficiency" J. Mater. Chem. A. 2019, DOI: 10.1039/C9TA05855A.

72. Qizheng Li, Jingjing Liu, Xiao Zhang, Shaobo Tan, Junyong Lu, Zhicheng Zhang*. " Tuning Dielectric and Energy Storage Properties of Polystyrene Based Polymer 

Dielectric by Manipulating Dipoles and Their Polarizing Behavior" Phys. Chem. Chem. Phys. 2019. DOI: 10.1039/C9CP01798D.

71. Jingjing Liu, Jiani Liao, Yu Liao* and Zhicheng Zhang*  “High field antiferroelectric-like dielectric of poly (vinylidene fluoride-co-trifluoroethylene-cochlorotrifluoroethylene)-graft-poly(styrene-methyl methacrylate) for high pulse capacitors with high energy density and low loss” Poly. Chem. 2019, 10, 3547- 3555.

70. Zhicheng Zhang*, Xiao Wang, Shaobo Tan, Qing Wang*. "Superior electrostrictive strain achieved under low electric fields in relaxor ferroelectric polymers" J. Mater. Chem. A. 2019. 7, 5201-5208 DOI:10.1039/c8ta11938d.

69. Jie Xiong, Tao Fu, Ling Yue, Baobao Qiao, Shengnan Wang, Zhicheng Zhang, Xin Tian. "Hydrogenation of poly(vinylidene fluoride-chlorotrifluoroethylene) via a

light initiated radical chain transfer reaction toward silane" Reactive and Functional Polymers. 2019, 136, 167–172.

♦ 2018

68. Yunchuan Xie, Wanrong Jiang, Tao Fu, Jingjing Liu, Zhicheng Zhang*, Shengnan Wang*. "Achieving High Energy Density and Low Loss in PVDF/BST Nanodielectrics with Enhanced Structural Homogeneity" ACS Appl. Mater. Interfaces. 2018, 10(34), 29038-29047.

67. Wenhua Xu, Gang Yang, Lan Jin, Jie Liu, Yunhe Zhang*, Zhicheng Zhang*, Zhenhua Jiang. "High-k Polymer Nanocomposites Filled with Hyperbranched Phthalocyanine Coated BaTiO3 for High Temperature and Elevated Field Applications“ ACS Appl. Mater. Interfaces. 2018. 10(13):11233-11241.

66. Yifei Zhao, Qian Li, Xiao Zhang, Huayi Li, Junyong Lu, Zhicheng Zhang*. "High Energy Density and Discharging Efficiency Achieved in Chlorinated Polyethylene Films for High Energy Storage Applications". Macromol. Chem. & Phys. 2018, 219(8):1700621 

65. Yunchuan Xie, Jian Wang, Yangyang Yu, Wanrong Jiang, Zhicheng Zhang*. "Enhancing Breakdown Strength and Energy Storage Performance of PVDF-based Nanocomposites by Adding Exfoliated Boron Nitride" Appl. Surf. Sci. 2018, 440:1150-1158.  

64. Weimin Xia, Zhicheng Zhang*. "PVDF Based Dielectric Polymers and Their Applications in Electronic Materials" IET nanodielectrics. 2018, 1(1):17-31. 

63. Yanan Zhang, Shaobo Tan, Jian Wang, Xiao Wang, Weiwei Zhu*, Zhicheng Zhang* "Regulating Dielectric and Ferroelectric Properties of Poly(vinylidene fluoride-trifluoroethylene) with Inner CH=CH Bonds" Polymers. 2018, 10(3), 339; https://doi.org/10.3390/polym10030339 

62. Shaobo Tan, Dan Li, Yanan Zhang, Zhijing Niu, Zhicheng Zhang* "Base Catalyzed Thiol-Ene Click Chemistry toward Inner -CH=CF- Bonds for Controlled Functionalization of Poly(vinylidene fluoride)" Macromol. Chem. & Phys. 2018, 219, 1700632

61. Shaobo Tan, Jie Xiong, Yifei Zhao, Jingjing Liu, Zhicheng Zhang*"Synthesis of Low Dielectric Loss Poly(vinylidene fluoride-co-chlorotrifluoroethylene)-g-poly(methyl methacrylate) with Photo-induced Metal-free ATRPJ. Mater. Chem. C. 2018, 6(15):4131-4139. 

60. Shaobo Tan, Yifei Zhao, Wanwan Zhang, Pin Gao, Weiwei Zhu*, Zhicheng Zhang* “A Light-mediated Metal-free Atom Transfer Radical Chain Transfer Reaction for the Controlled Hydrogenation of Poly(vinylidene fluoride-chlorotrifluoroethylene)Polymer Chemistry. 2018, 9,221-227 DOI: 10.1039/C7PY01870C.  

59. Shaobo Tan, Yanan Zhang, Zhijing Niu, Zhicheng Zhang* "Copper(0) Mediated Single Electron Transfer Controlled Radical Polymerization toward C-F Bonds on Poly(vinylidene fluoride)" Macromol. Rapid. Comm. 2018,39(4), 1700561. https://doi.org/10.1002/marc.201700561. 

♦ 2017

58. Yingke Zhu, Pingkai Jiang, Zhicheng Zhang*, Xingyi Huang* “Dielectric phenomena and electrical energy storage of poly(vinylidene fluoride) based high-k polymers” Chinese Chemical Letters. 2017, 28(11), 2027-2035, DOI: https://doi.org/10.1016/j.cclet.2017.08.053 

57. Jingjing Liu, Yifei Zhao, Chao Chen, Xiaoyong Wei,  Zhicheng Zhang*. "Study on the Polarization and Relaxation Processes of Ferroelectric Polymer Films Using Sawyer-Tower Circuit with Square Voltage Waveform". J. Phys. Chem. C. 2017. 23, 12531-12539. DOI: 10.1021/acs.jpcc.7b02099.

56. Xiao Wang, Yanan Zhang, Shaobo Tan, Zhicheng Zhang*. "Multiple relaxation in Uniaxially Stretched P(VDF-TrFE) Films after Crosslinking". IEEE Transactions on Dielectrics and Electrical Insulation. 2017. 24(4), 2531-2540.

55. Wanwan Zhang, Jian Wang, Pin Gao, Shaobo Tan, Weiwei Zhu, Zhicheng Zhang*. "Synthesis of Poly(vinylidene fluoride-trifluoroethylene) via a Controlled Silyl Radical Reduction of Poly(vinylidene fluoride-chlorotrifluoroethylene)". J. Mater. Chem. C. 2017, 5. 6433-6441 DOI:10.1039/C7TC01051F

54. Xiaomeng Zhang, Yifei Zhao, Yuhao Wu, Zhicheng Zhang*. " Poly(tetrafluoroethylene-hexafluoropropylene) Films for High-Temperature Pulse Capacitors with Low Energy Loss". Polymer. 2017,114, 311-318, DOI: 10.1016/j.polymer.2017.03.022.

53. Yanan Zhang, Yifei Zhao, Shaobo Tan, Zhicheng Zhang* “Inserting -CH=CH- into P(VDF-TrFE) by C-F Activation Mediated with Cu(0) in a Controlled Atom Transfer Radical Elimination Process” Polymer Chemistry. 2017, 8, 1840-1849. Feb 10, 2017. DOI: 10.1039/c6py02119k.

52. Yunchuan Xie, Yangyang Yu, Yefeng Feng, Wanrong Jiang, and Zhicheng Zhang* “Fabrication of Stretchable Nanocomposites with High Energy Density and Low Loss from Cross-Linked PVDF Filled with Poly(dopamine) Encapsulated BaTiO3”. ACS Appl. Mater. Interfaces. 2017, 9 (3), pp 2995–3005 Publication Date (Web): January 9, 2017  DOI: 10.1021/acsami.6b14166

51. Yefeng Feng, Yuhao Wu, Yunchuan Xie, Xiaoyong Wei, Zhicheng Zhang* “Tunable permittivity in polymer composites filled with Si-based semiconductors by regulating induced polarization”, Materials Science in Semiconductor Processing. 2017, 61, 63-70. April 2017, Pages 63–70. http://dx.doi.org/10.1016/j.mssp.2016.12.029

♦ 2016

50. Pin Gao*, Wanwan Zhang, Zhicheng Zhang. Copper-Catalyzed Oxidative ipso-Annulation of Activated Alkynes with Silanes: An Approach to 3-Silyl Azaspiro[4,5]trienones”. Org. Lett. 2016,18, 5820-5823.  

49. Bei Miao, Jingjing Liu, Xiao Zhang, Junyong Lu, Shaobo Tan, Zhicheng Zhang*. “Ferroelectric relaxation dependence of poly(vinylidene fluoride-co-trifluoroethylene) on frequency and temperature after grafting with poly(methyl methacrylate)” RSC Adv. 2016,6, 84426-84438.  

48.  Honghong Gong, Xiaomeng Zhang, Yanan Zhang, Aqun Zheng, Shaobo Tan, Zhicheng Zhang* “Chemical composition characterization of poly(vinylidene fluoride-chlorotrifluoroethylene)-based copolymers with F–H decoupled 1H NMR”. RSC Advances. 2016, 6, 75880-75889.

47.Feng, Yefeng; Miao, Bei; Gong, Honghong; Xie, Yunchuan; Wei, Xiaoyong; Zhang, Zhicheng* “High Dielectric and Mechanical Properties Achieved in Crosslinked PVDF/α-SiC Nanocomposites with Elevated Compatibility and Induced Polarization at Interface” ACS Applied Materials & Interfaces. 2016, 8(29), 19054-19065. DOI10.1021/acsami.6b04776  

 46.Zuochen Wang, Jingjing Liu, Honghong Gong, Xiao Zhang, Junyong Lu*, Zhicheng Zhang* “Synthesis of Poly(methyl methacrylate-methallyl alcohol) via Controllable Partial Hydrogenation of Poly(methyl methacrylate) towards High Pulse Energy Storage Capacitors Application”. RSC Advances. 2016, 6, 34855-34865.

45. Jian Wang, Zhong Li, Yuan Yan, Xiao Wang, Yunchuan Xie, Zhicheng Zhang*. “Improving Ferro- and Piezo- electric Properties of Hydrogenised Poly(vinylidene fluoride-trifluoroethylene) Films by Annealing at Elevated Temperature” Chinese Journal of Polymer Science. 2016534, 649-658.

44. Yefeng Feng, Honghong Gong, Yunchuan Xie, Xiaoyong Wei*, Zhicheng Zhang*. “Significantly elevated dielectric permittivity of Si-based semiconductor/polymer 2-2 composites induced by high polarity polymers”. Journal of Physics D: Applied. Physics. 2016, 49, 075503. doi:10.1088/0022-3727/49/7 /075503

43. Honghong Gong,Bei Miao,Xiao Zhang, Junyong Lu* and Zhicheng Zhang* "High-field Anti-ferroelectric-like Behavior in Uniaxially Stretched Poly(vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene) -grafted-poly(methyl methacrylate) Films with High Energy Density." RSC Advances. 2016, 6, 1589 - 1599.

♦ 2015

42. Zhong Li, Jian Wang, Xiao Wang, Qinghao Yang, Zhicheng Zhang*. "Ferro- and piezo-electric properties of a poly(vinyl fluoride) film with high ferro- to para-electric phase transition temperature." RSC Advances. 2015, 5, 80950-80955.

41. Yefeng Feng, Honghong Gong, Yunchun Xie, Xiaoyong Wei, Lanjun Yang, Zhicheng Zhang*. "Strong induced polarity between Poly(vinylidene fluoride-co-chlorotrifluoroethylene) and α-SiC and its influence on dielectric permittivity and loss of their composites". Journal of Applied Physics. 2015, 117, 094104.

40. Honghong Gong, Junjie Li, Daming Di, Na Li, Zhicheng Zhang*. "Influence of less initiator on the living performance of atom transfer radical polymerization and the structure of the synthesized grafted copolymer". RSC Advances. 2015, 5, 19117-19127.

♦ 2014

39. Xin Hu, Shaobo Tan, Guoxin Gao, Yunchuan Xie, Qinzhuo Wang, Na Li,  Zhicheng Zhang*. "Synthesis of Unsaturation Containing P(VDF-co-TrFE-co-CTFE) from (VDF-co-CTFE) in One-Pot Catalyzed with Cu(0)-Based Single Electron ransfer Living Radical Polymerization System".  Journal of Polymer Science Part A: Polymer Chemistry. 2014, 2, 3429-34401.

38. Junjie Li, Honghong Gong, Qi Yang, Yunchuan Xie, Lanjun Yang, Zhicheng Zhang*. "Linear-like dielectric behavior and low energy loss achieved in poly(ethyl methacrylate) modified poly(vinylidene-co-trifluoroethylene) ". Applied Physics Letters. 2014, 104, 263901.

37. Weimin Xia, Qingping Zhang, Xiao Wang, Zhicheng Zhang*. "Electrical Energy Discharging Performance of Poly(vinylidene fluoride-co-trifluoroethylene) by Tuning Its Ferroelectric Relaxation with Polymethyl Methacrylate". Journal of Applied Polymer Science. 2014, 131(7): 40114.

36. Jing Chen, Shaobo Tan, Guoxin Gao, Huayi Li, Zhicheng Zhang* “Synthesis and Characterization of Thermally Self-curable Fluoropolymer Triggered by TEMPO in One-pot for High Performance Rubber Application” Polymer Chemistry. 2014,5, 2130-2141.

♦ 2013

35. Fei Wen, Zhuo Xu, Weimin Xia, Hongjun Ye, Xiaoyong Wei, Zhicheng Zhang " High-Energy-Density Poly(styrene-co-acrylonitrile) Thin Films" Journal of Electronic Materials. 2013, 42, 3489-3493.

34. Fei Wen, Zhuo Xu, Weimin Xia, Xiaoyong Wei, Zhicheng Zhang* “High dielectric permittivity and low dielectric loss nanocomposites based on poly(VDF-TrFE-CTFE) and graphene nanosheets” Journal of Advanced Dielectrics. 2013, 3(2): 1350010.

33. Fei Wen, Zhuo Xu, Shaobo Tan, Weimin Xia, Xiaoyong Wei, Zhicheng Zhang*. "Chemical Bonding Induced Low Dielectric Loss and Low Conductivity in High-K poly (vinylidene fluoride trifluorethylene/Graphene Nanosheets Nanocomposites" ACS Applied Materials & Interfaces. 2013, 5(19), 9411-9420.

32.Shaobo Tan, Xin Hu, Shujiang Ding, Zhicheng Zhang*, Huayi Li, Lanjun Yang “Significantly improving dielectric and energy storage properties via uniaxially strething crosslinked P(VDF-co-TrFE) films”. Journal of Materials Chemistry A. 2013, 1 (35), 10353 - 10361.

31.Xin Hu, Junjie Li, Huayi Li, Zhicheng Zhang*. “Cu(0)/2,6-bis(imino)pyridines catalyzed SET-LRP of MMA initiated with P(VDF-co-CTFE)”. Journal of Polymer Science Part A: Polymer Chemistry. 2013, 51(20), 4378-4388. 

30. Weimin Xia, Zhuo Xu*, Zhicheng Zhang*, Huayi Li “Dielectric, piezoelectric and ferroelectric properties of a poly (vinylidene fluoride-co-trifluoroethylene) synthesized via a hydrogenation process”. Polymer. 2013, 54, 440-446.

29. Junjie Li, Xin Hu, Guoxin Gao, Shujiang Ding, Huayi Li, Lanjun Yang, Zhicheng Zhang* “Tuning Phase Transition and Ferroelectric Properties of Poly(vinylidene fluoride-co-trifluoroethylene) via Grafting with Desired Poly(methacrylic ester)s as Side Chains”. Journal of Materials Chemistry C. 2013,1,1111-1121.

28. Fei Wen, Zhuo Xu, Weimin Xia, Xiaoyong Wei, Zhicheng Zhang*. “High energy density nanocomposites based on poly (vinylidene fluoride-chlorotrifluoroethylene) and barium titanate”. Polymer Engineering and Science. 2013, 53(4), 897-904.

27. Qiuping Zhang, Weimin Xia, Zhigang Zhu, Zhicheng Zhang*.“Crystal Phase of Poly(vinylidene fluoride-co-trifluoroethylene) Synthesized via Hydrogenation of Poly(vinylidene fluoride-co- chlorotrifluoroethylene)”. Journal of Applied Polymer Science. 2013,127(4), 3002-3008.

♦ 2012

26. Shaobo Tan, Junjie Li, Guoxin Gao, Huayi Li, Zhicheng Zhang*. “Synthesis of fluoropolymer containing tunable unsaturation by a controlled dehydrochlorination of P(VDF-co-CTFE) and its curing for high performance rubber applications”. Journal of Materials Chemistry. 2012, 22, 18496-18505.

25. Junjie Li, Shaobo Tan, Shujiang Ding, Huayi Li, Lanjun Yang, Zhicheng Zhang* “High-field antiferroelectric behaviour and minimized energy loss in poly(vinylidene-co-trifluoroethylene)-graftpoly(ethyl methacrylate) for energy storage application” Journal of Materials Chemistry. 2012, 22(44), 23468-23476.

24. Xin Hu, Junjie Li, Huayi Li, Zhicheng Zhang*. “Synthesis and characterization of poly(vinylidene fluoride-co-chlorotrifluoroethylene)-grafted-poly(acrylonitrile) via single electron transfer-living radical polymerization process”. Journal of Polymer Science Part A: Polymer Chemistry. 2012, 50(15), 3126-3134.

23. Weimin Xia, Zhuo Xu, Qiuping Zhang, Zhicheng Zhang*. Yuanqing Chen “Dependence of Dielectric, Ferroelectric, and Piezoelectric Properties on    Crystalline Properties of P(VDF-co-TrFE) Copolymers”. Journal of Polymer Science Part B: Polymer Physics. 2012, 50, 1271-1276.

22. Weimin Xia, Zhuo Xu, Fei Wen, Zhicheng Zhang*. “Electrical energy density and dielectric properties of poly(vinylidene fluoride-chlorotrifluoroethylene)/BaSrTiO3 nanocomposites”. Ceramics International. 2012, 38,1071-1075.

♦ 2011

21. Shaobo Tan, Erqiang Liu, Qiuping Zhang, Zhicheng Zhang*. “Controlled Hydrogenation of P(VDF-co-CTFE) to Prepare P(VDF-co-TrFE-co-CTFE) in the Presence of CuX(X=Cl, Br) Complexes”. Chemical Communications. 2011, 47(15), 4544–4546.

20. Shaobo Tan, Junjie Li, Zhicheng Zhang*.“Study of Chain Transfer Reaction in the Initiation Stage of Atom Transfer Radical Polymerization”. Macromolecules. 2011, 44, 7911-7916.

19. Junjie Li, Qingjie Meng, Wenjing Li, Zhicheng Zhang*. “Influence of Crystalline Properties on the Dielectric and Energy Storage Properties of Poly(vinylidene fluoride)”. Journal of Applied Polymer Science. 2011, 122(3), 1659-1668.

♦ 2010

18. Weimin Xia, Fei Wen, Zhuo Xu, Wenjing Li, Zhicheng Zhang*. “Crystalline Properties Dependence of Dielectric and Energy Storage Properties of Poly (vinylidene fluoride-chlorotrifluoroethylene)”. Applied Physics Letters. 2010, 97, 222905.

17. Wenjing Li, Qingjie Meng, Yuansuo Zheng, Zhicheng Zhang*. Weimin Xia, Zhuo Xu. “Energy Storage Properties of Poly(vinylidene fluoride)”. Applied Physics Letters. 2010, 96, 192905.

16. Qingjie Meng, Zhicheng Zhang*, T. C. Mike Chung. “Energy storage study of ferroelectric poly(vinylidene fluoride-trifluoroethylene-chlorotrifluoro ethylene) terpolymers”. Polymer. 2009, 50, 707-715.

15. Qingjie Meng, Wenjing Li, Zhicheng Zhang*. “Effect of Poly(methylmethacrylate) (PMMA) Addition on Dielectric and Energy Storage Properties of Poly(vinylidene fluoride)(PVDF)”. Journal of Applied Polymer Science. 2010, 116(5), 2674.

14. Shaobo Tan, Qinghao Yang, Zhicheng Zhang*. “Synthesis and Characterization of P(VDF-TrFE-CTFE)-g-SPS”. Acta Polymerica Sinica. 2010,11,1269-1275.

13. Erqiang Liu, Zhicheng Zhang*. “A New Method Preparing VDF/CTFE/TrFE Terpolymer by Reductive Dechlorination of VDF/CTFE Copolymer”. Acta Polymerica Sinica. 2010, 8, 1087-1093.

♦ 2009

12. Zhicheng Zhang, T. C. Mike Chung. “The structure-Property relationship of PVDF-based polymers with energy storage and loss under applied electric fields”. Macromolecules. 2007, 40, 9391-9397.

11. Zhicheng Zhang, E. Chalkova, M. Fedkin, C. M. Wang, S. N. Lvov, S. Komaneni, T. C. Mike Chung. “Synthesis and Characterization of Poly(vinylidene fluoride)-g-sulfonated Polystyrene Graft Copolymers for Proton Exchange Membrane”. Macromolecules. 2008, 41, 9130-9139.

10. Zhicheng Zhang, Zhiming Wang, T. C. Mike Chung. “Synthesis of Chain End Functionalized Fluoropolymers by Functional Borane Initiators and Application in the Exfoliated Fluoropolymer/Clay Nanocomposites”. Macromolecules. 2007, 40, 5235-5240.

09. Zhicheng Zhang, T.C. Mike Chung. “Study of Fluoropolymers for High Pulsed Capacitor with High Energy Density and Low Energy Loss”. Macromolecules. 2007, 40, 783-785.

08. Zhicheng Zhang, T.C. Mike Chung. “Reaction Mechanism of Borane/Oxygen Radical Initiators during the Polymerization of Fluoromonomers”. Macromolecules. 2006, 39(16), 5187-5189.

07. Zhicheng Zhang, Zhanxia Lu, Shangtao Chen, Huayi Li, Xiaofan Zhang, Yingying Lu, Youliang Hu. “Synthesis of branched polyethylene from ethylene stock by an interference-free tandem catalysis of TiCl4/MgCl2 and iron catalyst”. Journal of Molecular Catalysis A: Chemical. 2005, 236(1-2), 87-93.

06. Zhicheng Zhang, Junfeng Zou, Nannan Cui, Yucai Ke,, Youliang Hu “Ethylene Oligomerization Catalyzed by a Novel Iron Complex Containing Fluoro and Methyl Substituents”. Journal of Molecular Catalysis A: Chemical. 2004, 219(2), 249-254.

05. Zhicheng Zhang, Shangtao Chen, Xiaofan Zhang, Huayi Li, Yucai Ke, Yingying Lu, Youliang Hu. “A series of novel 2,6-bis(imino)pyridyl iron catalysts: synthesis, characterization and ethylene oligomerization”. Journal of Molecular Catalysis A: Chemical. 2005, 230(1), 1-8.

04. Zhicheng Zhang, Nannan Cui, Yingying Lu, Yucai Ke, Youliang Hu “Preparation of LLDPE by in situ Copolymerization of Ethylene with a New Iron Oligomerization Catalyst and rac-Et(Ind)2ZrCl2”. Journal of Polymer Science A: Polymer Chemistry. 2005,43, 984-993.

03. Zhicheng Zhang, Ruyi Wang, Yucai Ke, Yuansuo Zheng, Cunyue Guo, Nannan Cui, Youliang Hu. “A metalloncene catalyst supported on MMT used in in situ polymerization to prepare LLDPE”. Acta Polymerica Sinica. 2004, (5), 713-718.

02. Zhang Zhicheng, Ke Yucai, Lu Yingying, Cui Nannan, Hu Youliang “Synthesis of a novel bis(imino)pyridyl iron complexes and study on oligomerization of ethylene”. Acta Polymerica Sinica. 2005, (2),191-196.

01. Zhicheng Zhang, Cunyue Guo, Nannan Cui, Yucai Ke, Youliang Hu. “Preparation of LLDPE by in situ copolymerization of ethylene with Zr supported on MMT/Fe/MAO catalyst system”. Journal of Applied Polymer Science. 2004, 94(4), 1690-1696.

 

 

专利
名称 申请号 专利类型 申请日期
一种表征电介质极化、铁电相弛豫和漏导的方法 201611022592.2发明 2016.11.21
一种制备聚(偏氟乙烯-三氟乙烯)和聚(偏氟乙烯-三氟氯乙烯-三氟乙烯)的方法) 201611033072.1发明 2016.11.03
由聚(偏氟乙烯-三氟氯乙烯)制备荧光聚合物的方法 ZL 201510430455.1发明 2015.07.21
可交联耐高电压高储能聚偏氟乙烯塑料薄膜的制备方法” 中国发明专利 ZL 201410132737.4发明 2014.10.13
制备聚(偏氟乙烯-三氟乙烯)或聚(偏氟乙烯-三氟氯乙烯-三氟乙烯)的方法 ZL 201210086186.8发明 2014.02.13
高储能密度聚偏氟乙烯基接枝改性聚合物的制备方法 ZL 201310294444.6发明 2013.10.21
头-头连接的氢化P(VDF-TrFE)制备驻极体压电材料的应用和方法 ZL201210408794.6发明 2012.10.04
一种由聚(偏氟乙烯-三氟氯乙烯)制备聚(偏氟乙烯-三氟氯乙烯-三氟乙烯)或聚(偏氟乙烯-三氟乙烯)的方法 200910024186.3发明 2009.05.01
Chain End Functionalized Fluoropolymer Having Good Electrical Properties 0081195A1发明 2008.01.01
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成果推广

 

高性能能量转换器件用新型P(VDF-TrFE)聚合物膜制备

 

一、项目介绍
1. 压电聚合物P(VDF-co-TrFE)研究现状
P(VDF-co-TrFE) 在常温下是一种半结晶型的热塑性所料[Aimi K, Ando S, Avalle P, et al. Polymer, 2004, 45 (7): 2281-2290]1979年,日本学者T. Yagi M. Tatemoto首先报道了P(VDF-co-TrFE)的分子结构[Yagi T, Tatemoto M. Polymer Journal, 1979, 11 (6): 429-436]。值得关注的是,TrFE单元的引入使此二元共聚物出现了类似于βPVDFTc,即聚合物分子有从TTTTTGTG’的变化[Furukawa T, Johnson GE. Applied Physics Letters, 1981, 38 (12): 1027-1029],而且随着TrFE含量的增加,Tc点降低。随后的研究说明,在TrFE摩尔分数在2050 %之间时,未经拉伸的P(VDF-co-TrFE)在室温下也表现为明显的β相特征,在高极化电场下电滞回线变宽,即饱和与剩余极化强度均随极化电场增加。H. Ohigashi 1995年报道了Pr10 μC·cm-2P(VDF-co-TrFE)厚膜,TrFE的摩尔含量为25% [Ohigashi H, Omote K, Gomyo T. Applied Physics Letters, 1995, 66 (24): 3281-3283]。后续的研究表明,此类聚合物经热处理后,其结晶度可以大幅提高,铁电和压电性能也随之改善[Fang F, Yang W, Jia C, et al. Applied Physics Letters, 2008, 92 (22)]1998年,Q. M. Zhang等人通过研究发现高能电子辐照可以打断P(VDF-co-TrFE)晶区中的大尺寸铁电畴,使铁电畴的尺寸缩小至纳米尺度。处理后的聚合物从原来的铁电体转化为铁电弛豫体,电滞回线变细,电致伸缩为4%[Zhang QM, Bharti V, Zhao X. Science, 1998, 280 (5372): 2101-2104]
由于P(VDF-co-TrFE)具有良好的铁电、压电、热释电性能和优异的电能-机械能转换性能,其应用得到了迅速的发展,它已经成为国际压电聚合物领域的热点。2007年,韩国Jong Soon Lee等人报道了P(VDF-co-TrFE)薄膜在数据存储方面的应用,他们利用C-F健与C-H键形成的偶极距在电场作用下的翻转形成的“±Pr模拟数据记录中的01”[Jong Soon L, Anand Prabu A, You Min C, et al. Advanced Polymers for Emerging Technologies, 2007: 13-20]。在性能表述中测试了厚度为200nm铁电聚合物的剩余极化强度和矫顽电场,该项研究中电畴类似于磁记录中的磁畴。2007年,Cheng Chao等人报道了P(VDF-co-TrFE)在压电微机械超声换能器中的应用,该聚合物的厚度方向压电常数d33=-20 pC/N,并完成了器件的制作[Chen C, Tin-Yan L, Kin-Wing K, et al. Proceedings of the 15th IEEE International Symposium on Applications of Ferroelectrics ISAF 2006, 2007: 120-123]P(VDF-co-TrFE)在压电和电致伸缩性能方面应用也很广泛,2002年,美国宾州州立大学的Q. M. Zhang教授就连续报到了其在激励器中的应用,该类聚合物在厚度方向上的电致伸缩系数S33高达-5%[Xu TB, Cheng ZY, Zhang QM. Applied Physics Letters, 2002, 80 (6): 1082-1084]
在我国,早在上世纪70年代,先后有中科院上海有机所、锦州塑料八厂、清华大学( 七五国家重点科技攻关项目)、哈尔滨船舶工程学院、电子部三所、中科院物理研究所、武汉大学等单位参与研制纯PVDF压电器件。P(VDF-co-TrFE)聚合物压电材料主要用于机械能-电能转换,在军事上利用压电聚合物的特点,研制运用其它现行技术难以实现的、而且具有特殊电声功能的器件,如抗噪声电话、宽带超声信号发射系统等。如用于水下探测的大面积传感器阵列和监视系统等,随后应用领域逐渐拓展到地球物理探测、声波测试设备等方面。也可以生产电声器件如麦克风、立体声耳机和高频扬声器。压电聚合物换能器还可应用于生物医学传感器领域,尤其是超声成像中,获得了最为成功的应用、PVDF薄膜优异的柔韧性和成型性,使其易于应用到许多传感器产品中。
然而, 目前我国的树脂由于产品纯度和稳定性等原因不能满足该领域的要求,因此所用到的PVDF树脂原料依赖进口,导致器件应用研究和市场开拓严重落后于发达国家。更为严重的是,目前还没有国内单位开展二元共聚物P(VDF-co-TrFE)的生产和应用。
研究表明,VDF摩尔分数在2050%之间的P(VDF-co-TrFE)具有较大的Pr,经高电场或热极化后,它的d31d33分别可以达到甚至高于25-25 pC/N,优于βPVDF的压电性。而且,和传统的铁电压电材料相比,P(VDF-co-TrFE)具有较高的机电耦合系数(kt)。早在上世纪90年代,美国的Glass A. M就详细比较了P(VDF-co-TrFE)和其他材料介电和压电性能,如表1所示。
1铁电聚合物和传统铁电压电材料性能比较
材料
密度
/kg·m-3
介电常数
εr
压电常数d33
/pC·N-1
热释电系数
/μC·m-2·K-1
机电耦合
系数(kt
PVDF
1.76
12
-20
40
0.16
P(VDF-co-TrFE)
1.9
13-20
-25~-30
30~40
0.20~0.30
Nylon 11尼龙
1.1
4
3
3
-
PZT-5
7.75
1700
374
60~500
0.34
BaTiO3
5.7
>2000
191
200
0.21
石英
2.66
4.5
2.31
-
0.09
TGS
1.7
5.0
-
350
-
 
2. P(VDF-co-TrFE)主要应用领域
P(VDF-co-TrFE)压电材料是一种经特殊加工后能将动能转化成电能的材料,可以用来制作换能器、水听器、医用超声成像、扬声器、麦克风、热释电传感器、压力传感器、应变传感器、振动控制、加速度传感器、捕能系统、新型不易失存储器。在国防、环境、农业、工业监测和控制、建筑物自动控制、安全和财产跟踪等领域发挥着独特作用。
与传统的单晶和陶瓷压电材料相比,它具有良好可塑性、较低的弹性模量,可以通过简单的制备工艺做成各种形状,如薄膜、纤维和块体等。P(VDF-co-TrFE)压电膜主要应用于以下领域:
1)水声传感器和换能器
压电聚合物P(VDF-co-TrFE)水声换能器研究初期均瞄准军事应用,如用于水下探测的大面积传感器阵列和监视系统等,随后应用领域逐渐拓展到地球物理探测、声波测试设备等方面。美国曾把水声与雷达、原子弹并列为三大发展计划。随着潜艇技术的发展,潜艇噪声越来越小,用被动拖曳线阵列声纳探测目标越来越困难。为此,各国海军又把目标投向了主动式探测声纳,开始研制低频主动拖曳线阵列声纳。经过高能射线辐照的P(VDF-co-TrFE)聚合物材料的声阻抗与水数量级相同,使得制备的水听器可以放置在被测声场中,感知声场内的声压,且不致由于其自身存在使被测声场受到扰动。因此是非常理想的主动式声纳传感器材料,目前我国船舶总公司这方面的需求非常迫切。
2)超声传感器和换能器
机器人安装接近觉传感器主要目的有以下三个:其一,在接触对象物体之前,获得必要的信息,为下一步运动做好准备工作;其二,探测机器人手和足的运动空间中有无障碍物。如发现有障碍,则及时采取一定措施,避免发生碰撞,其三,为获取对象物体表面形状的大致信息。超声波因其波长较短、绕射小并定向传播,利用P(VDF-co-TrFE)聚合物制造的超声传感器,使得机器人能够灵活地探测周围物体的存在与距离,该领域蕴藏着巨大的市场潜力。
3)医疗传感器和换能器
PVDF及其共聚物与压电陶瓷相比,其声阻抗(4MRayls)与人体组织(1. 5MRay ls)相当,在超声成像方面具有明显的优势。具有宽频响应、强度和稳定性良好的优点,在超声成像中有助于实现短脉冲响应,提高轴向成像分辨率。利用延时频谱方法可使聚合物传感器的信噪比在140MHz之间不低于6075 dB。压电聚合物在生物医学领域的应用可以分为探头、超声源和成像系统三类。非介入聚合物探头心肺检测系统可以重复可靠地检测心肺功能。PVDF 薄膜较高的机械损耗使得PVDF超声发射源在较宽频率范围内具有比较平坦的发射电压响应,使其在宽带超声频率绝对校准应用中具有优异特性。其超声发射源可以发射频率超过30MH z的超声冲击波,在非介入肾结石超声破碎和超声应用中具有良好前景。由其拍摄的甲状腺超声图像大大优于压电陶瓷传感器的结果。采用P(VDF-co-TrFE)共聚物,可以进一步增强聚合物的压电效用,由工作频率为7. 5MH zP(VDF-co-TrFE)传感器获得的乳房超声图像表明,由于采用共聚物,图像质量获得了显著提高。
3)驱动器
压电/电致伸缩驱动器已成功地应用在精密定位、精密加工、智能结构、生物工程、航空航天、电子通讯、汽车工业、机器人关节、医疗器械等众多技术领域,并已经形成一个巨大的产业。电子束辐照的P(VDF-co-TrFE)含氟共聚物具备驰豫铁电体特征,使该材料具备了产生大伸缩应变的能力,最大应变量可超过4%,大大超出传统压电陶瓷材料0. 2% 的应变水平,这一优异特性赋予了该材料在微驱动领域的应用潜力。医疗上的应用主要是人工器官的驱动。例如人工肺(氧合器)、人工心脏(血泵)、人工肾(血液透析器)以及定向给药等,市场前景非常广阔。
二、本项目研究思路
由于目前市场上关键原材料三氟乙烯(TrFE)紧缺,价格奇高,导致PVDF-TrFE)除军工部分产品外,难以在民用行业生存。同时,PVDF压电聚合物薄膜近年来也暴露出越来越多的问题,包括:膜的成功率极低,导致大量原材料被浪费,难以获得大面积或者厚度为1mm以上膜,也使得其价格很高;其次,用户反馈信息表明PVDF压电膜的稳定性较差,压电信号随使用时间的延长出现明显的削弱,主要是由于拉伸后的薄膜应力集中松弛导致。
本项目中采用的氢化P(VDF-CTFE)法制备P(VDF-TrFE),不需要采用三氟乙烯作为单体,而是以价格便宜易得的商业P(VDF-CTFE)聚合物为原料,进行催化氢化还原的办法,将其中的Cl原子替换为H原子,从而得到P(VDF-TrFE),可以大幅度降低原材料的制作成本,并解决原材料紧缺的问题。其次,课题组反复试验证明,氢化得到的P(VDF-TrFE)性能与直接共聚法得到的P(VDF-TrFE)铁电、压电性能非常接近,完全能够满足现有领域的使用。同时,由于得到的P(VDF-TrFE)在任何情况下成膜都是高纯度的铁电相,因此,无需对膜进行拉伸,熔体流延、吹膜、甚至溶液流延等方法都可以作为大面积成膜的方式,不会出现PVDF压电膜性能稳定性差、信号衰减快的问题。制备的膜可以进行退火获得更高性能,其相变温度为100-110oC,该膜可以长时间在不高于90oC温度下工作,不会出现退极化、应力松弛变形等问题。
 
三、产品性能指标
2 压电膜技术指标
指标     样品
PVDF-TrFE)压电膜
有效面积
≥200×150mm2
膜厚
2030 μm
平整度
≤5%
有效压电常数
d33≥-20pC/N
相对介电常数
1015
使用温度(
-2090
拉伸强度
≥5.7 MPa
电极剥离强度
≥10 kg/cm2
 
四、联系我们:
      张志成,029-82663937 15029553337