铝合金类水滑石/微弧氧化复合膜层的超疏水及耐蚀性能
|
摘要
为解决铝合金表面耐蚀性差的问题,采用两种方法在铝合金表面制备一种复合膜层。首先利用微弧氧化(MAO)技术在铝合金表面原位生长陶瓷层。然后利用化学方法在陶瓷层表面原位生长出类水滑石薄膜(LDH)。最后利用硬脂酸对复合膜层进行表面修饰,以达到超疏水表面。利用扫描电镜(SEM)、 X射线衍射(XRD)、接触角测量仪及电化学工作站分别分析了微弧氧化陶瓷层及复合膜层的表面形貌、物相结构、疏水性以及耐腐蚀性能。结果表明:类水滑石片层物将微弧氧化陶瓷层的缺陷(微孔及微裂纹)完全封闭,并且制备的复合膜层构建出了微/纳二元结构。经表面修饰剂修饰后复合膜层的接触角为155.2°,而微弧氧化陶瓷层的接触角为17.5°。利用电化学工作站测试的极化曲线结果显示,超疏水复合膜层的腐蚀电流密度比微弧氧化陶瓷层降低了约两个数量级;而阻抗图谱分析表明,超疏水复合膜层具有更优异的耐蚀性。
In order to solve the poor corrosion resistance of aluminum alloy surface, two methods were used to prepare a composite film on the surface of aluminum alloy. Firstly, the ceramic layer was grown in situ on the surface of aluminum alloy by micro-arc oxidation(MAO). Then the hydrotalcite-like film(LDH) film was grown in situ on the surface of ceramic layer by chemical method. Finally, the composite film surface was modified with stearic acid to achieve superhydrophobic surface. The surface morphology, phase structure, hydrophobicity and corrosion resistance of MAO ceramic layer and composite film were analyzed by scanning electron microscope(SEM), X-ray diffraction(XRD), contact angle measuring instrument and electrochemical workstation, respectively. The results showed that the micro-pores and micro-cracks of MAO ceramic layer were completely closed by LDH nano-sheet. Simultaneously, the micro/nano structure was built by the composite film. In addition, the contact angle of composite film after modification was 155.2°, while the MAO ceramic layer was 17.5 °. The results of the dynamic potential polarization curve showed that the corrosion current density of superhydrophobic composite film was reduced by 1～2 orders of magnitude than that of MAO ceramic layer. Similarly, the impedance spectra showed that the superhydrophobic composite film had more excellent corrosion resistance.
In order to solve the poor corrosion resistance of aluminum alloy surface, two methods were used to prepare a composite film on the surface of aluminum alloy. Firstly, the ceramic layer was grown in situ on the surface of aluminum alloy by micro-arc oxidation(MAO). Then the hydrotalcite-like film(LDH) film was grown in situ on the surface of ceramic layer by chemical method. Finally, the composite film surface was modified with stearic acid to achieve superhydrophobic surface. The surface morphology, phase structure, hydrophobicity and corrosion resistance of MAO ceramic layer and composite film were analyzed by scanning electron microscope(SEM), X-ray diffraction(XRD), contact angle measuring instrument and electrochemical workstation, respectively. The results showed that the micro-pores and micro-cracks of MAO ceramic layer were completely closed by LDH nano-sheet. Simultaneously, the micro/nano structure was built by the composite film. In addition, the contact angle of composite film after modification was 155.2°, while the MAO ceramic layer was 17.5 °. The results of the dynamic potential polarization curve showed that the corrosion current density of superhydrophobic composite film was reduced by 1～2 orders of magnitude than that of MAO ceramic layer. Similarly, the impedance spectra showed that the superhydrophobic composite film had more excellent corrosion resistance.
引文
[1] Starke Jr E A, Staley J T. Application of modern aluminum alloys to aircraft [J]. Prog. Aerosp., 1996, 32: 131.
[2] Zhao J M, Wang Y H, Zhang X F, Zuo Y. Preparation of hydrophilic anticorrosion film on aluminum alloy by sol-gel process [J]. Materials Protection, 2005, 3: 6.(赵景茂, 王禹慧, 张晓丰, 左禹. 利用溶胶-凝胶法制备铝合金耐蚀亲水涂膜[J]. 材料保护, 2005, 3: 6.)
[3] Wang C L, Zhang G Y, Gao Y, Song Y Z. Mechanism of Y2O3 affecting laser cladding of Ni-based coating on 6063 Al alloy substrate [J]. Chinese Journal of Rare Metals, 2016, 40(3): 201.(王成磊, 张光耀, 高原, 宋沂泽. Y2O3在6063铝合金表面激光熔覆Ni基熔覆层中的作用机制 [J]. 稀有金属, 2016, 40(3): 201.)
[4] Han D F, Lu D R, Zhou Y. Corrosion resistance of nickel electroplating on aluminum alloy [J]. Journal of Fudan University (Natural Science), 2012, 51(2): 222.(韩登峰, 鲁道荣, 周洋. 铝合金表面电镀镍的耐腐蚀性能 [J]. 复旦大学(自然科学版), 2012, 51(2): 222.)
[5] Tang T T, Dang P L, Zhao Q, Wang F. Different pretreatments and optimization of electroless nickel plating on aluminum alloy [J]. Journal of Materials Science and Engineering, 2017, 35(5): 820.(唐田田, 党沛淋, 赵倩, 王芳. 铝合金表面预处理及其镀镍工艺优化 [J]. 材料科学与工程学报, 2017, 35(5): 820.)
[6] Zhou K K, Huang Y B, Sang H R, Liu Q, Ba G Z. Effect of aluminum alloy anodic oxidation film structure on the adhesive property [J]. Surface Technology, 2016, 9: 188.(周科可, 黄燕滨, 桑浩然, 刘谦, 巴国召. 铝合金阳极氧化膜层结构对粘接性能的影响 [J]. 表面技术, 2016, 9: 188.)
[7] Xin T Z. Research on the Formation and Mechanism of Ceramic Coating Prepared by Micro-arc Oxidation on Surface of Aluminum Alloy [D]. Harbin: Harbin Institute of Technology, 2006. 21.(辛铁柱. 铝合金表面微弧氧化陶瓷膜生成及机理的研究 [D]. 哈尔滨: 哈尔滨工业大学, 2006. 21.)
[8] Dan M, Tong H H, Shen L R, Jin F Y, Li J. Enhancement of corrosion resistance of aluminum alloy through compound surfacetreatment of micro-arcoxidation and sol-gel [J]. Transactions of Materials and Heat Treatment, 2011, 32(8): 132.(但敏, 童洪辉, 沈丽如, 金凡亚, 李炯. 微弧氧化-溶胶凝胶复合表面技术改善铝合金的耐腐蚀性能 [J]. 材料热处理学报, 2011, 32(8): 132.
[9] Zhang Y J, Yao Z P, Xia Q X, Qi S F, Jiang Z H. Corrosion resistance of micro-arc oxidation/air sprayed composite coatingson magnesium alloy [J]. Materials Protection, 2011, 44(6): 25.(张亚军, 姚忠平, 夏琦兴, 齐素芳, 姜兆华. 镁合金微弧氧化/空气喷涂复合膜层的耐盐雾腐蚀性能 [J]. 材料保护, 2011, 44(6): 25.)
[10] Shi H Y, Dong L F, Jiang B L, Shen W N, Ge Y F. Microstructuce and corrosion propertise of micro-arc oxidation composite electrophoreti coating on AZ31B magnesium alloy [J]. Rare Metal Materials and Engineering, 2015, 44(7): 1679.(时惠英, 董利芳, 蒋百灵, 沈文宁, 葛延峰. AZ31B镁合金表面微弧电泳复合膜层微观结构及耐蚀性表征 [J]. 稀有金属材料与工程, 2015, 44(7): 1679.)
[11] Chen H Y, Zhang F Z, Fu S S, Duan X. In situ microstructure control of oriented layered double hydroxide monolayer films with curved hexagonal crystals as superhydrophobic materials [J]. ChemInform, 2006, 18(23): 3089.
[12] Wang J, Li D D, Liu Q, Yin X, Yin X, Zhang Y, Jing X Y, Zhang M L. Fabrication of hydrophobic surface with hierarchical structure on Mg alloy and its corrosion resistance [J]. Electrochimica Acta, 2010, 55(22): 6897.
[13] Guo Y G, Wang Q H, Wang T M. Facile fabrication of superhydrophobic surface with micro/nanoscale binary structures on aluminum substrate [J]. Applied Surface Science, 2011, 257(13): 5834.
[14] Wang S X, Zhao Q, Zhang X M, Liu D X, Du N. Effect of Cr2O3 macroparticle on microstructure and tribological behavior of microarc oxidation coating on Ti6Al4V alloy [J]. Transactions of Materials and Heat Treatment, 2014, 35(2): 180.(王帅星, 赵晴, 张小明, 刘道新, 杜楠. Cr2O3微粒对Ti6Al4V微弧氧化膜结构及磨损行为的影响 [J]. 材料热处理学报, 2014, 35(2): 180.)
[15] Wei T B, Guo B G, Liang J, Yan F Y, Tian J. Tribological properties of micro-arc oxidation coatings on Al alloy [J]. Journal of Materials Science and Engineering, 2004, 22(4): 564.(魏同波, 郭宝刚, 梁军, 阎逢元, 田军. 铝合金微弧氧化陶瓷膜的性能研究 [J]. 材料科学与工程学报, 2004, 22(4): 564.)
[16] Chen F, Yu P H, Zhang Y. Healing effects of LDHs nanoplatelets on MAO ceramic layer of aluminum alloy [J]. Journal of Alloys and Compounds, 2017, 711: 342.
[17] Liu X H, Zhu L Q, Liu H C, Li W P. Investigation of MAO coating growth mechanism on aluminum alloy by two-step oxidation method [J]. Applied Surface Science, 2014, 293: 12.
[18] Mohannad M S, Al Bosta, Ma Kung-Jeng. Suggested mechanism for the MAO ceramiccoating on aluminium substrates using bipolar current mode in the alkaline silicate electrolytes [J]. Applied Surface Science, 2014, 308: 121.
[19] Tillous E K, Toll-Duchanoy T, Bauer-Grosse E. Microstructure and 3D microtomographic characterization of porosity of MAO surface layers formed on aluminium and 2214-T6 alloy [J]. Surface and Coatings Technology, 2009, 203(13): 1850.
[20] Zhang F, Zhao L, Chen H, Xu S, Evans D G, Duan X. Corrosion resistance of superhydrophobic layered double hydroxide films on aluminum [J]. Angew. Chem. Int. Ed. Eng., 2008, 47: 2466.
[2] Zhao J M, Wang Y H, Zhang X F, Zuo Y. Preparation of hydrophilic anticorrosion film on aluminum alloy by sol-gel process [J]. Materials Protection, 2005, 3: 6.(赵景茂, 王禹慧, 张晓丰, 左禹. 利用溶胶-凝胶法制备铝合金耐蚀亲水涂膜[J]. 材料保护, 2005, 3: 6.)
[3] Wang C L, Zhang G Y, Gao Y, Song Y Z. Mechanism of Y2O3 affecting laser cladding of Ni-based coating on 6063 Al alloy substrate [J]. Chinese Journal of Rare Metals, 2016, 40(3): 201.(王成磊, 张光耀, 高原, 宋沂泽. Y2O3在6063铝合金表面激光熔覆Ni基熔覆层中的作用机制 [J]. 稀有金属, 2016, 40(3): 201.)
[4] Han D F, Lu D R, Zhou Y. Corrosion resistance of nickel electroplating on aluminum alloy [J]. Journal of Fudan University (Natural Science), 2012, 51(2): 222.(韩登峰, 鲁道荣, 周洋. 铝合金表面电镀镍的耐腐蚀性能 [J]. 复旦大学(自然科学版), 2012, 51(2): 222.)
[5] Tang T T, Dang P L, Zhao Q, Wang F. Different pretreatments and optimization of electroless nickel plating on aluminum alloy [J]. Journal of Materials Science and Engineering, 2017, 35(5): 820.(唐田田, 党沛淋, 赵倩, 王芳. 铝合金表面预处理及其镀镍工艺优化 [J]. 材料科学与工程学报, 2017, 35(5): 820.)
[6] Zhou K K, Huang Y B, Sang H R, Liu Q, Ba G Z. Effect of aluminum alloy anodic oxidation film structure on the adhesive property [J]. Surface Technology, 2016, 9: 188.(周科可, 黄燕滨, 桑浩然, 刘谦, 巴国召. 铝合金阳极氧化膜层结构对粘接性能的影响 [J]. 表面技术, 2016, 9: 188.)
[7] Xin T Z. Research on the Formation and Mechanism of Ceramic Coating Prepared by Micro-arc Oxidation on Surface of Aluminum Alloy [D]. Harbin: Harbin Institute of Technology, 2006. 21.(辛铁柱. 铝合金表面微弧氧化陶瓷膜生成及机理的研究 [D]. 哈尔滨: 哈尔滨工业大学, 2006. 21.)
[8] Dan M, Tong H H, Shen L R, Jin F Y, Li J. Enhancement of corrosion resistance of aluminum alloy through compound surfacetreatment of micro-arcoxidation and sol-gel [J]. Transactions of Materials and Heat Treatment, 2011, 32(8): 132.(但敏, 童洪辉, 沈丽如, 金凡亚, 李炯. 微弧氧化-溶胶凝胶复合表面技术改善铝合金的耐腐蚀性能 [J]. 材料热处理学报, 2011, 32(8): 132.
[9] Zhang Y J, Yao Z P, Xia Q X, Qi S F, Jiang Z H. Corrosion resistance of micro-arc oxidation/air sprayed composite coatingson magnesium alloy [J]. Materials Protection, 2011, 44(6): 25.(张亚军, 姚忠平, 夏琦兴, 齐素芳, 姜兆华. 镁合金微弧氧化/空气喷涂复合膜层的耐盐雾腐蚀性能 [J]. 材料保护, 2011, 44(6): 25.)
[10] Shi H Y, Dong L F, Jiang B L, Shen W N, Ge Y F. Microstructuce and corrosion propertise of micro-arc oxidation composite electrophoreti coating on AZ31B magnesium alloy [J]. Rare Metal Materials and Engineering, 2015, 44(7): 1679.(时惠英, 董利芳, 蒋百灵, 沈文宁, 葛延峰. AZ31B镁合金表面微弧电泳复合膜层微观结构及耐蚀性表征 [J]. 稀有金属材料与工程, 2015, 44(7): 1679.)
[11] Chen H Y, Zhang F Z, Fu S S, Duan X. In situ microstructure control of oriented layered double hydroxide monolayer films with curved hexagonal crystals as superhydrophobic materials [J]. ChemInform, 2006, 18(23): 3089.
[12] Wang J, Li D D, Liu Q, Yin X, Yin X, Zhang Y, Jing X Y, Zhang M L. Fabrication of hydrophobic surface with hierarchical structure on Mg alloy and its corrosion resistance [J]. Electrochimica Acta, 2010, 55(22): 6897.
[13] Guo Y G, Wang Q H, Wang T M. Facile fabrication of superhydrophobic surface with micro/nanoscale binary structures on aluminum substrate [J]. Applied Surface Science, 2011, 257(13): 5834.
[14] Wang S X, Zhao Q, Zhang X M, Liu D X, Du N. Effect of Cr2O3 macroparticle on microstructure and tribological behavior of microarc oxidation coating on Ti6Al4V alloy [J]. Transactions of Materials and Heat Treatment, 2014, 35(2): 180.(王帅星, 赵晴, 张小明, 刘道新, 杜楠. Cr2O3微粒对Ti6Al4V微弧氧化膜结构及磨损行为的影响 [J]. 材料热处理学报, 2014, 35(2): 180.)
[15] Wei T B, Guo B G, Liang J, Yan F Y, Tian J. Tribological properties of micro-arc oxidation coatings on Al alloy [J]. Journal of Materials Science and Engineering, 2004, 22(4): 564.(魏同波, 郭宝刚, 梁军, 阎逢元, 田军. 铝合金微弧氧化陶瓷膜的性能研究 [J]. 材料科学与工程学报, 2004, 22(4): 564.)
[16] Chen F, Yu P H, Zhang Y. Healing effects of LDHs nanoplatelets on MAO ceramic layer of aluminum alloy [J]. Journal of Alloys and Compounds, 2017, 711: 342.
[17] Liu X H, Zhu L Q, Liu H C, Li W P. Investigation of MAO coating growth mechanism on aluminum alloy by two-step oxidation method [J]. Applied Surface Science, 2014, 293: 12.
[18] Mohannad M S, Al Bosta, Ma Kung-Jeng. Suggested mechanism for the MAO ceramiccoating on aluminium substrates using bipolar current mode in the alkaline silicate electrolytes [J]. Applied Surface Science, 2014, 308: 121.
[19] Tillous E K, Toll-Duchanoy T, Bauer-Grosse E. Microstructure and 3D microtomographic characterization of porosity of MAO surface layers formed on aluminium and 2214-T6 alloy [J]. Surface and Coatings Technology, 2009, 203(13): 1850.
[20] Zhang F, Zhao L, Chen H, Xu S, Evans D G, Duan X. Corrosion resistance of superhydrophobic layered double hydroxide films on aluminum [J]. Angew. Chem. Int. Ed. Eng., 2008, 47: 2466.