疏水改性氧化石墨烯/环氧复合涂料的制备及其防腐性能研究
|
摘要
以叔碳酸缩水甘油酯(E-10P)为疏水单体,通过环氧与羧酸的共价键合,在氧化石墨烯(GO)表面引入疏水性支化碳链,改性后的氧化石墨烯(F-GO)作为防锈填料加入环氧树脂中得到FGO/环氧复合涂料。通过红外光谱、拉曼光谱、X-射线衍射、热重分析对F-GO的结构进行表征,通过场发射扫描电镜观察F-GO及复合涂料的微观形貌,并通过电化学阻抗、极化曲线和盐雾试验测试了复合涂料的防腐性能。结果表明:E-10P可利用其空间效应阻碍片层的团聚;疏水效应可提高F-GO的热稳定性和与环氧树脂的相容性;与空白环氧涂层相比,当复合涂料中F-GO质量分数为0.2%时,厚度为20~25μm的防腐涂层的腐蚀电流可由2.358 6×10~(-6)A/cm~2下降至2.000 2×10~(-11)A/cm~2,阻抗值可由1.1×107Ω·cm~2提升至6.9×10~9Ω·cm~2。
A highly branched hydrophobic carbon chain is introduced on the surface of graphene oxide( GO) by the covalent bonding of epoxy and carboxylic acid,wherein,glycidyl ester( Cardura TM E-10 P) is used as a hydrophobic monomer. The modified graphene oxide( FGO) is added as an anti-rust filler to epoxy resin to obtain the F-GO/epoxy composite material. Structural properties are characterized by Fourier transform infrared spectrometer( FT-IR),Raman spectroscopy,X-ray diffraction( XRD) and Thermal gravimetric( TG). In addition,morphological properties are observed with Field-emission scanning electron microscopy( FE-SEM). The corrosion behaviors of the coated steel substrates are evaluated by Neutral salt spray( NSS) and Electrochemical measurements. The results show that E-10 P can inhibit the agglomeration of lamellae by its steric effect. The hydrophobic effect enhances the thermal stability of F-GO and compatibility of epoxy resin. When the additive amount of the composite is 0. 2%,the corrosion current of anti-corrosive coating with a thickness of 20-25 μm can be reduced from 2. 358 6×10~(-6) A/cm~2 to 2. 000 2×10~(-11) A/cm~2 and the impedance value can be increased from 1. 1×10~7Ω·cm~2 to 6. 9×109Ω·cm~2.
A highly branched hydrophobic carbon chain is introduced on the surface of graphene oxide( GO) by the covalent bonding of epoxy and carboxylic acid,wherein,glycidyl ester( Cardura TM E-10 P) is used as a hydrophobic monomer. The modified graphene oxide( FGO) is added as an anti-rust filler to epoxy resin to obtain the F-GO/epoxy composite material. Structural properties are characterized by Fourier transform infrared spectrometer( FT-IR),Raman spectroscopy,X-ray diffraction( XRD) and Thermal gravimetric( TG). In addition,morphological properties are observed with Field-emission scanning electron microscopy( FE-SEM). The corrosion behaviors of the coated steel substrates are evaluated by Neutral salt spray( NSS) and Electrochemical measurements. The results show that E-10 P can inhibit the agglomeration of lamellae by its steric effect. The hydrophobic effect enhances the thermal stability of F-GO and compatibility of epoxy resin. When the additive amount of the composite is 0. 2%,the corrosion current of anti-corrosive coating with a thickness of 20-25 μm can be reduced from 2. 358 6×10~(-6) A/cm~2 to 2. 000 2×10~(-11) A/cm~2 and the impedance value can be increased from 1. 1×10~7Ω·cm~2 to 6. 9×109Ω·cm~2.
引文
[1]POURHASHEM S,RASHIDI A,VAZEI M R,et al.Excellent corrosion protection performance of epoxy composite coatings filled with amino-silane functionalized graphene oxide[J].Surface and Coatings Technology,2017,317:1-9.
[2]LI J,CUI J C,YANG J Y,et al.Reinforcement of graphene and its derivatives on the anticorrosive properties of waterborne polyurethane coatings[J].Composites Science and Technology,2016,129:30-37.
[3]马圣乾,裴立振,康英杰.石墨烯研究进展[J].现代物理知识,2009,21(4):44-47.
[4]罗健,王继虎,温绍国,等.石墨烯在防腐涂料中的研究进展[J].涂料工业,2017,47(11):69-76.
[5]ZHANG Z,ZHANG W,LI D,et al.Mechanical and anticorrosive properties of graphene/epoxy resin composites coating prepared by in-situ method.[J].International Journal of Molecular Sciences,2015,16(1):2239-2251.
[6]YU Z X,DI H H,MA Y,et al.Fabrication of graphene oxide-alumina hybrids to reinforce the anti-corrosion performance of composite epoxy coatings[J].Applied Surface Science,2015,351:986-996.
[7]ZHENG H P,SHAO Y W,WANG Y Q,et al.Reinforcing the corrosion protection property of epoxy coating by using graphene oxide-poly(urea-formaldehyde)composites[J].Corrosion Science,2017,123:267-277.
[8]GUERRERO-CONTRERAS J,CABALLERO-BRIONES F.Graphene oxide powders with different oxidation degree,prepared by synthesis variations of the Hummers method[J].Materials Chemistry and Physics,2015,153:209-220.
[9]GEIM A K,NOVOSELOV K S.The rise of graphene[J].Nature Materials,2007,6(3):183-191.
[10]彭博,李聪,池航,等.PEDOT/石墨烯复合材料的制备及其抗静电性能研究[J].涂料工业,2017,47(5):17-23.
[11]KUDIN K N,OZBAS B,SCHNIEPP H C,et al.Raman spectra of graphite oxide and functionalized graphene sheets[J].Nano Lett,2008,8(1):36-41.
[12]XUE Y H,LIU Y,LU F,et al.Functionalization of graphene oxide with polyhedral oligomeric silsesquioxane(POSS)for multifunctional applications[J].The Journal of Physical Chemistry Letters,2012,3(12):1607-1612.
[13]YANG H F,LI F H,SHAN C S,et al.Covalent functionalization of chemically converted graphene sheets via silane and its reinforcement[J].Journal of Materials Chemistry,2009,19(26):4632-4638.
[14]SHENG X X,CAI W X,ZHONG L,et al.Synthesis of functionalized graphene/polyaniline nanocomposites with effective synergistic reinforcement on anticorrosion[J].Industrial&Engineering Chemistry Research,2016,55(31):8576-8585.
[15]TREOSSI E,MELUCCI M,LISCIO A,et al.Highcontrast visualization of graphene oxide on dye-sensitized glass,quartz,and silicon by fluorescence quenching.[J].Journal of the American Chemical Society,2009,131(43):15576-15577.
[16]曹楚南,张鉴清.电化学阻抗谱导论[M].北京:科学出版社,2002.
[2]LI J,CUI J C,YANG J Y,et al.Reinforcement of graphene and its derivatives on the anticorrosive properties of waterborne polyurethane coatings[J].Composites Science and Technology,2016,129:30-37.
[3]马圣乾,裴立振,康英杰.石墨烯研究进展[J].现代物理知识,2009,21(4):44-47.
[4]罗健,王继虎,温绍国,等.石墨烯在防腐涂料中的研究进展[J].涂料工业,2017,47(11):69-76.
[5]ZHANG Z,ZHANG W,LI D,et al.Mechanical and anticorrosive properties of graphene/epoxy resin composites coating prepared by in-situ method.[J].International Journal of Molecular Sciences,2015,16(1):2239-2251.
[6]YU Z X,DI H H,MA Y,et al.Fabrication of graphene oxide-alumina hybrids to reinforce the anti-corrosion performance of composite epoxy coatings[J].Applied Surface Science,2015,351:986-996.
[7]ZHENG H P,SHAO Y W,WANG Y Q,et al.Reinforcing the corrosion protection property of epoxy coating by using graphene oxide-poly(urea-formaldehyde)composites[J].Corrosion Science,2017,123:267-277.
[8]GUERRERO-CONTRERAS J,CABALLERO-BRIONES F.Graphene oxide powders with different oxidation degree,prepared by synthesis variations of the Hummers method[J].Materials Chemistry and Physics,2015,153:209-220.
[9]GEIM A K,NOVOSELOV K S.The rise of graphene[J].Nature Materials,2007,6(3):183-191.
[10]彭博,李聪,池航,等.PEDOT/石墨烯复合材料的制备及其抗静电性能研究[J].涂料工业,2017,47(5):17-23.
[11]KUDIN K N,OZBAS B,SCHNIEPP H C,et al.Raman spectra of graphite oxide and functionalized graphene sheets[J].Nano Lett,2008,8(1):36-41.
[12]XUE Y H,LIU Y,LU F,et al.Functionalization of graphene oxide with polyhedral oligomeric silsesquioxane(POSS)for multifunctional applications[J].The Journal of Physical Chemistry Letters,2012,3(12):1607-1612.
[13]YANG H F,LI F H,SHAN C S,et al.Covalent functionalization of chemically converted graphene sheets via silane and its reinforcement[J].Journal of Materials Chemistry,2009,19(26):4632-4638.
[14]SHENG X X,CAI W X,ZHONG L,et al.Synthesis of functionalized graphene/polyaniline nanocomposites with effective synergistic reinforcement on anticorrosion[J].Industrial&Engineering Chemistry Research,2016,55(31):8576-8585.
[15]TREOSSI E,MELUCCI M,LISCIO A,et al.Highcontrast visualization of graphene oxide on dye-sensitized glass,quartz,and silicon by fluorescence quenching.[J].Journal of the American Chemical Society,2009,131(43):15576-15577.
[16]曹楚南,张鉴清.电化学阻抗谱导论[M].北京:科学出版社,2002.