磷化聚苯胺固化含环氧基硅树脂涂层的制备及性能
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摘要
为了改善有机硅树脂的固化条件及其涂层的防腐蚀性能,以γ-缩水甘油醚氧丙基三甲氧基硅烷(GPTMS)、硅酸乙酯(TEOS)、二甲基二乙氧基硅烷(DMDMS)为硅烷单体,采用溶胶-凝胶法制备了含环氧基的硅树脂(ESiR),并以磷化聚苯胺(PANI)为固化剂制备了硅树脂防腐蚀涂层,分析了PANI固化含环氧基硅树脂的固化反应。通过测试固化时间、涂层的柔韧性和硬度、热失重曲线等考察了PANI添加量对涂层固化程度的影响;通过附着力、接触角、吸水率、电化学阻抗谱和极化曲线测试了PANI添加量对涂层性能的影响。结果表明:当PANI添加量(质量分数)为3%时,得到的涂层固化效果较好,涂层既具有良好的柔韧性,又有较高的硬度;且涂层表现出较好的疏水性、附着力和优异的防腐蚀性能,其接触角为103.5°,吸水率为8.91%;涂层的干、湿附着力均为0级;腐蚀电流密度为7.58×10~(-8) A/cm~2,电化学阻抗值达到3.4×10~6Ω·cm~2。
To improve the curing condition of the silicone resin and the corrosion resistance of the coatings, silicone resin containing epoxide group(ESiR) was synthesized by sol-gel method with γ-glycidoxypropyl trime thoxy silane(GPTMS),tetraethoxy silicate(TEOS), and dimethyl diethoxy silane(DMDMS) as silane monomer. The silicone resin anticorrosion coatings were then prepared by using phosphated polyaniline(PANI) as curing agent. The curing reaction of PANI cured silicone resin containing epoxide group was analyzed. The effect of PANI amount on curing degree of the coatings was investigated by the curing time, flexibility, hardness and thermo gravimetric curve. The effects of PANI amount on the coatings properties were investigated by adhesion, contact angle, water absorption, electrochemical impedance spectroscopy(EIS) and potential polarization curve. Results show that the coating has better curing degree, hydrophobicity property,adhesion, and excellent anticorrosion properties when the amount of PANI is 3%. The coating has both good flexibility and high hardness. The water contact angle of the coating is 103.5° and the water absorption rate is 8.91%. The dry adhesion and wet adhesion are grade 0, respectively. The corrosion current density is 7.58×10~(-8) A/cm~2, and the electrochemical impedance value reaches 3.4×10~6 Ω·cm~2.
To improve the curing condition of the silicone resin and the corrosion resistance of the coatings, silicone resin containing epoxide group(ESiR) was synthesized by sol-gel method with γ-glycidoxypropyl trime thoxy silane(GPTMS),tetraethoxy silicate(TEOS), and dimethyl diethoxy silane(DMDMS) as silane monomer. The silicone resin anticorrosion coatings were then prepared by using phosphated polyaniline(PANI) as curing agent. The curing reaction of PANI cured silicone resin containing epoxide group was analyzed. The effect of PANI amount on curing degree of the coatings was investigated by the curing time, flexibility, hardness and thermo gravimetric curve. The effects of PANI amount on the coatings properties were investigated by adhesion, contact angle, water absorption, electrochemical impedance spectroscopy(EIS) and potential polarization curve. Results show that the coating has better curing degree, hydrophobicity property,adhesion, and excellent anticorrosion properties when the amount of PANI is 3%. The coating has both good flexibility and high hardness. The water contact angle of the coating is 103.5° and the water absorption rate is 8.91%. The dry adhesion and wet adhesion are grade 0, respectively. The corrosion current density is 7.58×10~(-8) A/cm~2, and the electrochemical impedance value reaches 3.4×10~6 Ω·cm~2.
引文
[1]EDUOK U,FAYE O,SZPUNAR J.Recent developments and applications of protective silicone coatings:A review of PDMS functional materials[J].Progress in Organic Coatings,2017,111:124-163.
[2]KENDIG M,MILLS D J.An historical perspective on the corrosion protection by paints[J].Progress in Organic Coatings,2017,102:53-59.
[3]邵鸿飞,高翔,冀克俭,等.冷轧钢表面植酸-硅烷双膜复合层的耐蚀性能[J].中国表面工程,2018,31(2):122-129.SHAO H F,GAO X,JI K J,et al.Anti-corrosion performance of phytic acid-silane composite coating on cold-rolled steels[J].China Surface Engineering,2018,31(2):122-129(in Chinese).
[4]向美苏,李非,张延宗.溶胶凝胶法制备甲基三甲氧基硅烷-γ-(2,3-环氧丙氧)丙基三甲氧基硅烷复合超疏水涂层[J].涂料工业,2017,47(1):1-11.XIANG M S,LI F,ZHANG Y Z.Preparation of MTMS-KH560 complex superhydrophobic coatings by sol-gel method[J].Paint&Coatings Industry,2017,47(1):1-11(in Chinese).
[5]任志威,董泽.有机-无机杂化聚硅氧烷涂层的制备及其常温固化研究[J].涂料工业,2017,47(4):1-5.REN Z W,DONG Z.Preparation and curing behavior of organic-Inorganic hybrid polysiloxane coatings[J].Paint&Coatings Industry,2017,47(4):1-5(in Chinese).
[6]ZHANG Y J,SHAO Y W,LIU X L,et al.A study on corrosion protection of different polyaniline coatings for mild[J].Progress in Organic Coatings,2017,111:240-247.
[7]FU T Z,LIU J,WANG J,et al.Cure kinetics and conductivity of rigid rod epoxy with polyaniline as a curing agent[J].Polymer Composites,2009,10:1394-1400.
[8]ZAAREI D,SARABI A A,SHARIF F,et al.A new approach to using submicron emeraldine-base polyaniline in corrosion-resistant epoxy coatings[J].Journal of Coatings Technology and Research,2012,9(1):47-57.
[9]YAO B,WANG G C,LI X W,et al.Anticorrosive properties of epoxy resin coatings cured by aniline/p-phenylenediamine copolymer[J].Journal of Applied Polymer Science,2009,10(1002):1988-1993.
[10]SIVA T,KAMARAJ K,SATHIYANARAYANAN S.Epoxy curing by polyaniline(PANI)-characterization and self-healing evaluation[J].Progress in Organic Coatings,2014,77:1095-1103.
[11]GAO X H,JING X Y,LI Y F,et al.Synthesis and characterization of phosphorized polyaniline doped with phytic acid and its anticorrosion properties for Mg-Li alloy[J].Journal of Macromolecular Science,Part A:Pure and Applied Chemistry,2017,1:24-35.
[12]胡杰,蔡智奇,文秀芳.耐高温油墨用清漆的制备[J].电镀与涂饰,2014,33(2):46-50.HU J,CAI Z Q,WEN X F.Preparation of varnish for hightemperature resistant ink[J].Electroplating and Finishing,2014,33(2):46-50(in Chinese).
[13]SULEIMAN R,ESTAITIE M,MIZANURAHMAN M.Hybrid organosiloxane coatings containing epoxide precursors for protecting mild steel against corrosion in a saline medium[J].Applied Polymer,2016,133(38):1-11.
[14]ZHANG L,SHI Z,HU W H,et al.Curing mechanism,heat resistance,and anticorrosion properties of a furan/methyl phenyl silicone coating[J].Polymers for Advanced Technologies,2018:1-9.
[15]JOVANOVIC J D,GOVEDARICA M N,DVORNIC P R.The thermogravimetric analysis of some polysiloxanes[J].Polymer Degradation and Stability,1998(61):87-93.
[2]KENDIG M,MILLS D J.An historical perspective on the corrosion protection by paints[J].Progress in Organic Coatings,2017,102:53-59.
[3]邵鸿飞,高翔,冀克俭,等.冷轧钢表面植酸-硅烷双膜复合层的耐蚀性能[J].中国表面工程,2018,31(2):122-129.SHAO H F,GAO X,JI K J,et al.Anti-corrosion performance of phytic acid-silane composite coating on cold-rolled steels[J].China Surface Engineering,2018,31(2):122-129(in Chinese).
[4]向美苏,李非,张延宗.溶胶凝胶法制备甲基三甲氧基硅烷-γ-(2,3-环氧丙氧)丙基三甲氧基硅烷复合超疏水涂层[J].涂料工业,2017,47(1):1-11.XIANG M S,LI F,ZHANG Y Z.Preparation of MTMS-KH560 complex superhydrophobic coatings by sol-gel method[J].Paint&Coatings Industry,2017,47(1):1-11(in Chinese).
[5]任志威,董泽.有机-无机杂化聚硅氧烷涂层的制备及其常温固化研究[J].涂料工业,2017,47(4):1-5.REN Z W,DONG Z.Preparation and curing behavior of organic-Inorganic hybrid polysiloxane coatings[J].Paint&Coatings Industry,2017,47(4):1-5(in Chinese).
[6]ZHANG Y J,SHAO Y W,LIU X L,et al.A study on corrosion protection of different polyaniline coatings for mild[J].Progress in Organic Coatings,2017,111:240-247.
[7]FU T Z,LIU J,WANG J,et al.Cure kinetics and conductivity of rigid rod epoxy with polyaniline as a curing agent[J].Polymer Composites,2009,10:1394-1400.
[8]ZAAREI D,SARABI A A,SHARIF F,et al.A new approach to using submicron emeraldine-base polyaniline in corrosion-resistant epoxy coatings[J].Journal of Coatings Technology and Research,2012,9(1):47-57.
[9]YAO B,WANG G C,LI X W,et al.Anticorrosive properties of epoxy resin coatings cured by aniline/p-phenylenediamine copolymer[J].Journal of Applied Polymer Science,2009,10(1002):1988-1993.
[10]SIVA T,KAMARAJ K,SATHIYANARAYANAN S.Epoxy curing by polyaniline(PANI)-characterization and self-healing evaluation[J].Progress in Organic Coatings,2014,77:1095-1103.
[11]GAO X H,JING X Y,LI Y F,et al.Synthesis and characterization of phosphorized polyaniline doped with phytic acid and its anticorrosion properties for Mg-Li alloy[J].Journal of Macromolecular Science,Part A:Pure and Applied Chemistry,2017,1:24-35.
[12]胡杰,蔡智奇,文秀芳.耐高温油墨用清漆的制备[J].电镀与涂饰,2014,33(2):46-50.HU J,CAI Z Q,WEN X F.Preparation of varnish for hightemperature resistant ink[J].Electroplating and Finishing,2014,33(2):46-50(in Chinese).
[13]SULEIMAN R,ESTAITIE M,MIZANURAHMAN M.Hybrid organosiloxane coatings containing epoxide precursors for protecting mild steel against corrosion in a saline medium[J].Applied Polymer,2016,133(38):1-11.
[14]ZHANG L,SHI Z,HU W H,et al.Curing mechanism,heat resistance,and anticorrosion properties of a furan/methyl phenyl silicone coating[J].Polymers for Advanced Technologies,2018:1-9.
[15]JOVANOVIC J D,GOVEDARICA M N,DVORNIC P R.The thermogravimetric analysis of some polysiloxanes[J].Polymer Degradation and Stability,1998(61):87-93.