Zirconium Oxide Coating on Anodized Aluminum by the Sol-Gel Process Combined with Ultraviolet Irradiation at Ambient Temperature

Instead of the conventional sol-gel process in which heat treatment is used to form a dense composite film after dipping/withdrawing a substrate into/from the sol, a new sol-gel process incorporating ultraviolet (UV) irradiation at ambient temperature has been attempted to improve the alkaline corrosion resistance of aluminum. A sol-gel film prepared by UV irradiation at ambient temperature indicated that alkaline corrosion resistance is superior in the range of 2.4 times to 2.6 times that of the conventional composite film heated at 573 K. The densification of the coating layer due to the elimination of residual organics induced by photoexcitation was responsible for the improvement in alkaline corrosion resistance. The high alkaline corrosion resistance of the irradiated film may be attributed to the formation of a dense coating layer and the self-repairing action caused by repetition for preparation and dissolution of the reactant in the penetrating path of NaOH solution into the composite film.     

汽车用2024铝合金阳极氧化膜性能的研究

对汽车用2024铝合金板材进行酒石酸阳极氧化处理,并研究了阳极氧化对铝合金的成分、结构、表面形貌及耐蚀性的影响。研究发现,铝合金阳极氧化膜是由表面多孔层和内部无孔层构成的。铝合金阳极氧化过程是一个氧化铝生成和溶解的动态过程。阳极氧化膜由刚玉结构的α-Al_2O_3和八面结构的γ-Al_2O_3构成,α相和γ相大大提高了阳极氧化膜的硬度和耐蚀性。阳极氧化膜为典型的多孔结构,孔洞分布均匀,孔径为50nm左右。     

Corrosion behavior of 2024 aluminum alloy anodized in presence of permanganate and phosphate ions

In this article, the effects of two inorganic corrosion inhibitors, permanganate and phosphate anions, on morphology, composition, thickness, and corrosion resistance of the anodic film formed on 2024 aluminum alloy in sulfuric acid were investigated. Surface morphology of the oxide films were studied by field emission scanning electron microscopy. Electrochemical impedance spectroscopy and potentiodynamic polarization tests were conducted to assess the corrosion resistance of the coatings. These analyses showed that the presence of the mentioned inhibitors changed the coating morphology, especially in the case of phosphate ions. Corrosion results indicated that using inhibitors during the anodizing process increased the corrosion resistance of the anodized samples. The increases were approximately 81% and 97% for 0.05 M of permanganate and phosphate ions, respectively, compared with the anodized coatings in the absence of additives. An increase in the inhibitor concentration results in better corrosion resistance of the aluminum anodic layer.     

Corrosion resistance of aluminum oxide film and electrolytically coloured film in sodium chloride solution

The main interest of this study is to compare the corrosion resistance of aluminum anodic oxide film anodized in sulfuric acid bath with that of preanodized and electrolytically coloured film.Examinations have been carried out referring to (1) potentiostatted polarization curves shown on the specimens in 0.5 M sodium chloride solution, (2) impedance diagrams of the specimens and barrier thickness by Hunter's method and (3) optical metallographical observations of the aspects of pitting corrosion which took place on these specimens, and dipping test in corrosive solution.The results obtained are summarized as follows: (1) Typical difference was observed in regard to the potentiostatted polarization curves (i-t curves) between the two types of specimens in 0.5 M sodium chloride solution. The corrosion current caused by pitting corrosion of the electrolytically coloured specimens was smaller than that of anodized ones on the measurement by i-t curves. (2) The survey through the interfacial impedance diagrams of the specimens made clear that the impedance of the electrolytically coloured film was larger than that of uncoloured anodic oxide film, especially this greater increasing part of impedance was achieved in 15 s. This tendency was similar for the measurement of barrier thickness by Hunter's method. (3) The optical metallographical observations have demonstrated that there were far more advanced pitting corrosion on the anodic oxide film than on the electrolytically coloured film. In the dipping test, uncoloured anodized aluminum showed high extent of pitting corrosion, while electrolytically coloured aluminum performed well during colouring. So the total result of above examinations reveals that electrolytically coloured films are definitely more resistive to corrosion than anodic oxide films and this is due to the thick barrier layer of the former films.     

Ellipsometric measurements of the barrier layer in composite aluminum oxide films

The composite oxide film (hydrous + anodic) formed on aluminum foil was chemically stripped to remove only the outer hydrous layer. Ellipsometry of the remaining barrier film showed it to be thinner and have a higher refractive index than conventional anodic barrier films grown to the same voltage. Reanodization to improve film stability gave a further increase in refractive index which indicated that the barrier film had contained some voids. The barrier film is almost entirely crystalline γ-Al₂O₃ and the higher field strength compared with conventional amorphous anodic films on aluminum is believed to be a characteristic of the denser oxide.     

排球挂钩用铝合金基材阳极氧化处理及耐蚀性研究

使用铝合金挂钩对装入网兜的排球进行悬挂和管理,具有取用方便、节约空间、美观等优点。使用硫酸阳极氧化技术对排球挂钩用5005铝合金基材进行了处理,并对阳极氧化膜的性能进行了研究。结果表明:阳极氧化膜主要由铝、氧、硫、碳元素构成,其中铝和氧的总质量分数超过80%,少量的硫来自硫酸。经过硫酸阳极氧化处理后,铝合金表面形成高硬度和高熔点的a-Al2O3和y-Al2O3,大大提高了铝合金的硬度。阳极氧化膜由高电阻的阻拦层和多孔层构成,可以有效地分散和降低自腐蚀电流密度,大大提高铝合金基材的耐蚀性。     

铝阳极氧化膜采用复合无镍封孔工艺的研究

通过分析锂盐与锆盐两种无镍封孔工艺各自对铝阳极氧化膜封孔所存在的优缺点,提出了一种二步法──复合无镍封孔工艺,即第1步用锂盐对铝阳极氧化膜进行封孔,第2步再用锆盐对相同铝阳极氧化膜进行复合封孔,从而既克服了锆盐和锂盐1步法封孔工艺存在的缺点,又保留了各自的优点,使工艺的适应性得到一定改善,使铝阳极氧化膜综合封闭孔质量及重要性能得到较大提高。     

Synthesis and electrochemical evaluation of polypyrrole coatings electrodeposited onto AA-2024 alloy

Polypyrrole coating was successfully deposited on anodized 2024 unclad aluminum alloy showing that the presence of the anodic film is the key factor to ensure better adhesion to the polymer coating. Corrosion resistance of the conductive polymer layers grown for three and five cycles were evaluated in a 3 wt.% NaCl solution using polarization curves and impedance spectroscopy. It was found that the thermally treated polymer coating with higher thickness (five cycles) exhibited the best corrosion performance. This best coating shifts the corrosion potential towards nobler values, about 650 mV, and the exchange current density decreases two orders of magnitude regarding the anodic layer. The partial reduction of the structure of the polymer promoted by the thermal treatment plays a key role in the corrosion resistance of the coating allowing to the thermally treated polymer layer to act as a physical barrier against corrosion.     

硫酸镧对汽车用铝合金阳极氧化膜性能的影响

在汽车用2024铝合金阳极氧化使用的电解液中添加硫酸镧,并研究了硫酸锢的质量浓度对阳极氧化膜的厚度、膜重、硬度、表面形貌及耐蚀性的影响。结果表明:硫酸镧的催化作用有利于提高氧化速率,减小多孔层的孔径,从而提高阳极氧化膜的硬度及耐蚀性。当硫酸镧的质量浓度为0.8 g/L时,阳极氧化膜具有最高的硬度和最佳的耐蚀性。但当硫酸镧的质量浓度大于0.8 g/L时,稀土的吸附作用会使阳极氧化膜的性能有所降低。     

Local deposition of polypyrrole on aluminum by anodizing, laser irradiation, and electrolytic polymerization and its application to the fabrication of micro-actuators

Polypyrrole was deposited at selected areas on aluminum by anodizing, laser irradiation, and electrolytic polymerization, and the application of the technique for fabricating micro-actuators was attempted. Aluminum specimens covered with porous type anodic oxide films were irradiated with a pulsed Nd-YAG laser to remove the oxide films locally, and then thin Ni layers were deposited at areas where film had been removed. Polypyrrole could be successfully deposited only on the Ni layer by anodic polarization of the specimens in pyrrole monomer solution, and a polypyrrole/Ni bilayer structure could be obtained by dissolution of the aluminum substrate and anodic oxide film in NaOH solutions. The bilayer structure was found to be inactive to doping and dedoping of ions during anodic and cathodic polarization. A three-layer structure, nitrocellulose/Ni/polypyrrole, fabricated by electrolytic polymerization after nitrocellulose coating on a Ni layer detached from the aluminum substrate, showed ion-doping and -dedoping activity, suggesting the possibility of fabricating micro-actuators in this manner.     

汽车用铝合金阳极氧化及钵转化膜封闭技术

采用阳极氧化和钵转化膜封闭技术提高汽车用2036铝合金的耐蚀性。研究发现:铝合金阳极氧化膜由外部的多孔层和内部的阻挡层构成,多孔层孔径均匀,约为30 nm0经过阳极氧化处理后,铝合金的自腐蚀电位正移,自腐蚀电流密度下降,耐蚀性提高。经过钵转化膜封闭处理后,大量钵的氢氧化物覆盖阳极氧化膜表面,进一步提高了铝合金的耐蚀性。     

电压对7N01铝合金阳极氧化膜结构及耐蚀性的影响

采用160 g/L硫酸溶液在17°C下对7N01铝合金阳极氧化30 min,氧化电压分别选取14、15、16、17和18 V。用扫描电镜观察所得阳极氧化膜的形貌,用能谱仪和电化学测量分析了它的成分、厚度和耐蚀性。结果表明,7N01铝合金经过不同电压下的阳极氧化处理后,表面均能形成凹凸不平并有孔洞的阳极氧化膜,电压为17 V时所制膜层致密、均匀,厚度约为7.6μm,耐蚀性最佳,在3.5%NaCl溶液中浸泡1440 h后没有明显的腐蚀。     

Formation of Ti-Si composite oxide films on Mg-Al-Zn alloy by electrophoretic deposition and anodization

TiO₂ or SiO₂ nanoparticles dispersed in an acetone solvent containing iodine were deposited on Mg-Al-Zn alloy by electrophoretic deposition (EPD). Subsequently, the composite oxide films were formed on the substrate by anodization in KOH-Na₂SiO₃ aqueous solutions containing TiO₂ or SiO₂ nanoparticles. The films formed by EPD were improved binding with the substrate by anodization under high voltages with sparking, and then the anodic films consisted of Si-Mg or Ti-Si-Mg composite oxides. The film thicknesses of TiO₂ and SiO₂ on the alloy increased with anodization time. In polarization tests, the films anodized under high voltages with sparking in the alkaline solutions had high corrosion resistance. Thus, the composite oxide films formed in the present method were successful in providing corrosion resistance to Mg alloy.     

铝合金直流电阳极氧化膜电解着色的研究

以工业纯铝L2为实验材料,采用硫酸直流电阳极氧化-电解着色工艺在铝合金表面制备黑色膜层.着重分析着色电压对黑色膜层表观颜色、厚度、硬度的影响.通过SEM表征、EDS测试及性能测试表明:在优化后的电解着色工艺条件下可以获得与工业纯铝L2基体结合力良好,且耐蚀性、耐热性、吸光性均较好的黑色膜层.     

AZ91D镁合金磁控溅射镀铝膜及其化学转化后的耐蚀性

采用磁控溅射镀铝与化学转化复合处理的方法对AZ91D镁合金表面进行处理,制得复合处理膜层,并与单纯磁控溅射镀铝膜层的耐蚀性进行了比较。结果表明,磁控溅射所得铝膜层结构致密,铝膜层与镁合金基体界面形成混合过渡层。沉积铝膜后再进行阿洛丁化学转化所得膜层表面存在裂纹,化学转化膜与铝膜之间结合良好。磁控溅射铝膜层使镁合金的腐蚀速率加快。镀铝与化学转化复合处理所得膜层的腐蚀电流密度比镁合金基体低1个数量级以上,表明镀铝与化学转化复合处理可明显提高镁合金的耐蚀性。中性盐雾试验4h后,铝膜表面腐蚀严重;而复合处理膜层在试验24h后表面只出现少量的腐蚀,48h后只有5%的面积被腐蚀。     

Top coating of low-molecular weight polymer MALPB used for enhanced protection on anodized AZ31B Mg alloys

A protective composite coating on an AZ31B magnesium alloy was prepared by anodic oxidation to form an oxide layer, followed by single immersion in maleic anhydride-g-liquid polybutadiene (MALPB) solution to cover a polymer coating on top. As a low-molecular weight polymer with low viscosity, MALPB had a tendency to infiltrate into the pores and cracks in the anodic layer to fill the defects among oxides so that a compact layer could be formed after it was cured by its hardeners, as observed by scanning electron microscopy (SEM). This compact layer, which was composed of anodic oxides integrated with solidified MALPB, possessed thickness around 0.7 μm as detected by energy dispersive X-ray (EDX). The anodized, MALPB-coated AZ31B alloy exhibited enhancement in corrosion resistance superior to that separately coated by anodizing oxides or MALPB, as reflected by its much higher corrosion potentials (E _ccor) and lower corrosion current density (i _corr) in DC polarization tests. Based on electrochemical impedance spectroscopy (EIS) data, we conclude that the anticorrosive performance of the composite coating can be attributed to the barrier effects provided by different layers when the electrolyte passed through the MALPB layer, compact layer, and then the inner anodic layer before it reached the surface of Mg alloy, and that among them, the compact layer acted as a much more effective barrier to the electrolyte. The appearance of damaged areas on the composite coating surface after a much longer duration in a salt spray environment revealed that the life-span of the AZ31B Mg alloy could be greatly prolonged if the pores and cracks on the anodizing films were properly sealed by suitable polymers.     

硅溶胶对无机磷酸铝涂料防腐性能的影响

采用化学合成法制备磷酸铝粘结剂,以球形铝粉为骨料,添加不同含量的硅溶胶,制备磷酸铝涂料,再经过热处理制备磷酸铝涂层。通过X射线衍射分析(XRD)表征粘结剂和涂层物相结构,采用扫描电子显微镜(SEM)表征涂层形貌,通过电化学测试和浸泡试验对比研究涂层腐蚀行为。分析结果表明:在磷酸铝涂层中添加适量硅溶胶可以改善涂层表面质量和耐腐蚀性能,从而使涂层腐蚀电位升高,腐蚀电流降低,阻抗值增大。添加10%硅溶胶的涂层质量最佳,耐腐蚀性能最优。     

汽车用铝合金阳极氧化及双重封闭工艺的研究

对汽车用2024铝合金进行了硫酸阳极氧化处理,并使用硫酸镍结合铬酸钾的双重封闭技术对阳极氧化膜进行了封闭处理。结果表明:在2024铝合金表面制备的阳极氧化膜属于典型的多孔膜。经过硫酸镍一次封闭处理后,大量镍的氢氧化物填充于膜孔内,有效地降低了阳极氧化膜的自腐蚀电流密度。经过铬酸钾二次封闭处理后,铬酸镍进一步覆盖在膜孔表面,大大提高了阳极氧化膜的均匀性和致密性。经过双重封闭处理后,阳极氧化膜的阻抗明显增大,耐蚀性大大提高。     

溶胶-凝胶法制备不锈钢表面SiO2-TiO2-Al2O3-ZrO2涂层

在乙醇中,分别以盐酸、醋酸为催化剂,以正硅酸乙酯、钛酸正丁酯、硝酸铝、氧氯化锆为金属醇盐前躯体,通过分步水解法制备了SiO2-TiO2-Al2O3-ZrO2复合溶胶,利用浸渍法将陈化后的复合溶胶涂覆到不锈钢表面制得透明的复合涂层。对SiO2-TiO2-Al2O3-ZrO2复合涂层进行了差热分析(DTA)、失重分析(TG)、红外光谱(IR)、X射线衍射分析(XRD)以及耐HCl、CuSO4和FeCl3溶液浸泡腐蚀实验。结果表明,涂层中存在TiO、SiO、AlO键的氧化物网状结构,其XRD图中出现了锐钛矿和板钛矿的相结构。该涂层致密,具有良好的耐蚀性能。     

Electrochemical behavior of hydrophobic silane–zeolite coatings for corrosion protection of aluminum substrate

The anticorrosive properties of a silane–zeolite composite coating applied on a 6061 aluminum substrate was investigated. The composite film, deposited by dip-coating technique, was prepared with different contents of SAPO34 powder (60–90 wt%) with the purpose of evaluating the protective action offered by the zeolite-filled silane matrix. Corrosion protection performance, during immersion in 3.5% NaCl solution, was evaluated by means of a potentiodynamic polarization test and electrochemical impedance spectroscopy (EIS). The coating evidenced good barrier properties and high hydrophobicity. The addition of zeolite in the silane matrix induced, as expected, a reduction of cathodic and anodic current. The zeolite improved the barrier properties of the hybrid sol–gel films, enhancing the resistance to localized corrosion attacks. Better results were observed for the sample with 80 wt% of zeolite filler that evidenced still acceptable protective action after 3 days of immersion in the sodium chloride solution.