静电纺双疏型聚丙烯腈基纳米纤维膜制备及其性能
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摘要
为制备耐磨性能良好的双疏型纤维膜并将其应用于油/水、油/油分离领域,以静电纺丝方法制备的聚丙烯腈(PAN)纳米纤维为基材,采用多巴胺(DA)与十三氟辛基三乙氧基硅烷(G617)对纤维膜进行改性制得双疏型PAN纤维膜。借助扫描电子显微镜、接触角测量仪、X射线光电子能谱仪等手段探讨纺丝条件、DA与G617用量等对改性前后PAN纤维膜表面形貌以及疏水疏油性能的影响。结果表明:纺丝液中PAN质量分数为13. 8%、纺丝电压为18 k V时,纤维形貌最佳;改性后PAN纤维膜的乙二醇接触角可达135. 1°,甲苯接触角为0°,水接触角可达141. 9°,色拉油接触角可达131. 2°;摩擦20次后PAN纤维膜的水、色拉油接触角均大于125°,可顺利实现水/甲苯、甲苯/乙二醇以及甲苯/水乳液的分离。
In order to prepare amphiphobic fiber materials with good wear resistance for oil/water or oil/oil separation,amphiphobic polyacrylonitrile( PAN) nanofiber materials were prepared by using PAN electrospun nanofibers as the substrate, and dopamine( DA) and tridecafluorooctyltriethoxysilane( G617) as the surface treatment agent. The effects of various electrospinning process factors,DA and G617 content on the surface morphology and hydrophobic/oleophobic properties of PAN electrospun films were investigated by scanning electron microscopy,contact angle measuring instrument,X-ray photoelectron spectroscopy and so on. The results show that when the mass ratio of PAN in spinning solution is 13. 8% and the spinning voltage is 18 kV,the fiber morphology is the best. And the ethylene glycol contact angle,the toluene contact angle,the water contact angle and the salad oil contact angle of the modified PAN electrospun films can be 135. 1°,0°,141. 9° and 131. 2°,respectively. Moreover,the water or salad oil contact angle of the modified PAN electrospun films can be larger than 125° after20 cycles of abrasion test. The results show that the modified PAN electrospun films exhibit good properties in the separation of water/toluene,toluene/ethylene glycol and toluene-water emulsion.
In order to prepare amphiphobic fiber materials with good wear resistance for oil/water or oil/oil separation,amphiphobic polyacrylonitrile( PAN) nanofiber materials were prepared by using PAN electrospun nanofibers as the substrate, and dopamine( DA) and tridecafluorooctyltriethoxysilane( G617) as the surface treatment agent. The effects of various electrospinning process factors,DA and G617 content on the surface morphology and hydrophobic/oleophobic properties of PAN electrospun films were investigated by scanning electron microscopy,contact angle measuring instrument,X-ray photoelectron spectroscopy and so on. The results show that when the mass ratio of PAN in spinning solution is 13. 8% and the spinning voltage is 18 kV,the fiber morphology is the best. And the ethylene glycol contact angle,the toluene contact angle,the water contact angle and the salad oil contact angle of the modified PAN electrospun films can be 135. 1°,0°,141. 9° and 131. 2°,respectively. Moreover,the water or salad oil contact angle of the modified PAN electrospun films can be larger than 125° after20 cycles of abrasion test. The results show that the modified PAN electrospun films exhibit good properties in the separation of water/toluene,toluene/ethylene glycol and toluene-water emulsion.
引文
[1]汪怀远,孟旸,赵景岩,等.双疏表面的制备及性能研究新进展[J].材料工程,2014(3):90-96.WANG Huaiyuan,MENG Yang,ZHAO Jingyan,et al.New progress on preparation and properties of amphiphobic surface[J]. Materials Engineering,2014(3):90-96.
[2]刘耀丰.基于疏水/疏油膜的镁空气电池结构设计及电化学性能研究[D].天津:天津理工大学,2015:23-57.LIU Yaofeng. The structure design and electrochemical properties of magnesium-air battery based on hydrophobic/oleophobic film[D]. Tianjin:Tianjin University of Technology,2015:23-57.
[3] HUANG Y X,WANG Z,HOU D,et al. Coaxially electrospun super-amphiphobic silica-based membrane for anti-surfactant-wetting membrane distillation[J].Journal of Membrane Science,2017,531:122-128.
[4] HU Z,WANG H,ZHU Y,et al. Rapid development of thickness-controllable superamphiphobic coating on the inner wall of long narrow pipes[J]. AICh E Journal,2017,63(9):3636-3641.
[5]薛朝华,尹伟,贾顺田.纤维基超疏水功能表面制备方法的研究进展[J].纺织学报, 2012,33(4):146-152.XUE Zhaohua,YIN Wei,JIA Shuntian. Progress in fabrication of fiber-based superhydrophobic surfaces[J]. Journal of Textile Research, 2012,33(4):146-152.
[6] TIAN X,YI L,MENG X,et al. Superhydrophobic surfaces of electrospun block copolymer fibers with low content of fluorosilicones[J]. Applied Surface Science,2014,307:566-575.
[7]周惠敏,谢婷婷,李智勇,等.等离子体表面改性协同静电喷雾在车饰毛织物疏水整理中的应用[J].纺织学报,2016,37(8):89-93.ZHOU Huimin, XIE Tingting, LI Zhiyong, et al.Application of plasma modification in combination with electrostatic spraying in hydrophobic finishing of wool textiles for automotive decoration[J]. Journal of Textile Research,2016,37(8):89-93.
[8] SANCHEZ L D,BRACK N,POSTMA A,et al.Surface modification of electrospun fibres for biomedical applications:a focus on radical polymerization methods[J]. Biomaterials,2016,106:24-45.
[9]冯雪,汪滨,王娇娜,等.空气过滤用聚丙烯腈静电纺纤维膜的制备及其性能[J].纺织学报,2017,38(4):6-11.FENG Xue, WANG Bin, WANG Jiaona, et al.Preparation and properties of polyacrylonitrile nanofiber membranes used for air filtering by electrospinning[J].Journal of Textile Research,2017,38(4):6-11.
[10] YI L, MENG X, TIAN X, et al. Wettability of electrospun films of microphase-separated block copolymers with 3,3,3-trifluoropropyl substituted siloxane segments[J]. The Journal of Physical Chemistry C,2014,118(46):26671-26682.
[11] SMITH S A,WILLIAMS B P,JOO Y L. Effect of polymer and ceramic morphology on the material and electrochemical properties of electrospun PAN/polymer derived ceramic composite nanofiber membranes for lithium ion battery separators[J]. Journal of Membrane Science,2017,526:315-322.
[12] ZHAO J,SUN Z,SHAO Z,et al. Effect of surfaceactive agent on morphology and properties of electrospun PVA nanofibres[J]. Fibers and Polymers, 2016,17(6):896-901.
[13] LIU Z, ZHAO J, LIU P, et al. Tunable surface morphology of electrospun PMMA fiber using binary solvent[J]. Applied Surface Science, 2016,364:516-521.
[14]罗必新.氟硅疏水疏油材料的制备与性质研究[D].武汉:华中师范大学,2009:30-51.LUO Bixin. The preparation and characterization of fluoro-silicone hydrophobic and oleophobic materials[D]. Wuhan:Central China Normal University,2009:30-51.
[15]张娇娇.聚多巴胺改性静电纺聚丙烯腈纤维膜及其油水分离性能[D].上海:东华大学,2017:22-54.ZHANG Jiaojiao. Study on PAN electrospun nanofiber membrane modified by polydopamine and its properties on oil/water separation[D]. Shanghai:Donghua University,2017:22-54.
[16] LEE H,DELLATORE S M,MILLER W M,et al.Mussel-inspired surface chemistry for multifunctional coatings[J]. Science,2007,318(5849):426-430.
[17]李珍,王军.静电纺丝可纺性影响因素的研究成果[J].合成纤维,2008,37(9):6-11.LI Zhen,WANG Jun. Studies on influential factors on nanofiber spinnability of electrospinning[J]. Synthetic Fiber in China,2008,37(9):6-11.
[18]杨豆,张卫波,刘锰钰,等.静电纺丝制备纳米纤维的影响因素研究进展[J].合成技术及应用,2017,32(1):25-29.YANG Dou, ZHANG Weibo, LIU Mengyu, et al.Research progress on the influence factors of preparing nanofibers by electrospinning[J]. Synthetic Technology and Application,2017,32(1):25-29.
[19]曹铁平,李跃军,王莹,等.静电纺丝法制备聚丙烯腈/聚苯胺复合纳米纤维及其表征[J].高分子学报,2010,7(12):1464-1469.CAO Tieping, LI Yuejun, WANG Ying, et al.Preparation and characterization of PAN/PANI composite nanofibers by eletrospinning[J]. Acta Polymerica Sinica,2010,7(12):1464-1469.
[2]刘耀丰.基于疏水/疏油膜的镁空气电池结构设计及电化学性能研究[D].天津:天津理工大学,2015:23-57.LIU Yaofeng. The structure design and electrochemical properties of magnesium-air battery based on hydrophobic/oleophobic film[D]. Tianjin:Tianjin University of Technology,2015:23-57.
[3] HUANG Y X,WANG Z,HOU D,et al. Coaxially electrospun super-amphiphobic silica-based membrane for anti-surfactant-wetting membrane distillation[J].Journal of Membrane Science,2017,531:122-128.
[4] HU Z,WANG H,ZHU Y,et al. Rapid development of thickness-controllable superamphiphobic coating on the inner wall of long narrow pipes[J]. AICh E Journal,2017,63(9):3636-3641.
[5]薛朝华,尹伟,贾顺田.纤维基超疏水功能表面制备方法的研究进展[J].纺织学报, 2012,33(4):146-152.XUE Zhaohua,YIN Wei,JIA Shuntian. Progress in fabrication of fiber-based superhydrophobic surfaces[J]. Journal of Textile Research, 2012,33(4):146-152.
[6] TIAN X,YI L,MENG X,et al. Superhydrophobic surfaces of electrospun block copolymer fibers with low content of fluorosilicones[J]. Applied Surface Science,2014,307:566-575.
[7]周惠敏,谢婷婷,李智勇,等.等离子体表面改性协同静电喷雾在车饰毛织物疏水整理中的应用[J].纺织学报,2016,37(8):89-93.ZHOU Huimin, XIE Tingting, LI Zhiyong, et al.Application of plasma modification in combination with electrostatic spraying in hydrophobic finishing of wool textiles for automotive decoration[J]. Journal of Textile Research,2016,37(8):89-93.
[8] SANCHEZ L D,BRACK N,POSTMA A,et al.Surface modification of electrospun fibres for biomedical applications:a focus on radical polymerization methods[J]. Biomaterials,2016,106:24-45.
[9]冯雪,汪滨,王娇娜,等.空气过滤用聚丙烯腈静电纺纤维膜的制备及其性能[J].纺织学报,2017,38(4):6-11.FENG Xue, WANG Bin, WANG Jiaona, et al.Preparation and properties of polyacrylonitrile nanofiber membranes used for air filtering by electrospinning[J].Journal of Textile Research,2017,38(4):6-11.
[10] YI L, MENG X, TIAN X, et al. Wettability of electrospun films of microphase-separated block copolymers with 3,3,3-trifluoropropyl substituted siloxane segments[J]. The Journal of Physical Chemistry C,2014,118(46):26671-26682.
[11] SMITH S A,WILLIAMS B P,JOO Y L. Effect of polymer and ceramic morphology on the material and electrochemical properties of electrospun PAN/polymer derived ceramic composite nanofiber membranes for lithium ion battery separators[J]. Journal of Membrane Science,2017,526:315-322.
[12] ZHAO J,SUN Z,SHAO Z,et al. Effect of surfaceactive agent on morphology and properties of electrospun PVA nanofibres[J]. Fibers and Polymers, 2016,17(6):896-901.
[13] LIU Z, ZHAO J, LIU P, et al. Tunable surface morphology of electrospun PMMA fiber using binary solvent[J]. Applied Surface Science, 2016,364:516-521.
[14]罗必新.氟硅疏水疏油材料的制备与性质研究[D].武汉:华中师范大学,2009:30-51.LUO Bixin. The preparation and characterization of fluoro-silicone hydrophobic and oleophobic materials[D]. Wuhan:Central China Normal University,2009:30-51.
[15]张娇娇.聚多巴胺改性静电纺聚丙烯腈纤维膜及其油水分离性能[D].上海:东华大学,2017:22-54.ZHANG Jiaojiao. Study on PAN electrospun nanofiber membrane modified by polydopamine and its properties on oil/water separation[D]. Shanghai:Donghua University,2017:22-54.
[16] LEE H,DELLATORE S M,MILLER W M,et al.Mussel-inspired surface chemistry for multifunctional coatings[J]. Science,2007,318(5849):426-430.
[17]李珍,王军.静电纺丝可纺性影响因素的研究成果[J].合成纤维,2008,37(9):6-11.LI Zhen,WANG Jun. Studies on influential factors on nanofiber spinnability of electrospinning[J]. Synthetic Fiber in China,2008,37(9):6-11.
[18]杨豆,张卫波,刘锰钰,等.静电纺丝制备纳米纤维的影响因素研究进展[J].合成技术及应用,2017,32(1):25-29.YANG Dou, ZHANG Weibo, LIU Mengyu, et al.Research progress on the influence factors of preparing nanofibers by electrospinning[J]. Synthetic Technology and Application,2017,32(1):25-29.
[19]曹铁平,李跃军,王莹,等.静电纺丝法制备聚丙烯腈/聚苯胺复合纳米纤维及其表征[J].高分子学报,2010,7(12):1464-1469.CAO Tieping, LI Yuejun, WANG Ying, et al.Preparation and characterization of PAN/PANI composite nanofibers by eletrospinning[J]. Acta Polymerica Sinica,2010,7(12):1464-1469.