水滑石前驱法制备的Al-Li复合阳极氧化膜的性能

利用水滑石前驱法在高纯铝表面引入Li元素,然后通过阳极氧化在高纯铝表面制备Al-Li复合阳极氧化膜。采用XPS、XRD、SEM、极化曲线及电化学阻抗谱技术研究氧化膜的性能。结果表明：通过水滑石前驱法能制备Al-Li复合阳极氧化膜,膜中Li含量可达8%;与纯铝氧化膜相比,复合氧化膜更加致密;无论是否封闭,Al-Li复合氧化膜在中性NaCl溶液中的耐蚀性都较纯铝氧化膜更好。     

Environmental friendly plasma electrolytic oxidation of AM60 magnesium alloy and its corrosion resistance

Plasma electrolytic oxidation of Mg-based AM60 alloys was investigated using 50 Hz AC anodizing technique in an alkaline borate solution, which contained a new kind of organic. The anodic film is relatively smooth with some micro pores and cracks, while the anodic film consists of MgO, MgAl2O4 and MgSiO3. The electrochemical behavior of anodic film was studied by electrochemical impedance spectroscopy and potentiodynamic polarization. Polarization results indicate the PEO treatment can decrease corrosion current by 3-4 magnitude compared with blank AM60 alloy. The anodic film presents a good level of corrosion protection for AM60 magnesium alloy, over 272 h of the salt spray test based on ASTM B 117. The effect of micro-structure and composition on corrosion protection efficiency was also investigated.     

Influence of molybdate species on the tartaric acid/sulphuric acid anodic films grown on AA2024 T3 aerospace alloy

AA2024 T3 alloy specimens have been anodised in tartaric acid/sulphuric media and tartaric acid/sulphuric media containing sodium molybdate; molybdate species were added to the anodising bath to enhance further the protection provided by the porous anodic film developed over the macroscopic alloy surface. Morphological characterisation of the anodic films formed in both electrolytes was undertaken using scanning electron and transmission electron microscopies; the chemical compositions of the films were determined by Rutherford backscattering spectroscopy that was complemented by elemental depth profiling using rf-glow discharge optical emission spectrometry. The electrochemical behaviour was evaluated using potentiodynamic polarisations and electrochemical impedance spectroscopy; the corrosion performance was examined after salt spray testing. The porous anodic film morphology was little influenced by the addition of molybdate salt, although thinner films were generated in its presence. Chemical composition of the anodic film was roughly similar; however, addition of sodium molybdate in the anodizing bath resulted in residues of molybdate species in the porous skeleton and improved corrosion resistance measured by electrochemical techniques that was confirmed by salt spray testing.     

铈盐对铝合金硼酸?硫酸阳极氧化膜的封闭效应

将铝合金硼酸-硫酸阳极氧化膜浸入铈盐转化液中进行封闭。采用交流阻抗谱技术研究各封闭参数对氧化膜耐蚀性的影响,比较了不同方法封闭的氧化膜的耐蚀性差异。结果表明:将硼酸-硫酸阳极氧化试样浸入30℃的铈盐转化液(5 g/L Ce(NO3)3+0.5%H2O2)中处理30 min后,多孔层电阻Rp大幅增加,且腐蚀电流密度降低1个数量级,耐蚀性明显优于沸水封闭氧化膜的,也稍优于稀铬酸封闭氧化膜的耐蚀性。结合EDS分析表明:铈盐转化封闭后硼酸-硫酸阳极氧化膜的外表面形成了一层完整致密的铈盐转化膜,多孔层内也充满了铈的封闭产物,二者的协同作用几乎完全封住了硼酸-硫酸阳极氧化膜的孔隙,从而有效地提高了氧化膜的耐蚀性。     

Plasma anodized ZE41 magnesium alloy sealed with hybrid epoxy-silane coating

Anodic coatings on magnesium ZE41 alloy were formed by DC plasma electrolytic oxidation (PEO) in spark regime in solution composed of NaOH, Na₂SiO₃ and KF. The positive effect of poly(ethylene oxide) addition into the anodizing electrolyte on PEO process, anodic film porosity and its protective performance was described. Anodic films were sealed with hybrid epoxy-silane formulation. The corrosion behavior of the coated ZE41 was studied through electrochemical impedance spectroscopy (EIS) in 0.6 M NaCl solution. Resulting duplex PEO/epoxy-silane coating provides good protective performance without significant signs of corrosion during 1 month of immersion test.     

铝阳极氧化膜的微观结构及沸水封闭处理对膜层显微硬度的影响

通过阳极氧化在铝合金表面获得稳定的阳极氧化膜,并对膜层进行沸水封闭处理,采用扫描电子显微镜(SEM)、电化学阻抗谱(EIS)等分析手段研究了氧化电流密度以及封闭处理对膜层显微硬度的影响。结果表明:随着电流密度的增加,铝合金阳极氧化膜的显微硬度先升高,后降低;沸水封闭会导致铝阳极氧化膜的显微硬度下降;铝阳极氧化膜表面形貌的优劣、多孔层的组织结构和屏蔽性与膜层显微硬度密切相关。     

Anodizing of magnesium alloy AZ31 in alkaline solutions with silicate under continuous sparking

Anodization is a useful technique for forming protective films on magnesium alloys and improves its corrosion resistance. Based on the alkaline electrolyte solution with primary oxysalt developed previously, the optimum secondary oxysalt was selected by comparing the anti-corrosion property of anodic film. The structure, component and surface morphology of anodic film and cross-section were analyzed using energy dispersion spectrometer (EDS), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The corrosion process was detected by electrochemical impedance spectroscopy (EIS). The results showed that secondary oxysalt addition resulted in different anodizing processes, sparking or non-sparking. Sodium silicate was the most favorable additive of electrolyte, in which anodic film with the strongest corrosion resistance was obtained. The effects of process parameters, such as silicate concentration, applied current density and temperature, were also investigated. High temperature did not improve anti-property of anodic film, while applying high current density resulted in more porous surface of film.     

The effect of phosphate on MAO of AZ91D magnesium using AC power source

A rapid and convenient anodization technology with AC power source to obtain the MAO films formed on magnesium alloy AZ91D in phosphate bath (base electrolyte + Na₃PO₄) with or without aluminate and silicate was studied. The corrosion resistance of the anodic films was studied by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization techniques and the microstructure and composition of films were examined by SEM and XRD. The results show that Na₃PO₄can promote the occurrence of sparking during the MAO process, while abundant heat generated by sparking might enhance the formation of the glassy phase of the compound when the electrolyte contains the additives of NaAlO₂and Na₂SiO₃simultaneously. The optimized MAO film is ivory‐white smooth by naked eye, while presents porous and microcracks in microscopic scale. The anodic film formed in the alkaline solution with optimized parameters possesses superior corrosion resistance by electrochemical test. The XRD pattern shows that the components of the anodized film consist of MgO, MgAlO₂, and MgSiO₃. No oxide crystal with P element can be found.     

Exfoliation corrosion of 7150 Al alloy with various tempers and its electrochemical impedance spectroscopy in EXCO solution

The exfoliation corrosion susceptibility and electrochemical impedance spectroscopy (EIS) of 7150 Al alloys with T6, T73, and RRA (retrogression at 175 °C for 3 h) tempers in EXCO solution were investigated. The anodic equilibrium precipitate η(MgZn₂) is continuous or closely spaced at the grain boundaries in the 7150‐T6 Al alloy, resulting in its greatest susceptibility to exfoliation corrosion. The grain boundary η precipitates in the RRA and T73 treated 7150 Al alloys are coarsened and show a clear discontinuous nature; they possess similar exfoliation corrosion sensitivity and their exfoliation corrosion resistance is greatly increased. At the beginning of immersion in EXCO solution, the EIS plot of the 7150 Al alloys is composed of a capacitive arc in the high to medium frequency range and an inductive component in the medium to low frequency range. As immersion time is increased, exfoliation corrosion with different corrosion ratings occurs on the surface of the 7150 Al alloy with various tempers, two capacitive arcs appear in the high to medium and medium to low frequency ranges, respectively. The fitted medium to low frequency capacitance C₂ of 7150‐T6 Al alloy, corresponding to the new surface caused by the exfoliation corrosion, is much greater than that of the T73 and RRA treated 7150 Al alloy, which is consistent with the greatest exfoliation corrosion susceptibility of the 7150‐T6 Al alloy.     

二次阳极氧化对6061铝合金氧化膜结构和耐蚀性的影响

目的 研究相同工艺参数下一次阳极氧化和二次阳极氧化对6061铝合金上氧化膜结构的影响,探究基体结构差异性与膜层生长行为及性能间的对应关系。方法 以商业6061铝合金和SPS粉末烧结铝合金为研究对象,针对不同基体在一次阳极氧化和二次阳极氧化过程中,围绕基体组织特征对膜层结构的影响展开系统研究。同时,对不同工艺方法制备出的不同结构特点的氧化膜进行封闭后处理,结合电化学测试方法对膜层的耐蚀性能进行分析对比。结果 相比一次氧化过程,商业6061铝合金和SPS铝合金的二次氧化电流密度分别由12.07、56.62 mA/cm2增加至13.68、64.8 mA/cm2,膜层生长速率增大。同时,一次氧化后在基体表面形成的有序凹坑结构有助于二次氧化中膜层多孔结构有序性的提升,其中SPS烧结铝合金膜层孔洞呈规则的“六边形”结构。二次阳极氧化过程可以有效减少基体表面阴极性金属间化合物颗粒的分布,提高氧化膜的连续性,增强相应膜层的耐蚀性。结论 二次阳极氧化可以使生成的氧化膜层更加均匀规整,且整体耐蚀性显著提高。     

The bonding strength and corrosion resistance of aluminum alloy by anodizing treatment in a phosphoric acid modified boric acid/sulfuric acid bath

The process of phosphoric/boric/sulfuric acids anodizing was studied as a new pre-treatment for adhesive bonding of aluminum alloys. The microstructure and topography of the anodic films were examined using SEM and AFM, and the adhesive strength and corrosion behavior were studied with lap-shear test, wedge test and electrochemical technology. The results showed that by the process of phosphoric/boric/sulfuric acids anodizing a thicker film with high porosity and big pores can be obtained. The porous film was beneficial to improve the durability and lap-shear strength of the bonding joints. The thicker film can also provide better corrosion resistance. Compared with the films by boric/sulfuric acids anodizing and phosphoric acid anodizing, under humid and hot environments the phosphoric/boric/sulfuric acids anodic film showed better corrosion resistance, higher bonding strength and durability, and is a promising pre-treatment for adhesive bonding of aluminum alloys instead of the chromic acid anodizing process.     

硼酸对7050铝合金硼酸-硫酸阳极氧化膜结构及耐蚀性的影响(英文)

通过 AFM、交流阻抗谱及扫描 Kelvin 探针技术,研究硼酸对 7050 铝合金硼酸?硫酸阳极氧化膜结构及耐蚀性的影响。结果表明,在硼酸-硫酸阳极氧化体系中,硼酸不会改变氧化膜阻挡层的结构,但会显著影响氧化膜多孔层的结构形式,进而影响氧化膜的耐蚀性。在 0～8 g/L 的范围内,随着电解液中硼酸含量的增加,氧化膜的多孔层电阻增大,电容减小,表面势正移,孔径缩小,耐蚀性变好。在高于 8 g/L 时,随着硼酸含量的增加,氧化膜的孔隙变大,阻抗变小,电子逸出功降低,耐蚀性变差。     

N80钢CO2腐蚀电极过程交流阻抗分析

利用交流阻抗技术研究了N80钢在不同介质条件下CO2腐蚀交流阻抗图谱的特征，结果表明，N80油套管钢CO2腐蚀EIS曲线具有三个时间常数，其中低频感抗弧与试样表面活化溶解有关，低频容抗弧与试样表面腐蚀产物膜生成有关。随着试样表面腐蚀产物膜覆盖度增大，EIS曲线低频区感抗弧逐渐缩小，容抗弧逐渐扩大。进一步讨论了试样表面腐蚀产物膜成膜情况与电极反应过程的有关。     

Exfoliation corrosion and electrochemical impedance spectroscopy of an Al‐Li alloy in EXCO solution

The exfoliation corrosion and electrochemical impedance spectroscopy (EIS) of an Al‐2.8%Cu‐1.5%Li‐0.3%Mg‐0.3%Zn‐0.3%Mn‐0.15%Zr alloy with various aging states in EXCO solution were investigated. The equilibrium precipitates at grain boundaries are anodic to the alloy base at their adjacent periphery. With prolonging aging time, the amount and the size of the equilibrium precipitates at grain boundaries are increased, resulting in an enhanced susceptibility to exfoliation corrosion. At the beginning of immersion in EXCO solution, the EIS plot of the alloys is composed of a capacitive arc in the high frequency range and an inductive loop in the low frequency range. As immersion time is increased, two capacitive arcs appear in the high‐mediate and mediate‐low frequency ranges respectively and the appearance time of two capacitive arcs could be an indication of the speed of localized corrosion development in EXCO solution. The longer appearance time of two capacitive arcs of the under‐aged alloy indicates its slower localized corrosion development.     

Electrochemical behaviors of anodic alumina sealed by Ce-Mo in NaCl solutions

1 Introduction Aluminum is a kind of material with active chemical behavior. It can form a thin oxide film on its surface in natural environment. The structure of this amorphous film is loose, so it could not provide good corrosion resistance. Anodizing i…     

Al-Zn-Sn-Ga阳极腐蚀过程的电化学阻抗谱

通过测定Al-Zn-Sn-Ga阳极在3.5%NaCl(质量分数)溶液中浸泡不同时间的电化学阻抗谱(EIS),研究该阳极的腐蚀发展过程和腐蚀特征。结果显示:当合金刚被浸入3.5%NaCl溶液时,EIS谱为反应电阻很大的容抗弧,表明此时合金处于钝化态;随着浸泡时间的延长,EIS谱中高频段的容抗弧明显减小且低频段出现感抗弧,合金进入点蚀期;继续延长浸泡时间,EIS谱中除高频段的容抗弧和中、低频段感抗弧外,在低频段出现另一容抗弧,合金处于点蚀扩展期;随着浸泡时间的继续增加,低频段感抗弧消失,EIS谱由两个容抗弧组成,合金达到均匀腐蚀期。因此,合金的腐蚀由钝化态开始,经点蚀期和点蚀扩展期,达到均匀腐蚀期。     

三种无铬封闭方法对铝合金阳极氧化膜耐蚀性的影响

研究了沸水封闭、醋酸镍封闭和电压加载下己二酸铵封闭对LY12铝合金阳极氧化膜耐蚀性的影响。通过场发射扫描电镜（FE-SEM）和电化学阻抗谱（EIS）对三种无铬封闭方法处理后铝合金阳极氧化膜的表面微观形貌和耐蚀性进行了研究。结果表明：封闭处理可以有效地闭合阳极氧化膜的微孔,提高氧化膜耐腐蚀性能。电压加载下己二酸铵封闭可以有效缓解氧化膜的腐蚀。三种无铬封闭方法处理后的氧化膜耐腐蚀性能从小到大依次为：沸水封闭,醋酸镍封闭,电压加载下己二酸铵封闭。     

7B04铝合金的一种阳极化膜层电化学性能研究

采用电化学交流阻抗技术(EIS)对7B04铝合金的一种阳极化膜层在加速老化试验过程中的阻抗变化进行了原位测试,分析了其腐蚀失效的特征.结果表明,随加速试验的进行,硫酸阳极化膜层的失光率和色差变化较小,属不失光或很轻微失光和不变色;腐蚀前,阳极化膜的多孔层常相位元件的幂指数n相对较小,仅0.61,说明多孔层孔洞分布比较不均匀.随试验时间增加,n值逐渐增大并接近1,多孔电阻Rpo也逐渐增加,且后期增加幅度加大,这是由于沉淀物的部分封堵与耐蚀钝化膜的共同作用;阳极化膜划痕处的局部交流阻抗随试验时间增加不断减小,是由于划痕处金属发生了腐蚀反应所致,划痕处的阻抗增大则是由于划痕处被腐蚀产物覆盖所致.     

Improvement in corrosion resistance of commercial pure titanium for the enhancement of its biocompatibility

A new surface modification protocol encompassing an anodization treatment has been developed to improve the surface properties of biomedical titanium. Anodization in presence of nickel sulfate is one of a good way to improve the resistance of commercial pure titanium (cp‐Ti) in phosphate saline buffer solution (PSB). The potentiostatic behavior of anodized titanium in sulfuric acid with nickel sulfate differed markedly from that of titanium anodized in sulfuric acid free from nickel sulfate. Polarization and electrochemical impedance spectroscopy (EIS) recorded an increase in the corrosion resistance of the passive film. Scanning electron microscopy (SEM) and energy diffraction X‐ray (EDX) analysis were used to investigate the morphology and structure of the anodized film in absence and in presence of nickel sulfate. On the other hand, sealed anodized titanium samples exposed to PSB for up to 3 days have been studied by EIS to obtain detailed information concerning the electrochemical properties of sealed anodized titanium. An equivalent circuit that reproduces the impedance results of porous cp‐Ti oxide (TiO₂) films is proposed. These observations indicate that anodization of cp‐Ti in presence of nickel sulfate and sealing the anodized film can serve as a simple low‐temperature method to enhance the corrosion resistance of cp‐Ti when used as an implant material.     

Effect of La2O3 on corrosion resistance of laser clad ferrite-based alloy coatings

The ferrite-based alloy powders with different contents of La₂O₃ were laser clad on a steel substrate. The microstructural features and phase structure of these coatings were studied by scanning electron microscope (SEM) and X-ray diffraction (XRD), respectively. The results showed that the microstructure of the coatings with La₂O₃ was refined and purified. The main phase of the coatings was γ (Fe, Ni). Moreover, the electrochemical properties of the coatings were investigated by anodic polarization curves and electrochemical impedance spectroscopy (EIS). Anodic polarization results indicated that both polarizing voltage and polarization current density were reduced with the addition of La₂O₃. EIS results showed that, with the increment of La₂O₃, the inductive arcs shrunk and capacitive arcs expanded. The inductive arc at low frequency was disappeared and changed to capacitive arc thoroughly when the content of La₂O₃ reached 1.2 wt.%. The corrosion weight loss experiment results showed that the corrosion rate was lower and the corrosion attack was lighter in the coatings with La₂O₃ than that without La₂O₃, resulting in a substantial improvement of the corrosion resistance.