POSS/PVDF材料的制备及其力学性能的表征
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摘要
倍半硅氧烷(POSS)作为一种特殊的有机-无机杂化材料,在近几年的研究中备受人们关注。聚偏二氟乙烯(PVDF)是目前实际应用中压电性能最好的含氟塑料。利用两种材料的各自特点,通过改变POSS的有机-无机官能团能将POSS与PVDF结合成复合材料。本文对PVDF材料及POSS/PVDF材料的熔融共混制备方法进行了详细的研究,并表征了材料的力学性能,详细研究了合成条件(温度、转速、时间)对材料力学性能的影响,获得了最佳的实验工艺。
熔融共混法加工过程中的混合温度、转速、时间对材料的成型和性质有着显著的影响,为得到最好的实验工艺。应用正交实验设计法设计出九组科学的实验工艺条件,并按上诉工艺将PVDF材料、质量比为5%和10%的POSS/PVDF材料制成α晶型膜材料,对三种不同配比九组不同工艺制备的薄膜进行力学性能测试。实验结果表明,少量的POSS单体杂化到PVDF材料中,能使材料的拉伸强度有显著的提高。且当混合温度为180°C、转速为140rpw和混合时间为5min时,材料的力学性能最好。
利用低温过拉伸的方法,对三组材料进行了从α晶型到β晶型的转变,通过进行力学实验,对三种不同配比九组不同工艺制备的薄膜进行力学性能测试。结果表明低温过拉伸后的材料呈明显的脆性断裂特征,得出了最佳实验工艺并对多组材料进行了力学上的分析和对比。
Polyhedral oligomeric silsesquioxane (POSS) as a special family of organic-inorganic hybrid material has attracted considerable interest in the last few years. Poly(vinylidene fluoride)(PVDF) is the fluoro-plastics which has the best properties of piezoelectric material in practical applications. These nanoparticles can be tailored to maximize the interactions in prominent merits of them between the POSS compounds and the PVDF polymer by the modification of the organic groups surrounding the inorganic cage. The paper studied the synthesis of methods of melt blending of PVDF and POSS/PVDF particularly. The mechanical properties of materials were characterized and Effect of different synthesis conditions to mechanical property such as temperature, rotation and time were investigated in detail. The optimizations were obtained.
There is significant effect on preparation and mechanical properties of method of melt blending conditions including temperature, rotation and time .Nine kinds of scientific conditions of methods were designed by orthogonal experiment method ,αphase of PVDF and the addition of five and ten weight percent of POSS were prepared . The mechanical properties of films of 9 different technologies of 3 different proportions were investigated.the result show that a small quantity of POSS can increase the modulus of hybrid materials observably.when the condition that the temperture was 180°C,the rotation speed was 140rpw and time was 5min was applied , the hybrid material had the best mechanical property.
The crystal form the hybrid materials had changed fromαtoβphase by using cryopanel tensile method, The mechanical properties of films of 9 different technologies of 3 different proportions were investigated.the result show the samples undergo a typical polymeric brittle fracture feature and the optimize experimental process was obtained. Mechanical of meterials had been analysed and constasted.
熔融共混法加工过程中的混合温度、转速、时间对材料的成型和性质有着显著的影响,为得到最好的实验工艺。应用正交实验设计法设计出九组科学的实验工艺条件,并按上诉工艺将PVDF材料、质量比为5%和10%的POSS/PVDF材料制成α晶型膜材料,对三种不同配比九组不同工艺制备的薄膜进行力学性能测试。实验结果表明,少量的POSS单体杂化到PVDF材料中,能使材料的拉伸强度有显著的提高。且当混合温度为180°C、转速为140rpw和混合时间为5min时,材料的力学性能最好。
利用低温过拉伸的方法,对三组材料进行了从α晶型到β晶型的转变,通过进行力学实验,对三种不同配比九组不同工艺制备的薄膜进行力学性能测试。结果表明低温过拉伸后的材料呈明显的脆性断裂特征,得出了最佳实验工艺并对多组材料进行了力学上的分析和对比。
Polyhedral oligomeric silsesquioxane (POSS) as a special family of organic-inorganic hybrid material has attracted considerable interest in the last few years. Poly(vinylidene fluoride)(PVDF) is the fluoro-plastics which has the best properties of piezoelectric material in practical applications. These nanoparticles can be tailored to maximize the interactions in prominent merits of them between the POSS compounds and the PVDF polymer by the modification of the organic groups surrounding the inorganic cage. The paper studied the synthesis of methods of melt blending of PVDF and POSS/PVDF particularly. The mechanical properties of materials were characterized and Effect of different synthesis conditions to mechanical property such as temperature, rotation and time were investigated in detail. The optimizations were obtained.
There is significant effect on preparation and mechanical properties of method of melt blending conditions including temperature, rotation and time .Nine kinds of scientific conditions of methods were designed by orthogonal experiment method ,αphase of PVDF and the addition of five and ten weight percent of POSS were prepared . The mechanical properties of films of 9 different technologies of 3 different proportions were investigated.the result show that a small quantity of POSS can increase the modulus of hybrid materials observably.when the condition that the temperture was 180°C,the rotation speed was 140rpw and time was 5min was applied , the hybrid material had the best mechanical property.
The crystal form the hybrid materials had changed fromαtoβphase by using cryopanel tensile method, The mechanical properties of films of 9 different technologies of 3 different proportions were investigated.the result show the samples undergo a typical polymeric brittle fracture feature and the optimize experimental process was obtained. Mechanical of meterials had been analysed and constasted.
引文
1. Kawai H. The piezoelectricity of poly(vinylidene fluoride). Journal of Applied Physics, 1969, 8(6):975~979
2. Andrew J Lovinger. Ferroelectric Polymers. Science, 1983, 220(4602): 1115~1121
3. Mohajir Badr-Eddine El and Heymans Nicole. Changes in Structural and Mechanical Behaviour of PVDF with Processing and Thermomechanical Treatments. Polymer, 2001, (42): 5661-5667.
4. Nakanishi H.Jourbal of Polymer Science,Macromolecular Review,1972,10:1537
5. Tazaki M and Wade R,Journal of Applied Polymer Science Okuda K,Yoshida T.Journal of Polymer Science,Part B;Polymer Letters,1967,55:465
6. Tamer S A. Investigation of Multicomponent Sorption in Polymers from Fluid Mixtures at Supercritical Conditions: The Case of the Carbon Dioxide/Vinylidenefluoride/Poly(vinylidenefluoride) System Chemical Engineering Science,2004,59:5139
7. Scheinbeim J, Nakafuku C and Newman B A. High-pressurecrystallization of Poly(vinylidene fluoride) [J]. Appl Phys, 1979, 50(6):4399-4405.
8. Wang J J, Li H H and Liu J C. On theα->βTransition of Carbon-coatedhighly Oriented PVDF Ultrathin Film Induced by Melt Recrystallization [J]. JAm Chem Soc, 2003, 125: 1496-1497.
9. Sakata J and Mochizuki M. Preparation of Organic Thin Films by Anelectrospray Technique. Crystal Forms and their Orientation Inpoly(vinylidene fluoride) Films [J]. Thim Solid Films, 1991, 195: 175-184.
10. Liu Y Y, Yu J Y and Wang X Y. Effects of Drawing Ttemperature on PhaseTransitions in Poly(vinylidene fluoride) Films. Ferroelectrics, 2002, 273:3~8
11.欧阳萌,龚克成,高分子通报。1993,(2):105
12. She K J and Loy D A. A Mechanistic Investigation of Gelation. The Sol-Gel Polymerization of Precursors to Bridged Polysilsesquioxanes. Acc. Chem. Res. 2001, 34(9):707-716
13.卢婷利,梁国,正宫兆。含倍半硅氧烷的杂化聚合物;高分子通报,2004. 1: 15-20
14. Chen W., WangY and Kuo S. Thermal and Dielectric Properties and Curing Kinetics of Nanomaterial Formed From Poss-epoxy and Meta-phenylenediamine. Polymer 45(2004)897-6908
15.张剑桥.八乙烯基多面体低聚硅倍半氧烷及其环氧化物的合成与表征北京化工大学精细化工2007年1月
16.赵春宝.多面体低聚倍半硅氧烷(POSS)杂化材料南京理工大学材料化学实验室材料导报2008年2月第22卷第2期
17.薛裕华.多面体低聚倍半硅氧烷及多面体低聚倍半硅氧烷-聚合物的研究进展浙江大学材料化工学院现代化工2005年7月第25卷
18. Fu B X, Gelfer M Y and Hsiao B S. Polym., 2003,44: 1499~1506.
19. Li G Z, Wang L C and Ni H L. J. Inorg. Organo-met. Polym., 2001, 11: 123~154.
20. Fu B X, Hsiao B S and White H. Polymers. Internatl.,2000, 49: 437~440.
21. Timothy S H, Patrick T M and Hong G J. Mat.Res. Soc. Symp. Proc., 2000, 628: 261~267.
22. Joseph M. Mabry and Timothy S. Haddad.Polymer Nanocomposites Designed with Polyhedral Oligomeric Silsesquioxanses and Plastics (POSS) Air ForceResearch Laboratory RC Incorporated, Air Force Research LaboratoEdwards Air Force Base, CA 93524
23. Ichiro Imae and Yusuke Kawakami.Development of a Novel POSS-based Matertial having Carbazole Moiety School of Materials Science,Japan Advanced Institute of Science and Technology Ishikawa 923-1292,Japan
24. J.E. Mark and Y C. Lee. Hybrid polymer-inorganic nanocomposites Mater Chem,1996, 6(4): 511.
25. J. Jang, J,Bae and D. Kang. J Appli Polym Sci, 2002, 82(8): 2310.
26. Lee J. D. Lichtenhan, Organic–inorganic Nanocomposites From Cubic Silsesquioxane Epoxides: Direct Characterization of Interphase, and Thermomechanical Properties J. Appl. Polym, Sci,1999,73(S0): 1993.
27. Joseph M. Mabry Fluorinated Polyhedral Oligomeric Silsesquioxances Air Force Research Laboratory RC Incorporated, Air Force Research Laboraty
28. Joseph M.,Mabry,Darrell Marchant and Scott Barker ERC,Inc.Fluoropolymer Property Enhancement via Incorporation of Fluorinated Polyhedtal Oligomeric Silsesquioxances(FluoroPOSS), Air Force Research Laboraty Edwards Air Force Base
29. Lee J S, Lichtenhan J D. Polyhedral Oligomeric Silsesquioxane (POSS) Macromolecules, 1998, 31:4970~4974.
30. Franco M,Capaldi, Gregory C. Rutledge, and Mary C.Structure and Dynamics of Blends of Polyhedral Oligomeric Silsesquioxanes and Polyethylene by Atomistic Simulation Boyce Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 Macromolecules,2003,21-56
31. Jeon.H.G, Mather.P.T and Haddad.T.S. Polymers. Polyhedral OligomericSilsesquioxane (POSS) Macromolecules Inter-natl., 2000, 49: 453~457.
32. Li, Guizhi; Wang, Lichang; Ni, Hanli and Pittman, Charles U.Polyhedral Oligomeric Silsesquioxane (POSS) Polymers and Copolymers: A Review. Journal of Inorganic and Organometallic Polymers (2002), Volume Date 2001, 11(3), 123-154 Coden: 4; ISSN: 1053-0495. English
33. S. Brown. Aerospace America ,1999,20(6): 52
34. Haddad,TimothyS,Lichtenhan and JosephD. Hybrid Organic-Inorganic Thermoplastics: Styryl-Based Polyhedral Oligomeric Silsesquioxane Polymers Macromolecules (1996), 29(22), 7302-7304 Coden: Mamox; ISSN: 0024-9297. English
35. Haddad T. S,Choe, E and Lichtenhan, J. D. Hybrid Styryl-based Polyhedral Oligomeric Silsesquioxane (POSS) Polymers,Materials Research Society Symposium Proceedings (1996), 435(Better Ceramics through Chemistry VII: Organic/Inorganic Hybrid Materials), 25-32 CODEN: MRSPDH; ISSN: 0272-9172. English
36. Wang JS, Matyjaszewski K (1995) Am Chem Soc 117:5614
37. Pyun, Jeffrey; Matyjaszewski and Krzyszt.Synthesis of hybrid polymers Using Atom Transfer Radical Polymerization: Homopolymers and Block Copolymers from Polyhedral Oligomeric Silsesquioxane Monomers Macromolecules (2000), 33(1), 217-220
38. Matyjaszewski K, Xia J (2001) Chem Rev 101:2921
39. Patten TE and Matyjaszewski K (1999) Acc Chem Res 32:895
40. Xu, Hongyao,Kuo, Shiao-Wei,Chang and Feng-Chih.Significant Glass Transition Temperature Increase based on Polyhedral Oligomeric Silsesquioxane (POSS) Copolymer through Hydrogen Bonding PolymerBulletin (Berlin, Germany) (2002), 48(6), 469-474Choi J, Tamaki R, Kim SG, Laine RM (2003) Chem Mater 15:3365
41. Jiwon Choi.Organic/Inorganic Hybrid Composites from Cubic Silsesquioxanes Department of Materials Science and Engineering, University of Michigan,Macromolecules,2003,36(15)
42. Tamaki R, Choi J, Laine RM A Polyimide Nanocomposite from Octa(aminophenyl)silsesquioxane, Chem. Materials 15, 793- (2003)
43. Jeon HG, Mather PT, Haddad TS Shape Memory and Nanostructure in Poly(norbornyl-POSS) Copolymers Polymer International(2000) Polym Int 49:453
44. Mather,Patrick T,Jeo Hong G,Romo-Uribe, A,Haddad, Timothy S,Lichtenhan and Joseph D.Mechanical Relaxation and Microstructure of Poly(norbornyl-POSS) Copolymers Macromolecules (1999), 32(4)
45. B.X.Fu,M.Y.Gelfer,B.S.Hsiaoa,et al.Polymer,2003,44:1499
46. Milan Maric .Improving Polymer Blend Dispersions in Mini-Mixers Epartment of Chemical Engineering and Materials Science University of Minnesota Twin Citie Minneapolis, Minnesota 55455
47. K.M.Kim and T inakura.Polymer Bulletin,2001,46:351
48. ReneI. Gonzalez and Shawn H.Phillips U.S. In Situ Oxygen Atom Erosion Study of Polyhedral OligomericSilsesquioxane-Siloxane Copolymer Air Force Research Laboratory, Edwards Air Force Base, California 93524 and Gar B. Hound University of Florida,Gainesville,Florida32611 Journal of Spacecraft and rockers .Vol.37,No. 4,July August2000
49. Laura E.Moody,Darrell Marchant Determination of Mechanical and Surface Properties of Semicrystalline Poss Nanocomposites Air Force ResearchLaboratory,EdwardsAFB,CA93534
50.刘栋,姜胜林,仝金雨,金学淼.拉伸工艺对PVDF薄膜形貌与结构的影响.电子元件与材料.2007年3月第26卷
51.徐任信,陈文.拉伸速率对PVDF薄膜介电压电性能的影响.功能材料2004年第35卷
2. Andrew J Lovinger. Ferroelectric Polymers. Science, 1983, 220(4602): 1115~1121
3. Mohajir Badr-Eddine El and Heymans Nicole. Changes in Structural and Mechanical Behaviour of PVDF with Processing and Thermomechanical Treatments. Polymer, 2001, (42): 5661-5667.
4. Nakanishi H.Jourbal of Polymer Science,Macromolecular Review,1972,10:1537
5. Tazaki M and Wade R,Journal of Applied Polymer Science Okuda K,Yoshida T.Journal of Polymer Science,Part B;Polymer Letters,1967,55:465
6. Tamer S A. Investigation of Multicomponent Sorption in Polymers from Fluid Mixtures at Supercritical Conditions: The Case of the Carbon Dioxide/Vinylidenefluoride/Poly(vinylidenefluoride) System Chemical Engineering Science,2004,59:5139
7. Scheinbeim J, Nakafuku C and Newman B A. High-pressurecrystallization of Poly(vinylidene fluoride) [J]. Appl Phys, 1979, 50(6):4399-4405.
8. Wang J J, Li H H and Liu J C. On theα->βTransition of Carbon-coatedhighly Oriented PVDF Ultrathin Film Induced by Melt Recrystallization [J]. JAm Chem Soc, 2003, 125: 1496-1497.
9. Sakata J and Mochizuki M. Preparation of Organic Thin Films by Anelectrospray Technique. Crystal Forms and their Orientation Inpoly(vinylidene fluoride) Films [J]. Thim Solid Films, 1991, 195: 175-184.
10. Liu Y Y, Yu J Y and Wang X Y. Effects of Drawing Ttemperature on PhaseTransitions in Poly(vinylidene fluoride) Films. Ferroelectrics, 2002, 273:3~8
11.欧阳萌,龚克成,高分子通报。1993,(2):105
12. She K J and Loy D A. A Mechanistic Investigation of Gelation. The Sol-Gel Polymerization of Precursors to Bridged Polysilsesquioxanes. Acc. Chem. Res. 2001, 34(9):707-716
13.卢婷利,梁国,正宫兆。含倍半硅氧烷的杂化聚合物;高分子通报,2004. 1: 15-20
14. Chen W., WangY and Kuo S. Thermal and Dielectric Properties and Curing Kinetics of Nanomaterial Formed From Poss-epoxy and Meta-phenylenediamine. Polymer 45(2004)897-6908
15.张剑桥.八乙烯基多面体低聚硅倍半氧烷及其环氧化物的合成与表征北京化工大学精细化工2007年1月
16.赵春宝.多面体低聚倍半硅氧烷(POSS)杂化材料南京理工大学材料化学实验室材料导报2008年2月第22卷第2期
17.薛裕华.多面体低聚倍半硅氧烷及多面体低聚倍半硅氧烷-聚合物的研究进展浙江大学材料化工学院现代化工2005年7月第25卷
18. Fu B X, Gelfer M Y and Hsiao B S. Polym., 2003,44: 1499~1506.
19. Li G Z, Wang L C and Ni H L. J. Inorg. Organo-met. Polym., 2001, 11: 123~154.
20. Fu B X, Hsiao B S and White H. Polymers. Internatl.,2000, 49: 437~440.
21. Timothy S H, Patrick T M and Hong G J. Mat.Res. Soc. Symp. Proc., 2000, 628: 261~267.
22. Joseph M. Mabry and Timothy S. Haddad.Polymer Nanocomposites Designed with Polyhedral Oligomeric Silsesquioxanses and Plastics (POSS) Air ForceResearch Laboratory RC Incorporated, Air Force Research LaboratoEdwards Air Force Base, CA 93524
23. Ichiro Imae and Yusuke Kawakami.Development of a Novel POSS-based Matertial having Carbazole Moiety School of Materials Science,Japan Advanced Institute of Science and Technology Ishikawa 923-1292,Japan
24. J.E. Mark and Y C. Lee. Hybrid polymer-inorganic nanocomposites Mater Chem,1996, 6(4): 511.
25. J. Jang, J,Bae and D. Kang. J Appli Polym Sci, 2002, 82(8): 2310.
26. Lee J. D. Lichtenhan, Organic–inorganic Nanocomposites From Cubic Silsesquioxane Epoxides: Direct Characterization of Interphase, and Thermomechanical Properties J. Appl. Polym, Sci,1999,73(S0): 1993.
27. Joseph M. Mabry Fluorinated Polyhedral Oligomeric Silsesquioxances Air Force Research Laboratory RC Incorporated, Air Force Research Laboraty
28. Joseph M.,Mabry,Darrell Marchant and Scott Barker ERC,Inc.Fluoropolymer Property Enhancement via Incorporation of Fluorinated Polyhedtal Oligomeric Silsesquioxances(FluoroPOSS), Air Force Research Laboraty Edwards Air Force Base
29. Lee J S, Lichtenhan J D. Polyhedral Oligomeric Silsesquioxane (POSS) Macromolecules, 1998, 31:4970~4974.
30. Franco M,Capaldi, Gregory C. Rutledge, and Mary C.Structure and Dynamics of Blends of Polyhedral Oligomeric Silsesquioxanes and Polyethylene by Atomistic Simulation Boyce Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 Macromolecules,2003,21-56
31. Jeon.H.G, Mather.P.T and Haddad.T.S. Polymers. Polyhedral OligomericSilsesquioxane (POSS) Macromolecules Inter-natl., 2000, 49: 453~457.
32. Li, Guizhi; Wang, Lichang; Ni, Hanli and Pittman, Charles U.Polyhedral Oligomeric Silsesquioxane (POSS) Polymers and Copolymers: A Review. Journal of Inorganic and Organometallic Polymers (2002), Volume Date 2001, 11(3), 123-154 Coden: 4; ISSN: 1053-0495. English
33. S. Brown. Aerospace America ,1999,20(6): 52
34. Haddad,TimothyS,Lichtenhan and JosephD. Hybrid Organic-Inorganic Thermoplastics: Styryl-Based Polyhedral Oligomeric Silsesquioxane Polymers Macromolecules (1996), 29(22), 7302-7304 Coden: Mamox; ISSN: 0024-9297. English
35. Haddad T. S,Choe, E and Lichtenhan, J. D. Hybrid Styryl-based Polyhedral Oligomeric Silsesquioxane (POSS) Polymers,Materials Research Society Symposium Proceedings (1996), 435(Better Ceramics through Chemistry VII: Organic/Inorganic Hybrid Materials), 25-32 CODEN: MRSPDH; ISSN: 0272-9172. English
36. Wang JS, Matyjaszewski K (1995) Am Chem Soc 117:5614
37. Pyun, Jeffrey; Matyjaszewski and Krzyszt.Synthesis of hybrid polymers Using Atom Transfer Radical Polymerization: Homopolymers and Block Copolymers from Polyhedral Oligomeric Silsesquioxane Monomers Macromolecules (2000), 33(1), 217-220
38. Matyjaszewski K, Xia J (2001) Chem Rev 101:2921
39. Patten TE and Matyjaszewski K (1999) Acc Chem Res 32:895
40. Xu, Hongyao,Kuo, Shiao-Wei,Chang and Feng-Chih.Significant Glass Transition Temperature Increase based on Polyhedral Oligomeric Silsesquioxane (POSS) Copolymer through Hydrogen Bonding PolymerBulletin (Berlin, Germany) (2002), 48(6), 469-474Choi J, Tamaki R, Kim SG, Laine RM (2003) Chem Mater 15:3365
41. Jiwon Choi.Organic/Inorganic Hybrid Composites from Cubic Silsesquioxanes Department of Materials Science and Engineering, University of Michigan,Macromolecules,2003,36(15)
42. Tamaki R, Choi J, Laine RM A Polyimide Nanocomposite from Octa(aminophenyl)silsesquioxane, Chem. Materials 15, 793- (2003)
43. Jeon HG, Mather PT, Haddad TS Shape Memory and Nanostructure in Poly(norbornyl-POSS) Copolymers Polymer International(2000) Polym Int 49:453
44. Mather,Patrick T,Jeo Hong G,Romo-Uribe, A,Haddad, Timothy S,Lichtenhan and Joseph D.Mechanical Relaxation and Microstructure of Poly(norbornyl-POSS) Copolymers Macromolecules (1999), 32(4)
45. B.X.Fu,M.Y.Gelfer,B.S.Hsiaoa,et al.Polymer,2003,44:1499
46. Milan Maric .Improving Polymer Blend Dispersions in Mini-Mixers Epartment of Chemical Engineering and Materials Science University of Minnesota Twin Citie Minneapolis, Minnesota 55455
47. K.M.Kim and T inakura.Polymer Bulletin,2001,46:351
48. ReneI. Gonzalez and Shawn H.Phillips U.S. In Situ Oxygen Atom Erosion Study of Polyhedral OligomericSilsesquioxane-Siloxane Copolymer Air Force Research Laboratory, Edwards Air Force Base, California 93524 and Gar B. Hound University of Florida,Gainesville,Florida32611 Journal of Spacecraft and rockers .Vol.37,No. 4,July August2000
49. Laura E.Moody,Darrell Marchant Determination of Mechanical and Surface Properties of Semicrystalline Poss Nanocomposites Air Force ResearchLaboratory,EdwardsAFB,CA93534
50.刘栋,姜胜林,仝金雨,金学淼.拉伸工艺对PVDF薄膜形貌与结构的影响.电子元件与材料.2007年3月第26卷
51.徐任信,陈文.拉伸速率对PVDF薄膜介电压电性能的影响.功能材料2004年第35卷