三聚磷酸铝/氧化石墨烯复合材料在水性防腐涂料中的应用
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摘要
采用球磨分散法制备得到三聚磷酸铝/氧化石墨烯水性复合防腐浆料(AlTP/GO),并与水性环氧树脂复配制得纳米复合防腐涂料(EP-AlTP/GO)。通过场发射扫描电镜(FE-SEM)观测到AlTP/GO可均匀分散到EP树脂内部。吸水率测试结果表明,氧化石墨烯的引入提高了涂层的耐水性和屏蔽性能;附着强度测试结果表明,三聚磷酸铝可提高涂层在金属基材上的附着强度;电化学测试(Bode)和环境扫描电镜测试(E-SEM)结果表明,AlTP/GO可有效增强水性环氧涂层对腐蚀介质的屏蔽作用,限制了腐蚀反应的扩散,在3.5%NaCl水溶液中浸泡40 d后其低频阻抗达到7.02×10~7Ω·cm~2,盐雾测试400 h后金属表面平滑,金属腐蚀未发生明显扩散,EP-AlTP/GO人工破损处周边含氧量低至15.66%,遏制了氧化铁的形成。
The water-based aluminum triphosphate/graphene oxide composite anticorrosion pigment millbase was prepared by ball-mill dispersion and then was formulated with a water-based epoxy resin to prepare EP-AlTP/GO nanocomposite coatings. The AlTP/GO could be evenly dispersed into EP resin which was observed by field emission scanning electron microscopy(FE-SEM). The water absorption test showed that the incorporation of graphene oxide improved the water resistance and barrierperformance of the coatings. The adhesion test results showed that aluminum triphosphate could improve the adhesion of the coatings on metal substrates. Electrochemical test(Bode)and environmental scanning electron microscopy test(E-SEM)showed that AlTP/GO effectively enhanced the barrier performance of water-based epoxy coatings to corrosion medium and limited the spreading of the corrosion reaction. The low frequency impedance was 7.02×10~7Ω cm~2 after immersion at 3.5 wt.%NaCl aqueous solution for 40 days,the metal surface remained smooth after salt spray test 400 h. EDX test showed that AlTP/GO could inhibitthe formation of iron oxide,the oxygen content around the damaged area of EP-AlTP/GO was as low as 15.66%.
The water-based aluminum triphosphate/graphene oxide composite anticorrosion pigment millbase was prepared by ball-mill dispersion and then was formulated with a water-based epoxy resin to prepare EP-AlTP/GO nanocomposite coatings. The AlTP/GO could be evenly dispersed into EP resin which was observed by field emission scanning electron microscopy(FE-SEM). The water absorption test showed that the incorporation of graphene oxide improved the water resistance and barrierperformance of the coatings. The adhesion test results showed that aluminum triphosphate could improve the adhesion of the coatings on metal substrates. Electrochemical test(Bode)and environmental scanning electron microscopy test(E-SEM)showed that AlTP/GO effectively enhanced the barrier performance of water-based epoxy coatings to corrosion medium and limited the spreading of the corrosion reaction. The low frequency impedance was 7.02×10~7Ω cm~2 after immersion at 3.5 wt.%NaCl aqueous solution for 40 days,the metal surface remained smooth after salt spray test 400 h. EDX test showed that AlTP/GO could inhibitthe formation of iron oxide,the oxygen content around the damaged area of EP-AlTP/GO was as low as 15.66%.
引文
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[3] FRAU A,PERNITES R B,ADVINCULA R C. A Conjugated polymer network approach to anticorrosion coatings:poly(vinylcarbazole)electrodeposition[J]. Industrial&Engineering Chemistry Research,2010,49(20):9789-9797.
[4] CHANG K C,HSU M H,LU H I. Room-temperature cured hydrophobic epoxy/graphene composites as corrosion inhibitor for cold-rolled steel[J]. Carbon,2014,66:144-153.
[5] LIU M,MAO X H,ZHU H,et al. Water and corrosion resistance of epoxy-acrylic-amine waterborne coatings:Effects of resin molecular weight,polar group and hydrophobic segment[J]. Corrosion Science,2013,75(7):106-113.
[6]吴校彬,付和,青黄洪,等.防腐涂料用水性聚氨酯-环氧树脂-丙烯酸酯复合分散液的合成与性能[J].腐蚀科学与防护技术,2007,19(4):296-299.
[7] SHUI X J,SHEN Y D,FEI G Q,et al. The effect of nonionic monomer ham on properties of cationic surfactant-free acrylic/alkyd hybrid emulsion[J]. Journal of Applied Polymer Science,2015,132(5):41406-41414.
[8] SABABI M,PAN J,AUGUSTSSON P E,et al. Influence of polyaniline and ceria nanoparticle additives on corrosion protection of a UV-cure coating on carbon steel[J]. Corrosion Science,2014,84(3):189-197.
[9]袁爱群,房伟,白丽娟,等.第二代无毒活性磷酸盐防腐颜料的研究进展[J].涂料工业,2008,38(8):68-71.
[10] BERRY V. Impermeability of graphene and its applications[J].Carbon,2013,62:1-10.
[11] QI K,SUN Y M,DUAN H W,et al. A corrosion-protective coating based on a solution-processable polymer-grafted graphene oxide nanocomposite[J]. Corrosion Science,2015,98:500-506.
[12] LI J Y,LI X R,ZHU K,et al. Reinforcement of phosphorylated graphene oxide on the anticorrosive properties of waterborne acrylate-epoxy resin coatings[J]. Journal of Macromolecular Science,Part A:Pure and Applied Chemistry,2018,55(9):649-657.
[13] CHEN C L,HE Y,XIAO G Q,et al. Synergistic effect of graphene oxide@phosphate-intercalated hydrotalcite for improved anti-corrosion and self-healable protection of waterborne epoxy coating in salt environments[J]. Journal of Materials Chemistry C,2019(7):2318-2326.
[14]朱科,李小瑞,李菁熠,等.水性异氰酸酯改性石墨烯/聚氨酯复合乳液防腐性能研究[J].功能材料,2016,47(6):6016-6021.
[15] WANG X,XING W Y,SONG L,et al. Preparation of UVcurable functionalized graphene/polyurethane acrylate nanocomposite with enhanced thermal and mechanical behaviors[J].Reactive&Functional Polymers,2013,73:854-858.
[16] POURHASHM S,RASHIDI A,VAEZI M R,et al. Excellent corrosion protection performance of epoxy composite coatings filled with amino-silane functionalized graphene oxide[J].Surface&Coatings Technology,2017,317:1-9.
[17] ZHU K,LI X R,WANG H H,et al. Electrochemical and anticorrosion behaviors of water dispersible graphene/acrylic modified alkyd resin latex composites coated carbon steel[J].Journal of Applied Polymer Science,2017,134:44445-44456.
[18] LOVEDAY D,PETERSON P,RODGER B S,Evaluation of organic coatings with electrochemical impedance apectroscopy,part 2:application of eis to coatings[J]. JCT Coating Tech,2004,1:46-52.
[19] GRAY L G,APPLEMAN B R. EIS electrochemical impedance spectroscopy-a tool to predict remaining coating life[J]. Journal of Protective Coatings&Linings,2003,20(2):66-74.
[20] ECCO L,FEDEL M,DEFLORIAN F,et al. Waterborne acrylic paint system based on nanoceria for corrosion protection of steel[J]. Progress in Organic Coatings,2016,96:19-25.
[21]张丽,霍东霞,刘大壮,等.三聚磷酸铝在水性乳胶涂层中的防锈机理研究[J].腐蚀科学与防护技术,2004,16(5):328-330.