铝阳极氧化膜的显微组织与性能研究

研究了ＬＹ１１硬铝合金硫酸法阳极氧化膜的组织结构及其性能,讨论了电解液组成和工艺条件对它们的影响。结果表明,电解液中Ｈ２ＳＯ４浓度增大,易得到较厚的多孔型氧化膜;而稀Ｈ２ＳＯ４（１０％体积比）电解液,可获得致密、无孔洞的相对较薄的氧化膜,其耐蚀性、电绝缘性和表面硬度均明显改善。工艺操作参量中,保持较低的电解液温度、合适的阳极电流密度及氧化时间,有利于膜层综合性能的提高。     

Effects of alternating current on corrosion of a coated pipeline steel in a chloride-containing carbonate/bicarbonate solution

In this work, the alternating current (AC)-induced corrosion of a coated pipeline steel was studied in a chloride-containing, concentrated carbonate/bicarbonate solution, which simulated the trapped high pH electrolyte under coating, by potentiodynamic polarization measurements, immersion tests and surface characterization technique. It was found that an application of AC resulted in a negative shift of corrosion potential of the steel, caused an oscillation of anodic current density, and degraded the steel passivity developed in the solution. With the increase of AC current density, the corrosion rate of the steel increased. At a low AC current density, a uniform corrosion occurred, while at a high AC current density, pitting corrosion occurred extensively on the steel electrode surface. At individual applied AC, there was a higher electrochemical dissolution activity of the coated steel electrode containing a 1 mm defect than that of the electrode containing a 10 mm defect.     

Corrosion and passivation mechanism of chromium diboride coatings on stainless steel

The corrosion resistance of fully crystalline CrB₂ coatings magnetron sputtered onto AISI 316L stainless steel was tested in acidic solutions. CrB₂ coatings showed excellent corrosion protection, but suffered a breakdown when an anodic potential of greater than about +1 V (SHE) was applied to the surface in a 1 M HCl electrolyte. The coating failure at high potentials is attributed to transpassive dissolution of the coating at volume defects, enabling the electrolyte to reach the underlying 316L substrate, resulting in its rapid corrosion and subsequent fracturing of the coating. Electrochemical data and potential-pH (Pourbaix) diagrams, constructed from thermodynamic data, indicate that the corrosion resistance of CrB₂ is due to the formation of a Cr(III) oxide passive film in the absence of activation corrosion.     

Effects of benzotriazole on anodized film formed on AZ31B magnesium alloy in environmental-friendly electrolyte

An environmental-friendly electrolyte of silicate and borate, which contained an addition agent of 1H-benzotriazole (BTA) with low toxicity (LD50 of 965 mg/kg), was used to prepare an anodized film on AZ31B magnesium alloy under the constant current density of 1.5 A/dm² at room temperature. Effects of BTA on the properties of the anodized film were studied by scanning electron microscopy (SEM), energy dispersion spectrometry (EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), loss weight measurement, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS), respectively. The results demonstrated that anodized growth process, surface morphology, thickness, phase structure and corrosion resistance of the anodized film were strongly dependant on the BTA concentration, which might be attributed to the formation of an BTA adsorption layer on magnesium substrate surface. When the BTA concentration was 5 g/L in the electrolyte, a compact and thick anodized film could provide excellent corrosion resistance for AZ31B magnesium alloy.     

Preparation of hydrophobic anodic film on AZ91D magnesium alloy in silicate solution containing silica sol

Anodic films were prepared on the AZ91D magnesium alloy in the electrolyte of 1.0 M Na₂SiO₃ with and without the addition of silica sol under the constant current density of 20 mA/cm² at 60 °C. The anodic films were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The results showed that the two main constituents of the anodic films were silicon and oxygen. However, no crystal compound including either silicon or oxygen could be detected by the XRD patterns. The addition of 10 vol.% silica sol increased the thickness of the anodic film and improved the roughness of the film surface. Furthermore, such anodic film revealed some hydrophobic property, which was not observed on the anodic film formed in the base electrolyte without addition of silica sol. And the electrochemical impedance spectroscopy (EIS) results showed that the addition of 10 vol.% silica sol improved the corrosion resistance of the anodic film for the AZ91D Mg alloy obviously.     

Electrochemical corrosion of X65 pipe steel in oil/water emulsion

The electrochemical corrosion behavior of X65 pipeline steel in the simulated oil/water emulsion was investigated under controlled hydrodynamic and electrochemical conditions by rotating disk electrode technique. Results demonstrated that mass-transfer of oxygen plays a significant role in the cathodic process of steel in both oil-free and oil-containing solutions. Electrode rotation accelerates the oxygen diffusion and thus the cathodic reduction. The higher limiting diffusive current density measured in oil-containing solution is due to the elevated solubility of oxygen in oil/water emulsion. The anodic current density decreases with the increase of electrode rotating speed, which is attributed to the accelerated oxygen diffusion and reduction, enhancing the steel oxidation. Addition of oil decreases the anodic dissolution of steel due to the formation of a layer of oily phase on steel surface, increasing the reaction activation energy. The steel electrode becomes more active at the elevated temperature, indicating that the enhanced formation of oxide scale is not sufficiently enough to offset the effect resulting from the enhanced anodic dissolution reaction kinetics. The corrosion reaction mechanism is changed upon oil addition, and the interfacial reaction is activation-controlled, rather than mass-transfer controlled. When sand particles are added in oil/water emulsion, there is a significant increase of corrosion of the steel. The presence of sands in the flowing slurry would impact and damage the oxide film and oily film formed on the steel surface, exposing the bare steel to the corrosive solution.     

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.     

Observations of anomalies in the anodic behaviour of microcrystalline aluminium

The anodic behaviour of sputtered microcrystalline Al (mc-Al) was investigated in neutral Na₂SO₄ electrolyte under varied conditions. Our results revealed that Cl⁻ addition led to a reduction in the anodic current density, which we considered unusual. Mott-Schottky analysis showed that Cl⁻ introduction altered the semiconducting property of the passive film from n-type to p-type, implying that the p-type film can possessed a relative higher stability. Immersion of mc-Al in other electrolytes yielded films with n-type, p-type and positive p-n junction structure. The results also indicate that the p-type film was most stable and the positive p-n junction film least stable.     

Anodic films formed on magnesium in organic, silicate-containing electrolytes

Anodic films were prepared on magnesium in electrolyte solutions consisting of 3.0 M KOH and various concentrations of sodium silicate and aqueous ethylene-glycol solutions. The anti-corrosion properties of the films formed in the ethylene-glycol electrolyte solutions ranging from 10 to 40 wt% far exceeded that of the anodic film produced using the HAE method. The film formed under optimal conditions had excellent anti-corrosion properties, which were more than 10-fold greater than those of the HAE anodic films. The anodic film consisted of two layers—a heterogeneous porous layer and a barrier layer; moreover, both carbon and silicate were detected in the anodic film.     

Preparation and electrochemical characterization of amoxicillin-doped cellulose acetate films for AA2024-T3 aluminum alloy coatings

Cellulose acetate films doped with amoxicillin were deposited onto AA2024-T3 aluminum alloy and the corrosion protection in 0.05 M NaCl was evaluated by Electrochemical Impedance Spectroscopy (EIS) and the Scanning Vibrating Electrode Technique (SVET). The doping of the cellulose acetate film with amoxicillin resulted in a significant increase in the high frequency resistance and a decrease in the capacitance of the material. The protective effect could be observed under anodic polarization by way of a marked decrease in the anodic current. These results show the promising potential for the deposition of cellulose acetate films doped with amoxicillin onto AA2024-T3.     

大风沙地区铝合金接触网零部件表面处理的优选

目的提高铝合金接触网零部件表面耐磨损性能,以增加其在大风沙地区的使用寿命。方法对接触网零件切割进行试样制备。在硅酸盐体系电解液中,采用20 k W直流脉冲微弧氧化设备对试样表面进行微弧氧化处理,电解液为硅酸盐,氧化时间为30 min。同时制备阳极氧化处理的平行试样。通过硬度测试、摩擦磨损试验以及扫描电子显微镜(SEM)测试,分别评价两种表面处理方式的表面硬度、耐磨性能,利用中性盐雾试验来评价其耐腐蚀性能,并通过扫描电子显微镜来观察两种膜层的差异。结果通过对铝合金接触网进行阳极氧化和微弧氧化处理能明显提高表面耐磨性。阳极氧化膜层硬度为350.3HV,微弧氧化膜层硬度约为阳极氧化膜硬度的4倍,达到1510.8HV。经过HT-600高温摩擦磨损试验机30 min的磨损试验,铝合金基体质量损失2 mg,阳极氧化膜质量损失0.8 mg,而微弧氧化膜的质量损失只有0.15 mg左右,且微弧氧化膜层表现出了更好的耐腐蚀性能。结论微弧氧化膜层能表现出更加优异的耐磨及耐腐蚀性能,因此微弧氧化更适合大风沙地区铝合金零件的表面处理。     

Pulse-reverse electroplating of chromium from Sargent baths: Influence of anodic time on physical and electrochemical properties of electroplated Cr

Herein, chromium film was successfully synthesized by pulse-reverse (PR) electrodeposition using various anodic current time in a Sargent bath which is mainly composed of hexavalent chromium (Cr⁶⁺) and sulfuric acid (H₂SO₄). The correlation between anodic time during electroplating and various physical properties was investigated. The crack density, hardness, and thickness of electrodeposited chromium was decreased with an increase in anodic time for PR electroplating. The chromium prepared by PR electroplating showed higher corrosion resistance than that prepared by direct current (DC) electroplating owing to low crack density. Consequently, the optimal anodic time for PR electroplating was found to be 0.001 s based on the crack density, hardness, current efficiency, and film thickness. The results obtained suggest that this optimized process is a promising route for electroplating chromium film with low crack density and high corrosion resistance.     

磷化处理对无铬钝化热镀锌板耐蚀性能的影响

研究了磷化处理工艺对无铬钝化热镀锌板耐腐蚀性能和表面形貌的影响。采用扫描电镜对其表面形貌进行分析，同时与未经过磷化处理的钝化板表面形貌进行对比；采用电化学阳极极化曲线方法和电化学阻抗法对磷化处理后钝化板的耐腐蚀性能进行了研究。在钝化板膜重为0.8 g/m²的情况下，经磷化处理的钝化板表面钝化膜完好，没有发现锈蚀或钝化膜剥落现象；经磷化处理的钝化板自腐蚀电位和阳极电流密度不变，阴极电流密度和自腐蚀电流密度有所提高；Nyquist图的高频部分在磷化处理前为容抗弧，磷化处理后出现具有Warburg阻抗的直线，说明磷化处理后钝化膜表面出现扩散过程。 研究表明，钝化板经过磷化处理后表面未形成磷化膜，耐腐蚀性能仍来自原钝化膜，经磷化处理的钝化板的耐腐蚀性能有所降低。因此，现有常规的磷化处理并没有增加钝化板的耐腐蚀性能，如果有需要提高钝化板耐腐蚀性能的要求，必须针对无铬钝化板研制专用的磷化液和磷化工艺。     

钛合金阳极氧化膜在Hank''''s溶液中的腐蚀行为

利用扫描电镜(SEM)和恒电位阶跃法，研究了不同工艺条件下得到的钛合金(TC4)阳极氧化膜在Hank’s模拟体液中的耐蚀性。分析了不同电解液组成、电解液温度及阳极氧化时间对其耐蚀性的影响。结果表明在磷酸溶液中生成的氧化膜耐蚀性较好，此外电解液的温度、极化时间对膜层耐蚀性也有显著影响。     

The effects of Cl ion concentration and relative humidity on atmospheric corrosion behaviour of PCB-Cu under adsorbed thin electrolyte layer

The effects of Cl⁻ ion concentration and relative humidity on atmospheric corrosion behaviour of PCB-Cu under adsorbed thin electrolyte layer were investigated by cathodic polarization curves and electrochemical impedance spectroscopy. Results indicated that the cathodic process of PCB-Cu corrosion was dominated by the reduction of oxygen and corrosion products. The cathodic current density increased with increasing relative humidity and Cl⁻ ion concentration. The corrosion rate was initially dominated by oxygen reduction, but at the later stage of corrosion, the anodic process began to affect the corrosion rate due to the accumulation of corrosion products.     

Monte Carlo simulation of uniform corrosion process under potentiostatic conditions

The aim of this paper is to study the corrosion resistance of industrial coatings of metallic alloys including certain amount of process-induced porosity. Surface damages during a simulated corrosion process are investigated using Monte Carlo simulation technique and compared to corrosion response (dissolution currents). In this simulation, a 3D grid of the coating is subject to an electrolyte attack under potentiostatic conditions. The surface damages are related to a controlled dissolution process governed by dissolution probability, roughness, porosity size and fraction. In order to validate the model results, theoretical I = f(t) curves are compared to corrosion behaviour of Fe-40Al samples pointing out critical parameters affecting current density and exposed area. Predictions relating the porosity level to corrosion behaviour are established and discussed. The main conclusions focus on a primary effect of pore size and connectivity and a secondary effect of porosity level in the considered process window (porosity levels between 5.8% and 7.8%). The experimental work shows that the porosity effect could not explain all observed trends and a deeper examination of the microstructure reveals another candidate (unmolten particles) which is expected to vary both pore connectivity and dissolution events.     

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。     

Identification of the selective corrosion existing at the seam weld of electric resistance-welded pipes

The selective corrosion existing at the seam weld of high frequency electric resistance welded pipes of carbon steel with low sulfur content in electrolyte solutions is revealed by localized electrochemical measurements. The seam weld, mainly consisted of ferrite, has more negative open circuit potential and higher anodic dissolution current density than the base metal consisting ferrite and pearlite. Between the seam weld and the base metal, there is a galvanic coupling effect accelerating the dissolution kinetics of the seam weld such that V-shaped corrosion groove preferentially occurs at the seam weld.     

AZ91D镁合金微弧氧化膜的腐蚀行为研究

利用双向全波脉冲电源对AZ91D镁合金在硅酸盐体系中进行了微弧氧化处理,通过电化学阻抗谱(EIS)测试、极化曲线分析并结合XRD和SEM等分析方法对微弧氧化处理的镁合金腐蚀行为进行了研究.结果表明,微弧氧化膜表面分布着几微米的微孔,微弧氧化膜中主要含有MgF2,Mg2SiO4和Al2O3.AZ91D镁合金经过微弧氧化处理之后,耐蚀性能明显提高,自腐蚀电流密度降低3个数量级,自腐蚀电位高出约300 mV,阻抗值高出3个数量级,研制的微弧氧化膜对镁合金具有很好的防腐保护性能.     

石墨烯掺杂对镁锂合金微弧氧化膜Cl?腐蚀敏感性的研究

为了研究添加石墨烯后镁锂合金微弧氧化膜在不同NaCl浓度下的腐蚀行为,通过向硅酸盐体系电解液中添加石墨烯,在镁锂合金表面制备出改性的MAO(Micro-arc oxidation)膜层,采用电化学极化曲线和阻抗谱方法研究改性膜层对NaCl溶液的腐蚀敏感性。结果表明:石墨烯的添加可有效改善由于微弧放电形成的孔洞及微裂纹等缺陷,提高膜层致密性和耐蚀性;改性的MAO膜层耐腐蚀性能随着NaCl溶液浓度的升高而降低,主要因为在较高的浓度梯度作用下,侵蚀性离子向膜层中扩散速率加快,进而加速了对MAO膜层的腐蚀破坏。