微量1,6-己二胺改性纳米Fe_3O_4对PVDF共混膜性能的影响
|
摘要
以微量的改性纳米四氧化三铁与聚偏氟乙烯(PVDF)共混,制备具有良好亲水性、纯水通量和防污性能的PVDF复合膜。通过溶剂热法合成了经1,6-己二胺改性的纳米四氧化三铁(H-Fe_3O_4),同时比较了未经改性的四氧化三铁(Fe_3O_4)和改性后的四氧化三铁(H-Fe_3O_4)的结构性能差异。通过相转化法制备了H-Fe_3O_4(质量分数小于1.0%)与PVDF的共混复合膜(H-Fe_3O_4@PVDF复合膜)。通过测试膜的晶相组成、表面和断面形貌、静态纯水接触角、平均孔隙率、平均孔径、纯水通量、牛白蛋白截留率以及通量恢复率,研究微量H-Fe_3O_4的投加对复合膜性能的影响。结果表明,经1,6-己二胺调控合成的H-Fe_3O_4,比Fe_3O_4拥有更小的粒径、更好的单分散性以及更多的亲水官能团。向膜中添加0.3%的H-Fe_3O_4,可使复合膜的静态纯水接触角由80.9°降到66.6°,亲水性得到良好的改善。复合膜的平均孔隙率、平均孔径、纯水通量以及通量恢复率随H-Fe_3O_4投加量的增加均明显提高。当H-Fe_3O_4质量分数为0.4%时,复合膜的纯水通量从原膜的10.4 L·(m~2·h)~(-1)增加到了144.0 L·(m~2·h)~(-1),通量恢复率也从原膜的51.4%增加到了87.5%。微量H-Fe_3O_4的添加较好地改善了PVDF膜的性能,具有较好的实用价值。
A composite polyvinylidene fluoride(PVDF) membrane with good hydrophilicity, pure water flux and antifouling property was prepared by blending trace modified nano-Fe_3O_4(H-Fe_3O_4) with PVDF. This H-Fe_3O_4 was synthesized in the presence of 1,6-hexadiamine via solvothermal method. The structure and performance differences between H-Fe_3O_4 and Fe_3O_4 were compared. H-Fe_3O_4@PVDF composite membranes with different amounts of H-Fe_3O_4(mass fraction less than 1.0%) were prepared by phase inversion process. Meanwhile, the effect of H-Fe_3O_4 adding amounts on the physiochemical properties of the composite membrane was studied through determining the crystal structure, surface and cross-section morphology, static pure water contact angle,average porosity, mean pore size, pure water flux, bovine albumin rejection rate and flux recovery ratio. The results showed that H-Fe_3O_4 had smaller particle size, better monodispersity and more hydrophilic functional groups than Fe_3O_4. In comparison with pure PVDF membrane, this composite membrane modified with 0.3% of H-Fe_3O_4 reduced its static pure water contact angle from 80.9° to the lowest 66.6°, improving its hydrophilicity accordingly. The average porosity, mean pore size, pure water flux and flux recovery ratio of this composite membrane increased with the increase of H-Fe_3O_4 adding amounts. When 0.4% of H-Fe_3O_4 was incorporated, the pure water flux of this composite membrane increased from 10.4 L·(m~2·h)~(-1) of pure PVDF membrane to 144.0 L·(m~2·h)~(-1), and the flux recovery ratio also increased from 51.4% of pure PVDF membrane to 87.5%. The addition of trace H-Fe_3O_4(mass fraction less than 1.0%) could improve the performance of the composite membrane,which shows a good potential for practical use.
A composite polyvinylidene fluoride(PVDF) membrane with good hydrophilicity, pure water flux and antifouling property was prepared by blending trace modified nano-Fe_3O_4(H-Fe_3O_4) with PVDF. This H-Fe_3O_4 was synthesized in the presence of 1,6-hexadiamine via solvothermal method. The structure and performance differences between H-Fe_3O_4 and Fe_3O_4 were compared. H-Fe_3O_4@PVDF composite membranes with different amounts of H-Fe_3O_4(mass fraction less than 1.0%) were prepared by phase inversion process. Meanwhile, the effect of H-Fe_3O_4 adding amounts on the physiochemical properties of the composite membrane was studied through determining the crystal structure, surface and cross-section morphology, static pure water contact angle,average porosity, mean pore size, pure water flux, bovine albumin rejection rate and flux recovery ratio. The results showed that H-Fe_3O_4 had smaller particle size, better monodispersity and more hydrophilic functional groups than Fe_3O_4. In comparison with pure PVDF membrane, this composite membrane modified with 0.3% of H-Fe_3O_4 reduced its static pure water contact angle from 80.9° to the lowest 66.6°, improving its hydrophilicity accordingly. The average porosity, mean pore size, pure water flux and flux recovery ratio of this composite membrane increased with the increase of H-Fe_3O_4 adding amounts. When 0.4% of H-Fe_3O_4 was incorporated, the pure water flux of this composite membrane increased from 10.4 L·(m~2·h)~(-1) of pure PVDF membrane to 144.0 L·(m~2·h)~(-1), and the flux recovery ratio also increased from 51.4% of pure PVDF membrane to 87.5%. The addition of trace H-Fe_3O_4(mass fraction less than 1.0%) could improve the performance of the composite membrane,which shows a good potential for practical use.
引文
[1]JI J,LIU F,HASHIM N A,et al.Poly(vinylidene fluoride)(PVDF)membranes for fluid separation[J].Reactive&Functional Polymers,2015,86:134-153.
[2]黄健平,邵玉敏,刘纳,等.PVDF/PMMA与PVDF/TPU共混膜抗污染性能研究及应用[J].环境工程学报,2012,6(5):1413-1418.
[3]王献昆,吕向红.PVDF-g-PAA共聚物的制备及其改性PVDF膜[J].华南师范大学学报(自然科学版),2017,49(4):28-33.
[4]苗继斌.基于碱式扩散渗析杂化膜的制备与性能研究[D].合肥:中国科学技术大学,2016.
[5]LAN L,LI Y S,XIANG C B.Preparation of poly(vinylidene fluoride)(PVDF)ultrafiltration membrane modified by nanosized alumina(Al2O3)and its antifouling research[J].Polymer,2005,46(18):7701-7706.
[6]ZENG G Y,HE Y,ZHAN Y Q,et al.Novel polyvinylidene fluoride nanofiltration membrane blended with functionalized halloysite nanotubes for dye and heavy metal ions removal[J].Journal of Hazardous Materials,2016,317:60-72.
[7]GUMUS H.Performance investigation of Fe3O4blended poly(vinylidene fluoride)membrane on filtration and benzyl alcohol oxidation;evaluation of sufficiency for catalytic reactors[J/OL].[2018-07-01].https://doi.org/10.1016/j.cjche.2018.05.006.
[8]HUANG Z Q,ZHENG F,ZHANG Z,et al.The performance of the PVDF-Fe3O4ultrafiltration membrane and the effect of a parallel magnetic field used during the membrane formation[J].Desalination,2012,292:64-72.
[9]WU G P,GAN S Y,CUI L Z,et al.Preparation and characterization of PES/TiO2composite membranes[J].Applied Surface Science,2008,254(21):7080-7086.
[10]付佳.溶剂热法制备纳米四氧化三铁研究[D].西安:西安建筑科技大学,2007.
[11]WANG L Y,BAO J,WANG L,et al.One-pot synthesis and bioapplication of amine-functionalized magnetite nanoparticles and hollow nanospheres[J].Chemistry:A European Journal,2006,12(24):6341-6347.
[12]ZHANG J,WANG Q Y,WANG Z W,et al.Modification of poly(vinylidene fluoride)/polyethersulfone blend membrane with polyvinyl alcohol for improving antifouling ability[J].Journal of Membrane Science,2014,466:293-301.
[13]山斓,王磊,王旭东,等.TiO2/PVDF编织管改性复合膜的制备及性能[J].环境工程学报,2016,10(9):4796-4802.
[14]徐兴龙.四氧化三铁纳米微结构的合成、表征及锂电性能[D].哈尔滨:哈尔滨工程大学,2015.
[15]苏雅拉.纳米四氧化三铁的制备及其性能研究[D].呼和浩特:内蒙古师范大学,2011.
[16]WATTS J F,WOLSTENHOLME J.表面分析(XPS和AES)引论[M].吴正龙,译.上海:华东理工大学出版社,2008:81-83.
[17]席得圣.氨基功能化磁性复合材料的制备及其吸附性能研究[D].天津:天津大学,2016.
[18]朱延松,韩延东,白丹,等.表面氨基化的Fe3O4/SiO2复合磁性纳米粒子提取白酒中羧酸的研究[J].食品科学,2010,31(9):86-88.
[19]张怀斌,屈桂君,王成,等.氨基化Fe3O4纳米粒子的制备及对胃癌细胞的毒性评价[J].广州化工,2018,46(4):36-38
[20]BAGHANI A N,MAHVI A H,GHOLAMI M,et al.One-pot synthesis,characterization and adsorption studies of amine-functionalized magnetite nanoparticles for removal of Cr(VI)and Ni(II)ions from aqueous solution:Kinetic,isotherm and thermodynamic studies[J].Journal of Environmental Health Science&Engineering,2016,14(1):11-22.
[21]HATTORI T,HIKOSAKA M,OHIGASHI H.The crystallization behavior and phase diagram of extended-chain crystal of poly(vinylidene fluoride)under high pressure[J].Polymer,1996,37(1):85-91.
[22]周雨,鲍建国,谢雄,等.ZrO2/TiO2/PVDF超滤膜的制备与性能研究[J].安全与环境工程,2015,22(6):29-34.
[23]ZHAO Q Q,HOU J W,SHEN J N,et al.Long-lasting antibacterial behavior of a novel mixed matrix water purification membrane[J].Journal of Materials Chemistry A,2015,3(36):18696-18705.
[24]VATANPOUR V,MADAENI S S,RAJABI L,et al.Boehmite nanoparticles as a new nanofiller for preparation of antifouling mixed matrix membranes[J].Journal of Membrane Science,2012,401-402:132-143.
[25]HWANG H Y,KIM D J,KIM H J,et al.Effect of nanoclay on properties of porous PVDF membranes[J].Transactions of Nonferrous Metals Society of China,2011,21(s1):141-147.
[26]张玉云.ZrO2、TiO2/PVDF杂化膜材料的制备及其过滤性能的研究[D].北京:清华大学,2010.
[27]李青青,朱振亚,王磊,等.氧化石墨烯改性PVDF/PET复合膜的制备及其抗污染性能[J].环境工程学报,2018,12(1):25-33.
[28]樊华,张琳,侯得印,等.混合添加剂对PVDF平板疏水膜结构及性能的影响[J].环境工程学报,2012,6(9):2985-2990.
[29]孙鸿,宋华,芦艳.Al2O3/TiO2/PVDF杂化超滤膜的制备及其性能研究[J].功能材料,2012,43(18):2558-2563.
[30]朱志超,朱小燕,雷新荣.硅烷偶联剂改性高岭土对PVDF膜性能的影响研究[J].膜科学与技术,2015,35(6):9-15.
[31]董华琳.功能性PVDF膜的制备及性能研究[D].天津:天津工业大学,2017.
[2]黄健平,邵玉敏,刘纳,等.PVDF/PMMA与PVDF/TPU共混膜抗污染性能研究及应用[J].环境工程学报,2012,6(5):1413-1418.
[3]王献昆,吕向红.PVDF-g-PAA共聚物的制备及其改性PVDF膜[J].华南师范大学学报(自然科学版),2017,49(4):28-33.
[4]苗继斌.基于碱式扩散渗析杂化膜的制备与性能研究[D].合肥:中国科学技术大学,2016.
[5]LAN L,LI Y S,XIANG C B.Preparation of poly(vinylidene fluoride)(PVDF)ultrafiltration membrane modified by nanosized alumina(Al2O3)and its antifouling research[J].Polymer,2005,46(18):7701-7706.
[6]ZENG G Y,HE Y,ZHAN Y Q,et al.Novel polyvinylidene fluoride nanofiltration membrane blended with functionalized halloysite nanotubes for dye and heavy metal ions removal[J].Journal of Hazardous Materials,2016,317:60-72.
[7]GUMUS H.Performance investigation of Fe3O4blended poly(vinylidene fluoride)membrane on filtration and benzyl alcohol oxidation;evaluation of sufficiency for catalytic reactors[J/OL].[2018-07-01].https://doi.org/10.1016/j.cjche.2018.05.006.
[8]HUANG Z Q,ZHENG F,ZHANG Z,et al.The performance of the PVDF-Fe3O4ultrafiltration membrane and the effect of a parallel magnetic field used during the membrane formation[J].Desalination,2012,292:64-72.
[9]WU G P,GAN S Y,CUI L Z,et al.Preparation and characterization of PES/TiO2composite membranes[J].Applied Surface Science,2008,254(21):7080-7086.
[10]付佳.溶剂热法制备纳米四氧化三铁研究[D].西安:西安建筑科技大学,2007.
[11]WANG L Y,BAO J,WANG L,et al.One-pot synthesis and bioapplication of amine-functionalized magnetite nanoparticles and hollow nanospheres[J].Chemistry:A European Journal,2006,12(24):6341-6347.
[12]ZHANG J,WANG Q Y,WANG Z W,et al.Modification of poly(vinylidene fluoride)/polyethersulfone blend membrane with polyvinyl alcohol for improving antifouling ability[J].Journal of Membrane Science,2014,466:293-301.
[13]山斓,王磊,王旭东,等.TiO2/PVDF编织管改性复合膜的制备及性能[J].环境工程学报,2016,10(9):4796-4802.
[14]徐兴龙.四氧化三铁纳米微结构的合成、表征及锂电性能[D].哈尔滨:哈尔滨工程大学,2015.
[15]苏雅拉.纳米四氧化三铁的制备及其性能研究[D].呼和浩特:内蒙古师范大学,2011.
[16]WATTS J F,WOLSTENHOLME J.表面分析(XPS和AES)引论[M].吴正龙,译.上海:华东理工大学出版社,2008:81-83.
[17]席得圣.氨基功能化磁性复合材料的制备及其吸附性能研究[D].天津:天津大学,2016.
[18]朱延松,韩延东,白丹,等.表面氨基化的Fe3O4/SiO2复合磁性纳米粒子提取白酒中羧酸的研究[J].食品科学,2010,31(9):86-88.
[19]张怀斌,屈桂君,王成,等.氨基化Fe3O4纳米粒子的制备及对胃癌细胞的毒性评价[J].广州化工,2018,46(4):36-38
[20]BAGHANI A N,MAHVI A H,GHOLAMI M,et al.One-pot synthesis,characterization and adsorption studies of amine-functionalized magnetite nanoparticles for removal of Cr(VI)and Ni(II)ions from aqueous solution:Kinetic,isotherm and thermodynamic studies[J].Journal of Environmental Health Science&Engineering,2016,14(1):11-22.
[21]HATTORI T,HIKOSAKA M,OHIGASHI H.The crystallization behavior and phase diagram of extended-chain crystal of poly(vinylidene fluoride)under high pressure[J].Polymer,1996,37(1):85-91.
[22]周雨,鲍建国,谢雄,等.ZrO2/TiO2/PVDF超滤膜的制备与性能研究[J].安全与环境工程,2015,22(6):29-34.
[23]ZHAO Q Q,HOU J W,SHEN J N,et al.Long-lasting antibacterial behavior of a novel mixed matrix water purification membrane[J].Journal of Materials Chemistry A,2015,3(36):18696-18705.
[24]VATANPOUR V,MADAENI S S,RAJABI L,et al.Boehmite nanoparticles as a new nanofiller for preparation of antifouling mixed matrix membranes[J].Journal of Membrane Science,2012,401-402:132-143.
[25]HWANG H Y,KIM D J,KIM H J,et al.Effect of nanoclay on properties of porous PVDF membranes[J].Transactions of Nonferrous Metals Society of China,2011,21(s1):141-147.
[26]张玉云.ZrO2、TiO2/PVDF杂化膜材料的制备及其过滤性能的研究[D].北京:清华大学,2010.
[27]李青青,朱振亚,王磊,等.氧化石墨烯改性PVDF/PET复合膜的制备及其抗污染性能[J].环境工程学报,2018,12(1):25-33.
[28]樊华,张琳,侯得印,等.混合添加剂对PVDF平板疏水膜结构及性能的影响[J].环境工程学报,2012,6(9):2985-2990.
[29]孙鸿,宋华,芦艳.Al2O3/TiO2/PVDF杂化超滤膜的制备及其性能研究[J].功能材料,2012,43(18):2558-2563.
[30]朱志超,朱小燕,雷新荣.硅烷偶联剂改性高岭土对PVDF膜性能的影响研究[J].膜科学与技术,2015,35(6):9-15.
[31]董华琳.功能性PVDF膜的制备及性能研究[D].天津:天津工业大学,2017.