静电纺丝技术制备光致变色超细纤维与表征
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摘要
在过去的十年中，静电纺丝技术作为一种简单而又快捷地制备一维纳米-亚微米材料的方法获得了迅速的发展，并逐渐成为纳米材料研究领域的热点之一。如何更好地利用这一技术制备出满足科研、生产需要的超细纤维已经对静电纺丝技术的发展提出了更高的要求。
金属双硫腙是一类比较典型的光致变色化合物，在军事伪装、染料工业及重金属盐的监测等方面有着广泛的应用前景。
本文采用静电纺丝技术制备了聚乙烯吡咯烷酮(PVP)超细纤维，研究了实验参数对静电纺丝纤维形貌的影响，结果表明聚合物浓度，外加电场电压对纤维直径粗细及分布均有一定影响。
本文采用静电纺丝技术分别制备了双硫腙汞／聚苯乙烯、双硫腙镉／聚苯乙烯、双硫腙锌／聚苯乙烯超细纤维，并采用SEM、XRD、UV-Vis、ESR、FTIR对其进行了表征。SEM表明，所用溶剂介电常数越大，所制备纤维越粗；XRD表明，纤维为无定型结构；UV-Vis表明，双硫腙汞光致变色效果最好，双硫腙锌光致变色效果较差，双硫腙镉光致变色效果最差；ESR表明，光照下纤维中有电子转移。
As a simple and quick method for preparing nano- or submicrometer fibers, great progress has been made in electrospinning technique in the past decade. Therefore, electrospinning technique has become one of the current studied subjects in the nanomaterials research field. How to better prepare various kinds of ultafine fibers using electrospinning technique to meet the needs of scientific research and production has proposed a higher demand for electrospinning technique.
Dithizonate salt is one of the typical photochromic compounds and has widely used in military, dye industry, as well as in heavy metal detections.
PVP ultrafine fibers were prepared via an electrospinning technique, and the effect of operating parameters on morphology and diameter of electrospun fibers of PVP had been investigated. It was showed that both concentration and applied potential had certain effect on the diameter and distribution of PVP ultrafine fibers.
Hg(HDz)2/PS, Cd(HDz)2/PS and Zn(HDz)2/PS ultrafine fibers were prepared by electrospinning technique separately, and characterized by SEM, FTIR, XRD, UV-Vis and ESR. The SEM analysis showed that the higher the dielectric constant, the bigger the diameter; XRD results showed that the non-woven mat was nearly amorphousn in structure; UV-Vis measurements indicated that Hg(HDz)2/PS showed the best photochromism of the three, and the Zn(HDz)2/PS was better than Cd(HDz)2/PS. One-electron transition was confirmed by ESR.
金属双硫腙是一类比较典型的光致变色化合物，在军事伪装、染料工业及重金属盐的监测等方面有着广泛的应用前景。
本文采用静电纺丝技术制备了聚乙烯吡咯烷酮(PVP)超细纤维，研究了实验参数对静电纺丝纤维形貌的影响，结果表明聚合物浓度，外加电场电压对纤维直径粗细及分布均有一定影响。
本文采用静电纺丝技术分别制备了双硫腙汞／聚苯乙烯、双硫腙镉／聚苯乙烯、双硫腙锌／聚苯乙烯超细纤维，并采用SEM、XRD、UV-Vis、ESR、FTIR对其进行了表征。SEM表明，所用溶剂介电常数越大，所制备纤维越粗；XRD表明，纤维为无定型结构；UV-Vis表明，双硫腙汞光致变色效果最好，双硫腙锌光致变色效果较差，双硫腙镉光致变色效果最差；ESR表明，光照下纤维中有电子转移。
As a simple and quick method for preparing nano- or submicrometer fibers, great progress has been made in electrospinning technique in the past decade. Therefore, electrospinning technique has become one of the current studied subjects in the nanomaterials research field. How to better prepare various kinds of ultafine fibers using electrospinning technique to meet the needs of scientific research and production has proposed a higher demand for electrospinning technique.
Dithizonate salt is one of the typical photochromic compounds and has widely used in military, dye industry, as well as in heavy metal detections.
PVP ultrafine fibers were prepared via an electrospinning technique, and the effect of operating parameters on morphology and diameter of electrospun fibers of PVP had been investigated. It was showed that both concentration and applied potential had certain effect on the diameter and distribution of PVP ultrafine fibers.
Hg(HDz)2/PS, Cd(HDz)2/PS and Zn(HDz)2/PS ultrafine fibers were prepared by electrospinning technique separately, and characterized by SEM, FTIR, XRD, UV-Vis and ESR. The SEM analysis showed that the higher the dielectric constant, the bigger the diameter; XRD results showed that the non-woven mat was nearly amorphousn in structure; UV-Vis measurements indicated that Hg(HDz)2/PS showed the best photochromism of the three, and the Zn(HDz)2/PS was better than Cd(HDz)2/PS. One-electron transition was confirmed by ESR.
引文
[1] 高凤悔．杂多酸／高分子纳米结构材料：[硕士学位论文]．长春：东北师范大学，2005
[2] 董晓东．纳米MoO_3／PMMA杂化材料的制备与表征：[硕士学位论文]．长春：长春理工大学，2003
[3] 倪永红，葛学武，徐相凌．陈家福等，纳米材料制备研究的若干新进展．无机材料学报，2000．15(1)：9-15
[4] 安林红，王跃．纳米纤维技术的开发及应用．当代石油石化．2002，2002，10(2)：41-5
[5] Huang Zhengming, Zhang YZ, Kotaki M, Ramakrishna. Composites Science and Technology, 2003,63:2223-53
[6] Li Dan, Xia Younan. Advanced Materials, 2004, 16(14):1152-70
[7] Frenot Audrey, Chronakis Ioannis S. Current Opinion in Colloid and Interface Science, 2003, 8: 64-75
[8] Hu J, Odom T W, Lieber C M. Acc. Chem. Res., 1999, 32:435-445
[9] Ma P X, Zhang R. J Biomed Mat Res, 1999, 46:60-72
[10] Liu G J, Ding J F, Qiao L J, Guo A, Dymov B P, Gleeson J T, et al. Chem-A European J, 1999, 5: 2740-2749
[11] Fong H, Reneker D H. In: Salem D R, editor. Munich: Hanser, 2001. 225-46
[12] Reneker D H, Chun I. Nanotechnology, 1996, 7:216-223
[13] Koski A, Yim K, Shivkumar S. Materials Letters, 2004,58:493-497
[14] Reneker D H, Yarin A L, Fong H, Koombhongse S. J. Appl. Phys., 2000, 87:4531-4547
[15] Yarin A L, Koombhongse S, Reneker D H. J. Appl. Phys., 2001, 90:4836-4846
[16] Shin Y M, Hohman M M, Brenner M P, Rutledge G C. Polymer, 2001, 42:9955-9967
[17] Hohman M M, Shin M, Rutledge G C, M. P. Brenner. Phys. Fluidics., 2001, 13:2201-2220
[18] Fridrish S V, Yu J H, Brenner M P, Rutledge G C. Phys. Fluidics., 2002, 14:3912-3917
[19] Feng J J. Phys. Fluidics, 2002, 14:3912-3926
[20] Theron A, Zussman E, Yarin A L. Nanotechnology, 2001, 12:384-390
[21] Bornat A. Production of electro-statically spun products. US Patent 4 689 186,1987
[22] Li D. Wang Y, Xia Y. Nano Lett., 2003, 3:1167-1171
[23] Ryu Y J, Kim H Y, Lee K H, Park H C, Lee D R. Eur. Polym. J., 2003, 39:1883-1889
[24] Kim S J, Shin K M, Kim S I. Scripta Materialia., 2004,5:31-35
[25] Zeng .J, Xu X, Chen X, Liang Q, Bian X, Yang L, Jing X. Journal of Controlled Release, 2003, 92:227-232
[26] Buchko C J, Chen L C, Shen Y, Martin D C. Polym., 1999, 40:7397-7407
[27] Madhugiri S, Zhou W, Ferraris John P, Balkus Jr Kenneth J. Microporous and Mesoporous Material, 2003, 63:75-84
[28] Liu H, Kameoka J, Czaplewski D A. Craighead H G. Nano Lett., 2004, 4(4): 671-675[29] Ding B, Kim J, Miyazak Y, Shiratori S. Sensor and Actuators B, 2004, 101:373-380
[30] Norris I D, Shaker Manal M, Ko Frank K, Macdiarmid A G. Synthetic Metals, 2000, 114:109-114
[31] 唐克光．光致变色化合物的用途和性能．浙江化工，2002，33(2)：5-9
[32] 杨武利，胡建华，府寿宽．光致变色高分子体系．高分子通报，1998，4：65-73
[33] 于明昕．周啸．金属双硫腙汞在聚合物中的光致变色行为．功能材料．2001，32(2)：203-205
[34] Theron S A, Zussman E, Yarin A L. Polymer, 2004, 45:2017-30
[35] Kim S J.Shin K M, Kim S I. Scripta Materialia, 2004, 51: 31-35
[36] Norris I D, Shaker M M, Ko F K, MacDiarmid A G.Synth. Met., 2000, 114:109-114
[37] Wang X, Drew C, Lee S-H, Senecal K J, Kumar J, Samuelson L A. Nano Lett., 2002, 2: 1273-1275
[38] Boland E D, Wnek G E, Simpson D G,.Pawlowski K J, Bowlin G L. J. Macromol. Sci. Pure Appl. Chem., 2001, A38:1231-1243
[39] Larsen G, Velarde-Ortiz R, Minchow K, Barrero A, Loscertales I G. J. Am. Chem. Soc., 2003, 125:1154-1155
[40] Hou H, Reneker D H. Adv. Mater., 2004, 16:69-73
[41] Hou H, Jun Z, Reuning A, Schaper A, Wendorff J H, Greiner A. Macromol., 2002, 35:2429-2431
[42] Seoul C, Kim Y-T, Baek C -K. J. Polym. Sci. Polym. Phys. Ed., 2003, 41:1572-1577
[43] Wang X, Kim Y -G, Drew C, Ku B -C, Kumar J, Samuelson L A. Nano Lett., 2004, 4:331-334
[44] Pinto N J, Carrion P, Quinones J X. Mater. Sci. Eng. A, 2004, 366:1-5
[45] H.M.N.H. Irving, G. Andrew, E.J. Risdon, J. Chem. Soc., 1949, 54:1949-1952
[46] L.S.Meriwether, E.C. Breitner, C.L. Sloan, J. Am. Chem. Soc., 1965, 87:4441-4442
[47] Won Keun Son, Ji Ho Youk, Taek Seung Lee, Won Ho Park. Poly., 2004, 45:2959-2966
[48] Kasaai MR, Charlet G, Arul J. Food Res Int 2000, 33:63-65
[49] Dong Hong, Nyame Verrad, Macdiarmid Alan G, Jones Wayne E. JR.Journal of Polymer Science: Part B: Polymer Physics, 2004, 42:3934-42
[50] Jae Shin Choi, Sung Won Lee, Lim Jeong, Su-Hyun Bae, Bum Chan Min, Ji Ho Youk, Won Ho Park. International Journal of Biological Macromolecules, 2004. 34:249-56
[51] N. Sertova, I. Petkov, J. M. Nunzi. Journal of Photochemistry and Photobiology A: Chemistry, 2000, 134, 163-168
[52] Deitzel JM, Kleinmeyer J, Harris D, Beck Tan NC. The effect of processing variable on the morphology of electrospun nanofibers and textiles. Polymer. 2001,42:261-72
[53] Koombhongse S, Liu WX, Reneker DH. Flat polymer ribbons and other shapes by electrospinning. J Polymer Sci: Part B: Polymer Physics, 2001, 39:2598-606
[54] A. Koski, K. Yim, S. Shivkumar. Effect of molecular weight on fibrous PVA produced by electrospinning. Mateials Letters, 2004, 58:493-97[55] 吴世康，沈燕清．双硫腙汞络合物在高分膜内的光色互变研究．功能高分子学报，1990，3：3-7
[56] Meriwether L S, Breither E C, Sloan C L et al. Kinetic and infrared study of photochromism of metal dithizonates. J Am Chem Soc., 1965, 87:4448
[57] N. Grassie, H.W. Melville. Proc. Roy. Soc. Lond., A1949, 199: 1.
[58] J.C. Benvington, H.W. Melville, R.P. Taylor, J. Polym. Sci., 1954, 14: 1696.
[59] I.C. McNeill, Eur. Polym. J., 1967, 3: 409.
[60] I.C. McNeill, Eur. Polym. J., 1970, 6: 373.
[61] M.A. Rauf, I.C. McNeill, Polym. Deg. Stab., 1993, 41 (1): 117.
[62] M.A. Rauf, I.C. McNeill, Polym. Deg. Stab., 1993, 40 (2): 263.
[63] M. Abdel-Aziz, S. Gwaily, Polym. Deg. Stab., 1997, 55: 269.
[64] K. El-Salmawi, M. Abu-Zeid, A. EI-Naggar, M. Mamdouh, J. Appl. Polym. Sci., 1999, 72: 509.
[65] M. Walickis, J. Kroh, Acad. Polon. Sci. Ser. Sci. Chim., 1965, 13: 635.
[66] M. Oelschager, E. Schwerz, Anal. Chem., 1972, 258: 203.
[67] W.G Hanna, A.M. Mekewi. E.H. EI-Mosallamy, J. Appl. Polym. Sci., 2001,82: 562.
[68] R.M. Smith, A.E. Martell, Critical Stability Constants, vol. 1-6, Pelsun, New York, 1989.
[69] J.L. Koenig, Spectroscopy of Polymers, Am. Chem. Soc., Washington, DC, 1992.
[70] El-Said H., Ei-Mohamed A.Mekewi. Materials Chemistry and Physics, 2003, 80:319-324
[2] 董晓东．纳米MoO_3／PMMA杂化材料的制备与表征：[硕士学位论文]．长春：长春理工大学，2003
[3] 倪永红，葛学武，徐相凌．陈家福等，纳米材料制备研究的若干新进展．无机材料学报，2000．15(1)：9-15
[4] 安林红，王跃．纳米纤维技术的开发及应用．当代石油石化．2002，2002，10(2)：41-5
[5] Huang Zhengming, Zhang YZ, Kotaki M, Ramakrishna. Composites Science and Technology, 2003,63:2223-53
[6] Li Dan, Xia Younan. Advanced Materials, 2004, 16(14):1152-70
[7] Frenot Audrey, Chronakis Ioannis S. Current Opinion in Colloid and Interface Science, 2003, 8: 64-75
[8] Hu J, Odom T W, Lieber C M. Acc. Chem. Res., 1999, 32:435-445
[9] Ma P X, Zhang R. J Biomed Mat Res, 1999, 46:60-72
[10] Liu G J, Ding J F, Qiao L J, Guo A, Dymov B P, Gleeson J T, et al. Chem-A European J, 1999, 5: 2740-2749
[11] Fong H, Reneker D H. In: Salem D R, editor. Munich: Hanser, 2001. 225-46
[12] Reneker D H, Chun I. Nanotechnology, 1996, 7:216-223
[13] Koski A, Yim K, Shivkumar S. Materials Letters, 2004,58:493-497
[14] Reneker D H, Yarin A L, Fong H, Koombhongse S. J. Appl. Phys., 2000, 87:4531-4547
[15] Yarin A L, Koombhongse S, Reneker D H. J. Appl. Phys., 2001, 90:4836-4846
[16] Shin Y M, Hohman M M, Brenner M P, Rutledge G C. Polymer, 2001, 42:9955-9967
[17] Hohman M M, Shin M, Rutledge G C, M. P. Brenner. Phys. Fluidics., 2001, 13:2201-2220
[18] Fridrish S V, Yu J H, Brenner M P, Rutledge G C. Phys. Fluidics., 2002, 14:3912-3917
[19] Feng J J. Phys. Fluidics, 2002, 14:3912-3926
[20] Theron A, Zussman E, Yarin A L. Nanotechnology, 2001, 12:384-390
[21] Bornat A. Production of electro-statically spun products. US Patent 4 689 186,1987
[22] Li D. Wang Y, Xia Y. Nano Lett., 2003, 3:1167-1171
[23] Ryu Y J, Kim H Y, Lee K H, Park H C, Lee D R. Eur. Polym. J., 2003, 39:1883-1889
[24] Kim S J, Shin K M, Kim S I. Scripta Materialia., 2004,5:31-35
[25] Zeng .J, Xu X, Chen X, Liang Q, Bian X, Yang L, Jing X. Journal of Controlled Release, 2003, 92:227-232
[26] Buchko C J, Chen L C, Shen Y, Martin D C. Polym., 1999, 40:7397-7407
[27] Madhugiri S, Zhou W, Ferraris John P, Balkus Jr Kenneth J. Microporous and Mesoporous Material, 2003, 63:75-84
[28] Liu H, Kameoka J, Czaplewski D A. Craighead H G. Nano Lett., 2004, 4(4): 671-675[29] Ding B, Kim J, Miyazak Y, Shiratori S. Sensor and Actuators B, 2004, 101:373-380
[30] Norris I D, Shaker Manal M, Ko Frank K, Macdiarmid A G. Synthetic Metals, 2000, 114:109-114
[31] 唐克光．光致变色化合物的用途和性能．浙江化工，2002，33(2)：5-9
[32] 杨武利，胡建华，府寿宽．光致变色高分子体系．高分子通报，1998，4：65-73
[33] 于明昕．周啸．金属双硫腙汞在聚合物中的光致变色行为．功能材料．2001，32(2)：203-205
[34] Theron S A, Zussman E, Yarin A L. Polymer, 2004, 45:2017-30
[35] Kim S J.Shin K M, Kim S I. Scripta Materialia, 2004, 51: 31-35
[36] Norris I D, Shaker M M, Ko F K, MacDiarmid A G.Synth. Met., 2000, 114:109-114
[37] Wang X, Drew C, Lee S-H, Senecal K J, Kumar J, Samuelson L A. Nano Lett., 2002, 2: 1273-1275
[38] Boland E D, Wnek G E, Simpson D G,.Pawlowski K J, Bowlin G L. J. Macromol. Sci. Pure Appl. Chem., 2001, A38:1231-1243
[39] Larsen G, Velarde-Ortiz R, Minchow K, Barrero A, Loscertales I G. J. Am. Chem. Soc., 2003, 125:1154-1155
[40] Hou H, Reneker D H. Adv. Mater., 2004, 16:69-73
[41] Hou H, Jun Z, Reuning A, Schaper A, Wendorff J H, Greiner A. Macromol., 2002, 35:2429-2431
[42] Seoul C, Kim Y-T, Baek C -K. J. Polym. Sci. Polym. Phys. Ed., 2003, 41:1572-1577
[43] Wang X, Kim Y -G, Drew C, Ku B -C, Kumar J, Samuelson L A. Nano Lett., 2004, 4:331-334
[44] Pinto N J, Carrion P, Quinones J X. Mater. Sci. Eng. A, 2004, 366:1-5
[45] H.M.N.H. Irving, G. Andrew, E.J. Risdon, J. Chem. Soc., 1949, 54:1949-1952
[46] L.S.Meriwether, E.C. Breitner, C.L. Sloan, J. Am. Chem. Soc., 1965, 87:4441-4442
[47] Won Keun Son, Ji Ho Youk, Taek Seung Lee, Won Ho Park. Poly., 2004, 45:2959-2966
[48] Kasaai MR, Charlet G, Arul J. Food Res Int 2000, 33:63-65
[49] Dong Hong, Nyame Verrad, Macdiarmid Alan G, Jones Wayne E. JR.Journal of Polymer Science: Part B: Polymer Physics, 2004, 42:3934-42
[50] Jae Shin Choi, Sung Won Lee, Lim Jeong, Su-Hyun Bae, Bum Chan Min, Ji Ho Youk, Won Ho Park. International Journal of Biological Macromolecules, 2004. 34:249-56
[51] N. Sertova, I. Petkov, J. M. Nunzi. Journal of Photochemistry and Photobiology A: Chemistry, 2000, 134, 163-168
[52] Deitzel JM, Kleinmeyer J, Harris D, Beck Tan NC. The effect of processing variable on the morphology of electrospun nanofibers and textiles. Polymer. 2001,42:261-72
[53] Koombhongse S, Liu WX, Reneker DH. Flat polymer ribbons and other shapes by electrospinning. J Polymer Sci: Part B: Polymer Physics, 2001, 39:2598-606
[54] A. Koski, K. Yim, S. Shivkumar. Effect of molecular weight on fibrous PVA produced by electrospinning. Mateials Letters, 2004, 58:493-97[55] 吴世康，沈燕清．双硫腙汞络合物在高分膜内的光色互变研究．功能高分子学报，1990，3：3-7
[56] Meriwether L S, Breither E C, Sloan C L et al. Kinetic and infrared study of photochromism of metal dithizonates. J Am Chem Soc., 1965, 87:4448
[57] N. Grassie, H.W. Melville. Proc. Roy. Soc. Lond., A1949, 199: 1.
[58] J.C. Benvington, H.W. Melville, R.P. Taylor, J. Polym. Sci., 1954, 14: 1696.
[59] I.C. McNeill, Eur. Polym. J., 1967, 3: 409.
[60] I.C. McNeill, Eur. Polym. J., 1970, 6: 373.
[61] M.A. Rauf, I.C. McNeill, Polym. Deg. Stab., 1993, 41 (1): 117.
[62] M.A. Rauf, I.C. McNeill, Polym. Deg. Stab., 1993, 40 (2): 263.
[63] M. Abdel-Aziz, S. Gwaily, Polym. Deg. Stab., 1997, 55: 269.
[64] K. El-Salmawi, M. Abu-Zeid, A. EI-Naggar, M. Mamdouh, J. Appl. Polym. Sci., 1999, 72: 509.
[65] M. Walickis, J. Kroh, Acad. Polon. Sci. Ser. Sci. Chim., 1965, 13: 635.
[66] M. Oelschager, E. Schwerz, Anal. Chem., 1972, 258: 203.
[67] W.G Hanna, A.M. Mekewi. E.H. EI-Mosallamy, J. Appl. Polym. Sci., 2001,82: 562.
[68] R.M. Smith, A.E. Martell, Critical Stability Constants, vol. 1-6, Pelsun, New York, 1989.
[69] J.L. Koenig, Spectroscopy of Polymers, Am. Chem. Soc., Washington, DC, 1992.
[70] El-Said H., Ei-Mohamed A.Mekewi. Materials Chemistry and Physics, 2003, 80:319-324