Corrosion protection of Mg alloys by cathodic electrodeposition coating pretreated with silane

The corrosion resistance characteristics of three coatings on magnesium alloy AZ31—conventional paint with phosphate film, cathodic electrodeposition coating (E-coating), and E-coating pretreated with silane (Mg/silane/E-coating)—have been studied by means of electrochemical impedance spectroscopy (EIS) in a 3.5 wt% NaCl neutral aqueous solution and salt spray test using ASTM B117. Silane film was obtained by dipping AZ31 specimens in diluted hydroalcoholic silanic solutions and successively curing. It was found that the corrosion resistance of the Mg alloy with E-coating was superior to conventional paint and could be further enhanced with silane pretreatment as an interfacial film. The results of water volume fraction (Φ_saturation) and diffusion coefficient (D) also indicated that the Mg/silane/E-coating possessed excellent compactness and corrosion resistance. A model of the corrosion mechanism for Mg/silane/E-coating has been presented through EIS analysis.     

Electrochemical study of modified bis-[triethoxysilylpropyl] tetrasulfide silane films applied on the AZ31 Mg alloy

This work investigates the protective behaviour of bis-[triethoxysilylpropyl] tetrasulfide silane pre-treatments on the AZ31 Mg alloy. The silane solution was modified by the addition of cerium nitrate or lanthanum nitrate in order to introduce corrosion inhibition properties in the silane film.The corrosion behaviour of the pre-treated AZ31 magnesium alloy was studied during immersion in 0.005 M NaCl solution, using electrochemical impedance spectroscopy and the scanning vibrating electrode technique (SVET). The electrochemical experiments showed that the presence of cerium ions or lanthanum ions improve the protective behaviour of the silane film. The SVET experiments evidenced that the presence cerium in the silane film led to an important reduction of the corrosion activity.The results demonstrate that either cerium ions or lanthanum ions can be used as additives to the silane solutions to improve the performance of the pre-treatments for the AZ31 magnesium alloy.     

Plasma interface engineered coating systems for magnesium alloys

In this study, a dc low-temperature plasma technique, including plasma treatment and plasma polymerization, was used to create interface engineered coating systems with a structure of Mg/plasma interlayer/cathodic electrocoating (E-coat) for machined AZ31B magnesium (Mg) alloy panels. The plasma interlayer deposited from trimethylsilane (TMS) precursor had a nano-scale thickness of ∼65 nm and well-controlled surface properties through subsequent plasma treatments in order to achieve different level of interfacial adhesion between the E-coat and the Mg substrates. The surface wettability of the plasma interlayer was monitored by water surface contact angle measurement. The interface adhesion of the coating system was evaluated using N-methylpyrrolidinone (NMP) paint removal test and ASTM tape test conducted under dry and wet conditions. Electrochemical impedance spectroscopy (EIS) was employed to investigate the effects of plasma interlayer properties including surface wettability and adhesion enhancement on corrosion protection properties of the coating systems. It was found that a more wettable interface enhanced the electrolyte penetration through the coating and thus reduced the corrosion resistance of the coating system. On the other hands, the improved interface adhesion had little effects on EIS results mainly due to the high chemical reactivity of the Mg alloy substrates.     

Deposition temperature effect on sputtered hydroxyapatite coatings prepared on AZ31B alloy substrate

The corrosion of Mg alloys is a provocative topic and it is still a challenge to find a solution for the improvement of their degradation rate into solution found in human body (Simulated Body Fluid, SBF). The aim of the present paper is to coat AZ31B alloy by hydroxyapatite (HAp) as a possible solution in order to change its degradation behaviour for medical implants. Since the Mg alloy is sensible to temperature while the HAp properties depend on the deposition temperature, in this study, the effect of deposition temperature on the properties of the AZ31Balloy was evaluated. The HAp coatings were prepared using the RF magnetron sputtering technique, ranging the temperature from the room one to 400 °C. It was found that the grain size of the investigated Mg alloy increased more than 100% when the deposition temperature was increased. By increasing the temperature, the hardness level was reduced of about 15%. All HAp coatings revealed corrosion behaviour much better than the uncoated AZ31B alloy; in particular, the coating deposited at 200 °C exhibited the best corrosion behavior. Moreover, the best protection to the corrosive attack of SBF was found for the HAp coating deposited at 200 °C (97.3%), which was also characterized by the lowest porosity. To conclude, HAp coatings can be used to improve the properties of AZ31B alloys, but just up to 200 °C; beyond this temperature, the mechanical and the anticorrosion properties are lost.     

Corrosion behavior study of AZ91 magnesium alloy coated with methyltriethoxysilane doped with cerium ions

The present work aims to investigate the corrosion behavior of AZ91 magnesium alloy treated with a 4% (v/v) methyltriethoxysilane (MTES) alcohol solution, with and without an alkaline pretreatment. The corrosion resistance was assessed by electrochemical impedance spectroscopy (EIS) and current densities were monitored by potentiodynamic polarization curves during immersion in a 0.1 M Na₂SO₄ solution. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were used to perform a surface analysis. The electrochemical results showed an improvement of anticorrosion properties of AZ91. Furthermore, alkaline pretreatment enhances adhesion between silane film and substrate surface. This can be attributed to a surface enrichment in hydroxyl groups after the alkaline step, which increases formation of Si–O–Mg covalent bonds. The addition of Ce(NO₃)₃ to the MTES bath was evaluated, and it was found that the electrochemical response depends on the cerium ions concentration used. It was shown that the addition of 6.0 × 10⁻⁵ M of Ce(NO₃)₃ to a MTES bath improves corrosion resistance. Higher concentration of cerium ions lead to destabilizing the siloxane network, decreasing the efficiency of the silane coatings.     

Corrosion protection of cold-rolled steel by low temperature plasma interface engineering: I. Enhancement of E-coat adhesion

An anode magnetron enhanced d.c. cathodic plasma treatment of a cold-rolled steel (CRS) plate and cathodic (plasma) polymerization were used to create interface engineered systems of cathodic E-coat/plasma polymer/plasma treated CRS. The adhesion of the E-coat and the corrosion protection characteristics of the systems were compared with the control, E-coat/Zn phosphate-chromate/alectro-galvanized steel (EGS). The adhesion of the E-coat to the plasma polymer coaled CRS was found to be excellent; the E-coat could not be removed by N-methyl pyrrolidone (60 °C) in 5 days, while the same E-coat applied on the control was removed in a few minutes. The plasma polymer of trimethylsilane (TMS) was found to yield excellent corrosion protection as used in the interface engineered systems, of which the corrosion (GM scab) test was found to be better than that for the control. The plasma pretreatment of the CRS surface prior to the cathodic polymerization of TMS was found to be a critically important factor. The corrosion-induced delamination of the first paint layer seems to play a key role in the corrosion of painted steel. It was demonstrated that good adhesion and durability of the entire interface system can produce a highly corrosion resistant painted CRS.     

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.     

Ni-W-Fe-P四元合金镀层在酸碱盐溶液中的腐蚀行为

在Ni-W-P合金镀液中加入硫酸亚铁,并通过适当的工艺在Q235钢表面制备了Ni-W-FeP四元合金镀层。采用扫描电子显微镜观察了镀层的表面形貌,通过能谱仪测试了镀层中各元素的质量分数,通过X射线衍射仪分析了镀层的结构,并借助极化曲线和交流阻抗曲线方法考察了镀层和Q235钢在体积分数为5%的H2SO4溶液、质量分数为5%的NaOH溶液和质量分数为3.5%的NaCl溶液中的腐蚀行为。结果表明:Ni-W-Fe-P合金镀层为非晶态结构,表面较为均匀,W和Fe的质量分数分别约为2.71%和1.56%。在上述三种腐蚀介质中,镀层的耐蚀性远优于Q235钢的,主要是镀层在酸、碱、盐介质中表面形成钝化膜所致。     

Corrosion behavior study of AZ91 magnesium alloy coated with methyltriethoxysilane doped with cerium ions

The present work aims to investigate the corrosion behavior of AZ91 magnesium alloy treated with a 4% (v/v) methyltriethoxysilane (MTES) alcohol solution, with and without an alkaline pretreatment. The corrosion resistance was assessed by electrochemical impedance spectroscopy (EIS) and current densities were monitored by potentiodynamic polarization curves during immersion in a 0.1 M Na₂SO₄ solution. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were used to perform a surface analysis. The electrochemical results showed an improvement of anticorrosion properties of AZ91. Furthermore, alkaline pretreatment enhances adhesion between silane film and substrate surface. This can be attributed to a surface enrichment in hydroxyl groups after the alkaline step, which increases formation of Si–O–Mg covalent bonds. The addition of Ce(NO₃)₃ to the MTES bath was evaluated, and it was found that the electrochemical response depends on the cerium ions concentration used. It was shown that the addition of 6.0 × 10⁻⁵ M of Ce(NO₃)₃ to a MTES bath improves corrosion resistance. Higher concentration of cerium ions lead to destabilizing the siloxane network, decreasing the efficiency of the silane coatings.     

AZ91D镁合金化学镀镍前处理工艺研究

对AZ 91D镁合金碱性化学镀镍的前处理工艺进行研究,得到了镁合金一步磷化的前处理工艺,确定了AZ 91D镁合金磷化液的组成及工艺条件,经一步磷化前处理后即可进行化学镀镍.采用扫描电镜(SEM)、能谱成分分析(EDS)对磷化后的试片的微观形貌和组成成分进行了分析,并测定了AZ 91D镁合金及其化学镀镍后的Tafel曲线...     

A novel approach to heal the sol-gel coating system on magnesium alloy for corrosion protection

Sol-gel-based coatings exhibit high potentiality to be as an alternative to toxic chromate coatings for surface pre-treatment of metals and alloys. However, as soon as even small defects appear in the coating, the coating cannot stop the development of corrosion process. Present work demonstrates the possibility to use zinc nitrate as healing agent to repair the organic silane coatings in NaCl solution. The zinc nitrate was added to the 0.005 M NaCl solution where AZ91D magnesium alloy coated with organic silane coating was immersed. The healing process and the healing mechanism were investigated by electrochemical measurements and scanning electron microcopy coupled with energy dispersive spectroscopy. The results demonstrated the introduction of zinc nitrate to the electrolyte could stop the development of corrosion process of the coating system and a remarkable recovery on corrosion resistance could be obtained. This effect may be attributed to the formation of zinc oxide/hydroxide on the defective areas, hindering the corrosion activities.     

Electrochemical behavior of magnesium alloys as biodegradable materials in Hank's solution

The electrochemical behavior of extruded AZ31E and AZ91E alloys was investigated in Hank's solution at 37 °C. The behavior of the two alloys was studied with immersion time using electrochemical impedance spectroscopy (EIS), potentiodynamic polarization and weight loss tests. It was found that the corrosion resistance of AZ31E alloy is higher than that of AZ91E. Also, the effect of adding different concentrations of a commercial drug called glucosamine sulphate (as inhibitor) to Hank's solution was studied for AZ31E alloy. The corrosion was effectively inhibited by the addition of 0.01 mM glucosamine sulphate that reacts with AZ31E alloy and forms a protective film on its surface. The results were confirmed by surface examination via scanning electron microscope.     

硅烷偶联剂预处理对Q235钢表面聚偏氟乙烯涂层性能的影响

先采用KH-560硅烷偶联剂体积分数不同的硅烷溶液处理Q235钢,再制备聚偏氟乙烯(PVDF)防腐涂层。研究了KH-560体积分数对硅烷溶液水解率及PVDF涂层的表面形貌、疏水性和耐蚀性的影响。结果表明,采用KH-560体积分数为9%的硅烷溶液预处理Q235钢后制备的PVDF涂层表面疏水性较强,在400°C内具有较好的热稳定性,硬度为5H,耐弯曲性、耐酸碱性、耐盐水性(14 d)均优于未采用硅烷溶液处理的O235钢上涂覆的PVDF涂层。     

Analytical and microscopic characterisation of modified bis-[triethoxysilylpropyl] tetrasulphide silane films on magnesium AZ31 substrates

In this work solutions of bis-[triethoxysilylpropyl] tetrasulphide silane modified with cerium nitrate are used as pre-treatments for the AZ31 Mg alloy.     

[V10O28]6-柱撑纳米水滑石在AZ31镁合金有机防腐涂层中的应用

研制了一种以钒酸盐阴离子([V10O28]6-)柱撑纳米水滑石防腐颜料替代铬酸盐,用于AZ31镁合金腐蚀防护的有机涂层.研究了水滑石在不同浓度的NaCl溶液里的吸附和离子交换性能,以及钒酸盐缓蚀剂的极化曲线:考察了该水滑石防腐颜料的添加比例对镁合金环氧防腐涂层性能的影响,并通过电化学交流阻抗(EIS)测试技术对各试样进行了性能检测.结果表明,添加了20%(质量分数)水滑石的环氧涂层对镁合金具有较好的防腐作用.     

The surface, microstructure and corrosion of magnesium alloy AZ31 sheet

This study investigates the effect of some industrial pre-treatments, including heat-treatment, surface grinding and polishing, acid cleaning and sandblasting, on the corrosion performance of Mg alloy AZ31 sheet. It is found that tempering accelerates the corrosion of AZ31. Surface grinding and acid cleaning dramatically improve its corrosion resistance, while sandblasting severely deteriorates its corrosion performance. Surface analysis indicates that the change in corrosion behavior of AZ31 by these pre-treatments can be associated with the alteration of its impurity contamination, surface state, grain size and intermetallic particles. A corrosion model concerning the dissolution and precipitation of tiny Al-Mn-(Fe) particles in grains and grain boundaries is proposed to explain the effect of mechanical deformation and heat-treatment on the corrosion performance of AZ31.     

A pretreatment with galvanostatic etching for copper electrodeposition on pure magnesium and magnesium alloys in an alkaline copper-sulfate bath

A pretreatment with galvanostatic etching is recommended to obtain an adherent and uniformly covered copper deposit on pure magnesium and magnesium alloy specimens (AZ31 and AZ61) in an alkaline copper-sulfate bath. The effect of galvanostatic etching on the surfaces of Mg and Mg alloy specimens can be realized by their potential variation during galvanostatic etching, in which four distinct stages could be distinguished. Galvanostatic etching to stage III, an activated surface of Mg or Mg alloy, was obtained for electroplating a uniformly covered Cu deposit in the alkaline Cu-sulfate bath. The Cu-deposited Mg or Mg alloy was used as the substrate for further Cu and then Ni electrodeposition in acid plating baths to obtain a protective Ni/Cu coating. The proposed electroplating baths are environmentally friendly, and the electrodeposition process is easy to conduct to achieve a protective coating for Mg and Mg alloys.     

AZ31B镁合金微弧氧化膜复合封孔工艺的研究

对AZ31B镁合金微弧氧化膜复合封孔工艺进行了研究。采用扫描电子显微镜观察了微弧氧化膜的表面形貌,采用X射线衍射仪分析了微弧氧化膜的结构,并采用电化学工作站测试了微弧氧化膜的极化曲线。通过实验得到最佳的微弧氧化电参数为:电流密度3 A/dm^2,脉宽100μs,频率800~1100 Hz。另外,采用质量分数为10%的硅烷溶液-质量浓度为20 g/L的PTFE悬浮液进行复合封孔后,得到的微弧氧化膜的耐蚀性好。     

Corrosion behaviors of Zn/Al-Mn alloy composite coatings deposited on magnesium alloy AZ31B (Mg-Al-Zn)

After being pre-plated a zinc layer, an amorphous Al-Mn alloy coating was applied onto the surface of AZ31B magnesium alloy with a bath of molten salts. Then the corrosion performance of the coated magnesium alloy was examined in 3.5% NaCl solution by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The results showed that the single Zn layer was active in the test solution with a high corrosion rate while the Al-Mn alloy coating could effectively protect AZ31B magnesium alloy from corrosion in the solution. The high corrosion resistance of Al-Mn alloy coating was ascribed to an intact and stable passive film formed on the coating. The performances of the passive film on Al-Mn alloy were further investigated by Mott-Schottky curve and X-ray photoelectron spectroscopy (XPS) analysis. It was confirmed that the passive film exhibited n-type semiconducting behavior in 3.5% NaCl solution with a carrier density two orders of magnitude less than that formed on pure aluminum electrode. The XPS analysis indicated that the passive film was mainly composed of AlO(OH) after immersion for long time and the content of Mn was negligible in the outer part of the passive film. Based on the EIS measurement, electronic structure and composition analysis of the passive film, a double-layer structure, with a compact inner oxide and a porous outer layer, of the film was proposed for understanding the corrosion process of passive film, with which the experimental observations might be satisfactorily interpreted.