静电喷涂高附着力疏水涂层及其性能
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摘要
目的提高静电喷涂疏水涂层的附着力。方法采用硅烷偶联剂和聚二甲基硅氧烷制备了表面改性疏水二氧化硅粉末。将一定比例的聚偏氟乙烯粉末、超高分子量聚乙烯粉末与疏水二氧化硅粉末混合,制备了复合型疏水粉末。使用环氧树脂、固化剂、活性剂等配制了导电环氧树脂。通过静电喷涂工艺将复合疏水粉末喷涂到已用导电环氧树脂覆盖的铝基板表面,经过中温固化,制得了铝合金疏水复合涂层。采用扫描电子显微镜(SEM)、傅里叶变换红外光谱仪(FTIR)、接触角测量仪(CA)、百格刀附着力测试仪等,对疏水复合涂层进行测试表征。结果 SEM结果表明涂层表面构建了微米-纳米的阶层粗糙结构,经CA测试,该表面具有较好的疏水性。当混合粉末中聚二甲基硅氧烷改性二氧化硅的比例占到20%时,环氧基疏水涂层的接触角最高可达到140°,滚动角最低可达5°,附着力的等级为0级,同时疏水涂层的耐磨性和耐腐蚀性良好。结论采用简单、易于工业化的静电喷涂工艺制备了高附着力的疏水涂层,具有广泛的应用前景。
The work aims to improve the adhesion of hydrophobic coating by electrostatic spraying. Hydrophobic silica powder was prepared by surface modification of silane coupling agent and poly two methylsiloxane. Mixed hydrophobic powders were prepared by mixing a certain proportion of polyvinylidene fluoride(PVDF) and ultra-high molecular weight polyethylene(UHMWPE) with hydrophobic silica powder. Epoxy resin, curing agent and active agent were used to prepare the conductive expoxy resin. Hydrophobic composite coatings of aluminum alloy were prepared by electrostatic spraying on the surface of aluminum substrate covered with conductive epoxy resin. The hydrophobic composite coatings were tested and characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, contact angle tester and Bagram knife adhesion tester.From SEM results, the coating surface had a micro-nano hierarchical rough structure, and the modified surface had good hydrophobicity by CA test. When the proportion of polydimethylsiloxane modified silica in the mixed powders was 20%, the contact angle of epoxy-based hydrophobic coatings reached 140°, the rolling angle reached 5°, and the adhesion grade was 0. At the same time, the hydrophobic coatings had good wear resistance and corrosion resistance. Hydrophobic coatings with high adhesion are prepared by simple and industrialized electrostatic spraying process and has a wide application prospect.
The work aims to improve the adhesion of hydrophobic coating by electrostatic spraying. Hydrophobic silica powder was prepared by surface modification of silane coupling agent and poly two methylsiloxane. Mixed hydrophobic powders were prepared by mixing a certain proportion of polyvinylidene fluoride(PVDF) and ultra-high molecular weight polyethylene(UHMWPE) with hydrophobic silica powder. Epoxy resin, curing agent and active agent were used to prepare the conductive expoxy resin. Hydrophobic composite coatings of aluminum alloy were prepared by electrostatic spraying on the surface of aluminum substrate covered with conductive epoxy resin. The hydrophobic composite coatings were tested and characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, contact angle tester and Bagram knife adhesion tester.From SEM results, the coating surface had a micro-nano hierarchical rough structure, and the modified surface had good hydrophobicity by CA test. When the proportion of polydimethylsiloxane modified silica in the mixed powders was 20%, the contact angle of epoxy-based hydrophobic coatings reached 140°, the rolling angle reached 5°, and the adhesion grade was 0. At the same time, the hydrophobic coatings had good wear resistance and corrosion resistance. Hydrophobic coatings with high adhesion are prepared by simple and industrialized electrostatic spraying process and has a wide application prospect.
引文
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[7]ZHANG Yong-lai,XIA Hong,KIM Eunkyoung,et al.Recent developments in superhydrophobic surfaces with unique structural and functional properties[J].Soft Matter,2012,8(44):11217-11231.
[8]罗晓民,魏梦媛,曹敏.耐腐蚀超疏水铜网的制备及其在油水分离中的应用[J].材料工程,2018,46(5):92-98.LUO Xiao-min,WEI Meng-yuan,CAO Min.Preparation of superhydrophobic Cu mesh with corrosion resistance and applications in oil-water separation[J].Journal of materials engineering,2018,46(5):92-98.
[9]CHENG Quan-yong,GUAN Cheng-shu,WANG Meng,et al.Cellulose nanocrystal coated cotton fabric with superhydrophobicity for efficient oil/water separation[J].Carbohydrate polymers,2018,199:456.
[10]FENG Lin,LI Shu-hong,LI Ying-shun,et al.Super-hydrophobic surfaces from natural to artificial[J].Advanced materials,2010,14(24):1857-1860.
[11]TUTEJA A,CHOI W,MA Ming-lin,et al.Designing superoleophobic surfaces[J].Science,2007,318(5856):1618-1622.
[12]LOMGE J,VARSHNEY P,NANDA D,et al.Fabrication of durable and regenerable superhydrophobic coatings with excellent self-cleaning and anti-fogging properties for aluminium surfaces[J].Alloys and compounds,20177(2):161-170.
[13]高帅,曹磊,张泉,等.金属铝表面超疏水薄膜的构筑及减摩特性[J].表面技术,2016,45(1):75-79.GAO Shuai,CAO Lei,ZHANG Quan,et al.Fabrication and frictionreducing performance of superhydrophobic film on aluminum[J].Surface technology,2016,45(1):75-79.
[14]SU Chang-hong,XU You-qian,GONG Feng,et al.The abrasion resistance of a superhydrophobic surface comprised of polyurethane elastomer[J].Soft matter,2010,6:6068-6071.
[15]侯和峰,陈玉清,綦晓峰.利用相分离制备透明超疏水纳米二氧化硅薄膜[J].化学工业与工程技术,2007(4):1-4.HOU He-feng,CHEN Yu-qing,QI Xiao-feng.Preparation of transparent and super-hydrophobic nanometer silica films by phase separation[J].Journal of chemical industry&engineering,2007(4):1-4.
[16]赵树国,陈阳,马宁,等.电化学刻蚀法制备铝合金超疏水表面及其润湿性转变[J].表面技术,2018,47(3):115-120.ZHAO Shu-guo,CHEN Yang,MA Ning,et al.Superhydrophobic surface of aluminum alloy prepared by electrochemical etching and wettability transition[J].Surface technology,2018,47(3):115-120.
[17]肖允恒,张红辉,杨泽达,等.基于磁流变弹性体膜的可控疏水表面制备与表征[J].中国表面工程,2018,31(2):8-14.XIAO Yun-heng,ZHANG Hong-hui,YANG Ze-da,et al.Preparation and characterization of tunable hydrophobic surfaces based on magnetorheological elastomer film[J].China surface engineering,2018,31(2):8-14
[18]秦加浩,金鑫,方帅帅,等.等离子喷涂WC/Co疏水涂层[J].中国表面工程,2017,30(6):26-33.QIN Jia-hao,JIN Xin,FANG Shuai-shuai,et al.Plasma sprayed WC/Co hydrophobic coating[J].China surface engineering,2017,30(6):26-33.
[19]李龙阳,李玉新,曾志翔,等.电弧喷涂Zn-Al合金与硅氧烷自组装制备超疏水涂层[J].中国表面工程,2014,27(6):50-57.LI Long-yang,LI Yu-xin,ZENG Zhi-xiang,et al.Preparation of superhydrophobic Zn-Al alloy coating and selfassembled siloxane by arc spraying[J].China surface engineering,2014,27(6):50-57.
[20]WU W C,WANG X L,LIU X J,et al.Spray-coated fluorine-free superhydrophobic coatings with easy repairability and applicability[J].Applied materials and interfaces,2009,1(8):1656-1661.
[21]YOON H,KIM H Y,SA S J,et al.A highly transparent self-cleaning super-hydrophobic surface by organosilanecoated alumina particles deposited via electrospraying[J].Journal of materials chemistry A,2015,3(21):11403-11411.
[22]刘琦,刘东霖,杨颖,等.采用高压静电喷涂技术制备超疏水硅橡胶表面的应用研究[J].高电压技术,2015,41(8):2818-2824.LIU Qi,LIU Dong-lin,YANG Ying,et al.Research on superhydrophobic silicon rubber surface made by high voltage electrospray[J].High voltage engineering,201541(8):2818-2824.
[23]谢国先,邱大健,李朝阳,等.氨基硅烷偶联剂对环氧涂层附着力的影响[J].材料保护,2008(3):22-24.XIE Guo-xian,QIU Da-jian,LI Chao-yang,et al.Effecct of amido-silane coupling angent on adhesion of epoxy resin coatings[J].Materials protection,2008(3):22-24.
[24]舒凡,夏桓桓,周良围,等.超疏水Si O2粒子的制备和性能研究[J].化学研究与应用,2016,28(4):512-515.SHU Fan,XIA Huan-huan,ZHOU Liang-wei,et al.Preparation and properties of super-hydrophobic silica particles[J].Chemical research and application,2016,28(4):512-515.
[25]谭秀民,冯安生,赵恒勤,等.硅烷偶联剂对纳米二氧化硅表面接枝改性研究[J].中国粉体技术,2011,17(1):14-17.TAN Xiu-min,FENG An-sheng,ZHAO Heng-qin,et al.Graft modification of SiO2 nano-particles with silane coupling agent[J].China powder science and technology2011,17(1):14-17.
[26]GB/T 9286-1998,附着力测试的基本规则[S].GB/T 9286-1998,Basic rules for adhesion testing[S].
[2]JAN G,KIRILL E.Recent developments in superhydrophobic surfaces and their relevance to marine fouling:a review[J].Biofouling,2006,22(5):339-360.
[3]杨钦,罗荘竹,谭生,等.超疏水自清洁涂层防结冰技术的研究进展[J].中国表面工程,2016,29(4):10-22.YANG Qin,LUO Zhuang-zhu,TAN Sheng,et al.Research progress in anti-icing technology of superhydrophobic self-cleaning coating[J].China surface engineering,2016,29(4):10-22
[4]肖利吉,田军,张博晓,等.超疏水自清洁涂层的研究进展[J].现代涂料与涂装,2017,20(3):32-35.XIAO Li-ji,TIAN Jun,ZHANG Bo-xiao,et al.Research progress of super-hydrophobic self-cleaning coatings[J].Modern paint&finishing,2017,20(3):32-35.
[5]王志博,牛志强.超疏水材料涂层对混凝土抗冻性能的影响[J].新型建筑材料,2017,44(2):107-110.WANG Zhi-bo,NIU Zhi-qiang.Effect of super hydrophobic material coating on frost resistance of concrete[J].New building materials,2017,44(2):107-110.
[6]LIU Zhi-chao,HANSEN Will.Effect of hydrophobic surface treatment on freeze-thaw durability of concrete[J].Cement&concrete composites,2016,69:49-60.
[7]ZHANG Yong-lai,XIA Hong,KIM Eunkyoung,et al.Recent developments in superhydrophobic surfaces with unique structural and functional properties[J].Soft Matter,2012,8(44):11217-11231.
[8]罗晓民,魏梦媛,曹敏.耐腐蚀超疏水铜网的制备及其在油水分离中的应用[J].材料工程,2018,46(5):92-98.LUO Xiao-min,WEI Meng-yuan,CAO Min.Preparation of superhydrophobic Cu mesh with corrosion resistance and applications in oil-water separation[J].Journal of materials engineering,2018,46(5):92-98.
[9]CHENG Quan-yong,GUAN Cheng-shu,WANG Meng,et al.Cellulose nanocrystal coated cotton fabric with superhydrophobicity for efficient oil/water separation[J].Carbohydrate polymers,2018,199:456.
[10]FENG Lin,LI Shu-hong,LI Ying-shun,et al.Super-hydrophobic surfaces from natural to artificial[J].Advanced materials,2010,14(24):1857-1860.
[11]TUTEJA A,CHOI W,MA Ming-lin,et al.Designing superoleophobic surfaces[J].Science,2007,318(5856):1618-1622.
[12]LOMGE J,VARSHNEY P,NANDA D,et al.Fabrication of durable and regenerable superhydrophobic coatings with excellent self-cleaning and anti-fogging properties for aluminium surfaces[J].Alloys and compounds,20177(2):161-170.
[13]高帅,曹磊,张泉,等.金属铝表面超疏水薄膜的构筑及减摩特性[J].表面技术,2016,45(1):75-79.GAO Shuai,CAO Lei,ZHANG Quan,et al.Fabrication and frictionreducing performance of superhydrophobic film on aluminum[J].Surface technology,2016,45(1):75-79.
[14]SU Chang-hong,XU You-qian,GONG Feng,et al.The abrasion resistance of a superhydrophobic surface comprised of polyurethane elastomer[J].Soft matter,2010,6:6068-6071.
[15]侯和峰,陈玉清,綦晓峰.利用相分离制备透明超疏水纳米二氧化硅薄膜[J].化学工业与工程技术,2007(4):1-4.HOU He-feng,CHEN Yu-qing,QI Xiao-feng.Preparation of transparent and super-hydrophobic nanometer silica films by phase separation[J].Journal of chemical industry&engineering,2007(4):1-4.
[16]赵树国,陈阳,马宁,等.电化学刻蚀法制备铝合金超疏水表面及其润湿性转变[J].表面技术,2018,47(3):115-120.ZHAO Shu-guo,CHEN Yang,MA Ning,et al.Superhydrophobic surface of aluminum alloy prepared by electrochemical etching and wettability transition[J].Surface technology,2018,47(3):115-120.
[17]肖允恒,张红辉,杨泽达,等.基于磁流变弹性体膜的可控疏水表面制备与表征[J].中国表面工程,2018,31(2):8-14.XIAO Yun-heng,ZHANG Hong-hui,YANG Ze-da,et al.Preparation and characterization of tunable hydrophobic surfaces based on magnetorheological elastomer film[J].China surface engineering,2018,31(2):8-14
[18]秦加浩,金鑫,方帅帅,等.等离子喷涂WC/Co疏水涂层[J].中国表面工程,2017,30(6):26-33.QIN Jia-hao,JIN Xin,FANG Shuai-shuai,et al.Plasma sprayed WC/Co hydrophobic coating[J].China surface engineering,2017,30(6):26-33.
[19]李龙阳,李玉新,曾志翔,等.电弧喷涂Zn-Al合金与硅氧烷自组装制备超疏水涂层[J].中国表面工程,2014,27(6):50-57.LI Long-yang,LI Yu-xin,ZENG Zhi-xiang,et al.Preparation of superhydrophobic Zn-Al alloy coating and selfassembled siloxane by arc spraying[J].China surface engineering,2014,27(6):50-57.
[20]WU W C,WANG X L,LIU X J,et al.Spray-coated fluorine-free superhydrophobic coatings with easy repairability and applicability[J].Applied materials and interfaces,2009,1(8):1656-1661.
[21]YOON H,KIM H Y,SA S J,et al.A highly transparent self-cleaning super-hydrophobic surface by organosilanecoated alumina particles deposited via electrospraying[J].Journal of materials chemistry A,2015,3(21):11403-11411.
[22]刘琦,刘东霖,杨颖,等.采用高压静电喷涂技术制备超疏水硅橡胶表面的应用研究[J].高电压技术,2015,41(8):2818-2824.LIU Qi,LIU Dong-lin,YANG Ying,et al.Research on superhydrophobic silicon rubber surface made by high voltage electrospray[J].High voltage engineering,201541(8):2818-2824.
[23]谢国先,邱大健,李朝阳,等.氨基硅烷偶联剂对环氧涂层附着力的影响[J].材料保护,2008(3):22-24.XIE Guo-xian,QIU Da-jian,LI Chao-yang,et al.Effecct of amido-silane coupling angent on adhesion of epoxy resin coatings[J].Materials protection,2008(3):22-24.
[24]舒凡,夏桓桓,周良围,等.超疏水Si O2粒子的制备和性能研究[J].化学研究与应用,2016,28(4):512-515.SHU Fan,XIA Huan-huan,ZHOU Liang-wei,et al.Preparation and properties of super-hydrophobic silica particles[J].Chemical research and application,2016,28(4):512-515.
[25]谭秀民,冯安生,赵恒勤,等.硅烷偶联剂对纳米二氧化硅表面接枝改性研究[J].中国粉体技术,2011,17(1):14-17.TAN Xiu-min,FENG An-sheng,ZHAO Heng-qin,et al.Graft modification of SiO2 nano-particles with silane coupling agent[J].China powder science and technology2011,17(1):14-17.
[26]GB/T 9286-1998,附着力测试的基本规则[S].GB/T 9286-1998,Basic rules for adhesion testing[S].