基于电化学方法在铝合金和碳钢表面制备TiO_2复合膜
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摘要
利用电化学方法在导电材料上制备TiO_2薄膜具有成本低、工艺简单、操作方便、适用于不同形状的工件、生成的薄膜具有良好的均匀性、在一定的沉积时间和电压范围内可控制膜的厚度等优点,具有广阔的应用前景。本课题基于电化学方法分别在铝合金表面制备Al_2O_3/TiO_2复合膜,并在碳钢表面制备NiP/ TiO_2复合膜,基体廉价且应用广泛,不需热处理,对TiO_2应用的推广具有重要的现实意义。
采用LY-12铝合金在呈酸性的TiPO_4电解液中、匀速上升的直流电压下进行阳极氧化同时沉积TiO_2的方法,使其表面生成了Al_2O_3/TiO_2复合膜。用SEM观察了其表面微观结构,并用EDS表征了其表面成分,结果显示:该复合膜的微观结构与多孔阳极Al_2O_3薄膜(PAA)不同,不存在微孔结构,且表面含Ti原子。通过在3.5%NaCl溶液中对含有Al_2O_3/TiO_2复合膜和PAA膜的铝合金电极进行自腐蚀电位随时间变化测试、电化学阻抗谱和极化曲线测试,分别比较和研究了两种膜电极于常温下在3.5%NaCl溶液中的耐蚀行为,结果表明:两种膜电极在在自然条件下的腐蚀机理不同,Al_2O_3/TiO_2复合膜的耐蚀性高于PAA膜;Al_2O_3/TiO_2复合膜电极(EDTA与Ti~(3+)的摩尔比为4 :1)的耐孔蚀能力强于PAA膜电极,且耐孔蚀能力均明显优于铝合金。
采用恒电位阳极沉积法于TiPO_4溶液中,在以NiP镀层为过渡层的Q235钢片上制备TiO_2薄膜。利用环境扫描电子显微镜(ESEM)观察了TiO_2薄膜的表面形貌,当电解液的pH=2时,显示的结果与NiP镀层的照片差别不大,而当电解液的pH=3时,试样表面出现了微裂纹;并用EDS分析了其表面显微成分,结果显示含Ti原子;用电化学阻抗谱法和动电位极化曲线测试方法研究了表面覆盖NiP/TiO_2复合膜的电极在3.5%NaCl溶液中的耐蚀行为,结果表明常温下在该腐蚀介质中,含有NiP/TiO_2复合膜的电极与含NiP镀层的电极的腐蚀机理不同,且前者的耐蚀性优于后者。本文在NiP镀层上制备TiO_2薄膜时选用电化学方法代替了溶胶-凝胶法,简化了工艺,降低了成本;另外,以TiPO_4溶液代替TiCl_3溶液做电解液,避免了易造成孔蚀的Cl~-的引入。
Using electrochemical method to prepare TiO_2 films on the conductive material has many advantages, such as low-cost, simple process, easy to operate, applicable to workpieces with different shapes. By this method, films could be prepared with good uniformity; in addition, their thickness could be controlled in certain deposition time and under a range of voltage. In a word, electrochemical method illustrated a good prospect of application and extension. On the basis of electrochemical methods, two improved approaches were drew out, one is preparing Al_2O_3/TiO_2 composite films on aluminum surface, and the other was preparing NiP/ TiO_2 composite films on the surface of the carbon steel. Due to these two kinds of substrate metal cheap and widely used, no treatment involved, promotion of these two methods to prepare TiO_2 composite films are of great realistic significance.
Al_2O_3/TiO_2 composite films were prepared on LY-12 Aluminum alloy sample surface in TiPO_4 electrolyte under D.C. voltage increased at a constant speed, by anode oxidizing and depositing TiO_2 at one time. The surface microstructure of composite films was observed by SEM, and composition was characterized by EDS. The results showed that the surface microstructure is different to porous anode alumina film (PAA), no micropore structure existing; and contained Ti atoms. The corrosion behavior of Aluminum alloy electrodes coated respectively by Al_2O_3/TiO_2 composite films and PAA films in 3.5% NaCl solution at room temperature were compared and studied by the measurements to corrosion potential changes over time, electrochemical impedance spectroscopy (EIS), and polarization curves. The results indicated that the corrosion mechanism of those two electrodes was different in this solution under natural condition; corrosion resistant in Al_2O_3/TiO_2 composite films was higher than that in PAA films; the same property in the electrode covered by Al_2O_3/TiO_2 composite films (EDTA : Ti~(3+)=4 : 1, by molar ratio) was higher than that in PAA electrode, and pitting corrosion resistant in both electrodes was much more better than that in Aluminum alloy.
TiO_2 films were formed on NiP transition layers of Q235 carbon steel in TiPO_4 solution by anode deposition with constant potential. The surface microstructure of TiO_2 films was observed by environmental scanning electron microscopy (ESEM), and surface composition was analyzed by EDS. The results showed that: there was little difference between NiP/TiO_2 composite films and NiP coating layers in the microstructure when the pH value of the electrolyte was around 2, however, micro-cracks generated when pH value reached 3; and contained Ti atoms. The corrosion behavior of Q235 carbon steel electrodes coated respectively by NiP/TiO_2 composite films and NiP coating layers were investigated and compared by measurements to EIS and polarization curves in 3.5% NaCl solution at room temperature. The results showed that their mechanisms of corrosion were different in the corrosive media, corrosion resistance of the former was higher than that in the latter. The paper introduced a new electrochemical approach to deposit TiO_2 film on the NiP coating to replace sol-gel method. The new method simplified technique, reduced costs; in addition, TiPO_4 electrolyte replaced TiCl_3 solution, avoided the introduction of Cl~- which could cause pitting corrosion easily on carbon steel.
采用LY-12铝合金在呈酸性的TiPO_4电解液中、匀速上升的直流电压下进行阳极氧化同时沉积TiO_2的方法,使其表面生成了Al_2O_3/TiO_2复合膜。用SEM观察了其表面微观结构,并用EDS表征了其表面成分,结果显示:该复合膜的微观结构与多孔阳极Al_2O_3薄膜(PAA)不同,不存在微孔结构,且表面含Ti原子。通过在3.5%NaCl溶液中对含有Al_2O_3/TiO_2复合膜和PAA膜的铝合金电极进行自腐蚀电位随时间变化测试、电化学阻抗谱和极化曲线测试,分别比较和研究了两种膜电极于常温下在3.5%NaCl溶液中的耐蚀行为,结果表明:两种膜电极在在自然条件下的腐蚀机理不同,Al_2O_3/TiO_2复合膜的耐蚀性高于PAA膜;Al_2O_3/TiO_2复合膜电极(EDTA与Ti~(3+)的摩尔比为4 :1)的耐孔蚀能力强于PAA膜电极,且耐孔蚀能力均明显优于铝合金。
采用恒电位阳极沉积法于TiPO_4溶液中,在以NiP镀层为过渡层的Q235钢片上制备TiO_2薄膜。利用环境扫描电子显微镜(ESEM)观察了TiO_2薄膜的表面形貌,当电解液的pH=2时,显示的结果与NiP镀层的照片差别不大,而当电解液的pH=3时,试样表面出现了微裂纹;并用EDS分析了其表面显微成分,结果显示含Ti原子;用电化学阻抗谱法和动电位极化曲线测试方法研究了表面覆盖NiP/TiO_2复合膜的电极在3.5%NaCl溶液中的耐蚀行为,结果表明常温下在该腐蚀介质中,含有NiP/TiO_2复合膜的电极与含NiP镀层的电极的腐蚀机理不同,且前者的耐蚀性优于后者。本文在NiP镀层上制备TiO_2薄膜时选用电化学方法代替了溶胶-凝胶法,简化了工艺,降低了成本;另外,以TiPO_4溶液代替TiCl_3溶液做电解液,避免了易造成孔蚀的Cl~-的引入。
Using electrochemical method to prepare TiO_2 films on the conductive material has many advantages, such as low-cost, simple process, easy to operate, applicable to workpieces with different shapes. By this method, films could be prepared with good uniformity; in addition, their thickness could be controlled in certain deposition time and under a range of voltage. In a word, electrochemical method illustrated a good prospect of application and extension. On the basis of electrochemical methods, two improved approaches were drew out, one is preparing Al_2O_3/TiO_2 composite films on aluminum surface, and the other was preparing NiP/ TiO_2 composite films on the surface of the carbon steel. Due to these two kinds of substrate metal cheap and widely used, no treatment involved, promotion of these two methods to prepare TiO_2 composite films are of great realistic significance.
Al_2O_3/TiO_2 composite films were prepared on LY-12 Aluminum alloy sample surface in TiPO_4 electrolyte under D.C. voltage increased at a constant speed, by anode oxidizing and depositing TiO_2 at one time. The surface microstructure of composite films was observed by SEM, and composition was characterized by EDS. The results showed that the surface microstructure is different to porous anode alumina film (PAA), no micropore structure existing; and contained Ti atoms. The corrosion behavior of Aluminum alloy electrodes coated respectively by Al_2O_3/TiO_2 composite films and PAA films in 3.5% NaCl solution at room temperature were compared and studied by the measurements to corrosion potential changes over time, electrochemical impedance spectroscopy (EIS), and polarization curves. The results indicated that the corrosion mechanism of those two electrodes was different in this solution under natural condition; corrosion resistant in Al_2O_3/TiO_2 composite films was higher than that in PAA films; the same property in the electrode covered by Al_2O_3/TiO_2 composite films (EDTA : Ti~(3+)=4 : 1, by molar ratio) was higher than that in PAA electrode, and pitting corrosion resistant in both electrodes was much more better than that in Aluminum alloy.
TiO_2 films were formed on NiP transition layers of Q235 carbon steel in TiPO_4 solution by anode deposition with constant potential. The surface microstructure of TiO_2 films was observed by environmental scanning electron microscopy (ESEM), and surface composition was analyzed by EDS. The results showed that: there was little difference between NiP/TiO_2 composite films and NiP coating layers in the microstructure when the pH value of the electrolyte was around 2, however, micro-cracks generated when pH value reached 3; and contained Ti atoms. The corrosion behavior of Q235 carbon steel electrodes coated respectively by NiP/TiO_2 composite films and NiP coating layers were investigated and compared by measurements to EIS and polarization curves in 3.5% NaCl solution at room temperature. The results showed that their mechanisms of corrosion were different in the corrosive media, corrosion resistance of the former was higher than that in the latter. The paper introduced a new electrochemical approach to deposit TiO_2 film on the NiP coating to replace sol-gel method. The new method simplified technique, reduced costs; in addition, TiPO_4 electrolyte replaced TiCl_3 solution, avoided the introduction of Cl~- which could cause pitting corrosion easily on carbon steel.
引文
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