Electroless Ni-Sn-P coating on AZ91D magnesium alloy and its corrosion resistance

An electroless Ni-Sn-P coating was deposited on AZ91D magnesium alloy in an alkaline-citrate-based bath where nickel sulphate and sodium stannate were used as metal ion sources and sodium hypophosphite was used as a reducing agent. The phase structure of the coating was amorphous. SEM and attached EDS observation revealed the presence of dense and uniform nodules in the ternary coating and the content of tin was 2.48wt.%. Both the electrochemical analysis and the immersion test in 10% HCl solution proved that the ternary Ni-Sn-P coating exhibited better corrosion resistance than the Ni-P coating in protecting the magnesium alloy substrate.     

Atmospheric corrosion of field-exposed magnesium alloy AZ91D

The magnesium alloy AZ91D was exposed in three different types of atmospheric environment, viz. urban, rural and marine exposure sites. Corrosion rates, corrosion products formed, and the influence of the microstructure on the corrosion behaviour of the alloy were investigated. The corrosion rate of AZ91D exposed in the marine environment was 4.2 μm/year, and in the rural and urban environments 2.2 and 1.8 μm/year, respectively. The main corrosion product found was magnesium carbonate hydromagnesite (Mg₅(CO₃)₄(OH)₂·4H₂O), which was formed at all three exposure sites. The corrosion attack started in the -phase in larger grains at the boundary between the -phase and the eutectic -/β-phase. Microgalvanic elements were formed with the eutectic -/β-Mg phase as cathodic site and the -Mg grains as anodes. The Al–Mn particles played a minor roll in the initiation process, even though these particles are the most noble in the microstructure and thus the driving force for a corrosion attack around these particles could be expected to be high. A close resemblance was observed between the corrosion mechanisms operating under the field-exposure conditions described here and the mechanisms operating under the previously reported laboratory conditions.     

Roles of β phase in the corrosion process of AZ91D magnesium alloy

For better understanding of the roles of β phase in the corrosion processes of AZ91D alloy, corrosion behavior of a cast (α + β phase) and a homogenized (α phase) AZ91D alloy was investigated in NaCl aqueous solution by gas collection and electrochemical measurements. According to the hydrogen evolution properties during corrosion, two different types of corrosion tend might be differentiated. For type I, hydrogen diffused into alloy, which evoked the decreasing of hydrogen evolution rate (HER) and the weakening of negative difference effect (NDE). For type II, in the corrosion process, hydrogen in the alloys diffused into the product film (P-type semiconductor), which suggested that hydrogen entering the film would be ionized. The generated electrons during ionization decreased the concentration of vacancies in the valence band of the product films, indicating an improvement of corrosion resistance of AZ91D alloy.     

Characterization of anodic films formed on AZ91D magnesium alloy

Anodization of die-casted AZ91D magnesium alloy was performed in 3 M KOH+0.21 M Na₃PO₄+0.6 M KF base electrolyte with and without Al(NO₃)₃ addition. The anodic film was characterized by using X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The corrosion resistance of the various anodized alloys was then evaluated in 3.5 wt % NaCl solution using electrochemical impedance spectroscopy (EIS) and immersion testing. The results showed that the anodic film was mainly composed of MgO. The addition of Al(NO₃)₃ into the base electrolyte results in the formation of Al₂O₃ and Al(OH)₃ in the anodic film. The maximum amount of Al₂O₃ was found in the anodic film when the alloy was anodized in the electrolyte containing 0.15 M Al(NO₃)₃. The results of EIS analysis and morphological examination showed that the MgO anodic film modified with Al₂O₃ exhibited the superior corrosiom resistance for AZ91D Mg alloy.     

Electroless Ni-P layer with a chromium-free pretreatment on AZ91D magnesium alloy

A phosphate-manganese conversion film was proposed as the pretreatment layer between Ni-P coating and AZ91D magnesium alloy substrate, to replace the traditional chromium oxide plus HF pretreatment. The subsequent Ni-P deposited on the layer was also characterized by its structure, morphology, microhardness and corrosion-resistance. The pretreatment layer on the substrate not only reduces the corrosion of magnesium during Ni-P plating process, but also reduces the potential difference between the matrix and the second phase. Thus, a Ni-P coating with fine and dense structure was obtained on the AZ91D magnesium alloy, which shows better corrosion resistance than the Ni-P with chromium oxide plus HF as pretreatment.     

Environmental friendly anodizing of AZ91D magnesium alloy in alkaline borate-benzoate electrolyte

A kind of environmental friendly anodizing routine for AZ91D magnesium alloy, based on an alkaline borate-sodium benzoate electrolyte (NaBz) was studied. The effect of NaBz on the properties of the anodized film was investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive spectrometry (EDS), potentiodynamic polarization and electrochemical impedance spectroscopy (EIS), respectively. The results showed that the anodizing process, surface morphology, thickness, phase structure and corrosion resistance of the anodized film were strongly dependent on the concentration of NaBz. In the presence of adequate NaBz, a thick, compact and smoothing anodized film with excellent corrosion resistance was produced. Moreover, the forming mechanism of the anodized film in the presence of NaBz additive was also approached, which was a suppression of arc discharge process by the adsorption of Bz⁻ on the surface of magnesium alloy substrate.     

Improvement of corrosion resistance of AZ91D magnesium alloy by holmium addition

The corrosion behaviour of two Mg–9Al–Ho alloys (Mg–9Al–0.24Ho and Mg–9Al–0.44Ho) was evaluated by general corrosion measurements and electrochemical methods in 3.5% NaCl solution saturated with Mg(OH)₂. The experimental results were compared with that of Mg–9Al alloy without Ho addition. Various corrosion rate tests showed that the addition of Ho obviously enhanced corrosion resistance of Mg–9Al alloy. The microstructure of the three magnesium alloys and the morphology of their corrosion product film were examined by Electron Probe Microanalysis (EPMA) and Energy Dispersion Spectroscopy (EDS). The alloys with Ho addition showed a microstructure characterized by α phase solid solution, which was surrounded by some β phase and grain-like Ho-containing phase. The improvement of corrosion resistance of the Mg–9Al–Ho alloys could be explained by the fact that the deposited Ho-containing phases were less cathodic. Moreover, the corrosion product films on the Ho-containing alloy surface demonstrated their ability to restrain further corrosion.     

Formation of an aluminum-alloyed coating on AZ91D magnesium alloy in molten salts at lower temperature

An aluminum-alloyed coating was formed on an AZ91D magnesium alloy in molten salts containing AlCl₃ at a lower temperature of 380 °C. The microstructure and phase constitution of the alloyed layer were investigated by optical microscopy, scanning electron microscopy, energy dispersive spectrum and X-ray diffraction. The nano-hardness of the coating was studied by nanoindentation associated with scanning probe microscopy. The corrosion resistance of the coated specimen was evaluated in a 3.5 wt.% NaCl solution by electrochemical impedance spectroscopy and cyclic potentiodynamic polarization. The results show that the aluminum-alloyed coating consists of Mg₂Al₃ and Mg₁₇Al₁₂ intermetallic layers. The formation of the coating is dictated by the negative standard free energy of the reaction: 2AlCl₃ + 3 Mg = 3MgCl₂ + 2Al. This process is associated with a displacement reaction mechanism and diffusion process that takes place during the molten salt treatment. High activity of Al elements in molten salts contributes to the lower temperature formation of the Al-alloyed coating. The alloyed coating markedly improves the hardness as well as the corrosion resistance of the alloy in comparison with the untreated AZ91D magnesium alloy, which is attributed to the formation of the intermetallic compounds.     

About some corrosion mechanisms of AZ91D magnesium alloy

The present work is dedicated to a study of the corrosion resistance of AZ91D (91% Mg) alloy in wet environments. Three industrial alloys obtained by die-casting or sand casting were subjected to salt spray corrosion tests (ASTM-B117 standard) and immersion tests. Weight loss kinetic curves were measured. Surface analysis was performed by X-ray photoelectron diffraction (XPS). After corrosion the sand cast alloy presents a surface mainly enriched in hydroxides and carbonates while the die-cast alloy presents a surface enriched also in mixed Mg-Al oxides. The quantitative analysis of the rate Mg/Al shows an enrichment in aluminium for the die-cast alloys in comparison to the sand cast alloy.     

Galvanic corrosion of magnesium alloy AZ91D in contact with an aluminium alloy, steel and zinc

An investigation was carried out into the galvanic corrosion of magnesium alloy AZ91D in contact with zinc, aluminium alloy A380 and 4150 steel. Specially designed test panels were used to measure galvanic currents under salt spray conditions. It was found that the distributions of the galvanic current densities on AZ91D and on the cathodes were different. An insulating spacer between the AZ91D anode and the cathodes could not eliminate galvanic corrosion. Steel was the worst cathode and aluminium the least aggressive to AZ91D. Corrosion products from the anode and cathodes appeared to be able to affect the galvanic corrosion process through an “alkalisation”, “passivation”, “poisoning” effect or “shortcut” effect.     

Effect of magnesium hydride on the corrosion behavior of an AZ91 magnesium alloy in sodium chloride solution

The effect of magnesium hydride on the corrosion behavior of an as-cast AZ91 alloy in 3.5 wt.% NaCl solution was investigated using gas collection method and potentiostatic test. The Pourbaix diagram of Mg–H₂O system was built using thermodynamic calculation. It was possible that magnesium hydride could form in the whole pH range in theory. The experimental results showed that at cathodic region, magnesium hydride formed on surface, which was the controlling process for the corrosion behavior of AZ91 alloy; at anodic region and free corrosion potential, magnesium hydride model and partially protective film model, monovalent magnesium ion model and particle undermining model were responsible for the corrosion process of AZ91 alloy.     

Chemical conversion coating on AZ31B magnesium alloy and its corrosion tendency

The morphology change of the magnesium matrix after pre-treatment and the mor-phology as well as the phase composition of chemical conversion coating formed by phosphate were studied using scanning electron microscope and X-ray diffraction. The corrosion resistance of the coating was studied by salt spray and damp test, and the corrosion tendency during salt immersion test was analyzed. The results show that the phase composition before and after pre-treatment is almost change- less, and the deep microflaw appears between α and β phases during acidic pickling. The phosphate conversion coating is mainly composed of Mg, MgO, and some amor-phous phase, and it can provide a good protection for the AZ31B alloy. Results from corrosive morphology indicate that the growth and the corrosion resistance of the phosphate conversion coating are related to the forming process of the AZ31B matrix.     

AZ91D镁合金在含SO_2大气环境中的初期腐蚀行为

采用室内加速的方法,利用金相显微镜、扫描电镜和X射线衍射等手段对AZ91D镁合金在含微量SO2工业污染环境中的初期腐蚀层形貌以及腐蚀产物进行了分析和研究。结果表明:SO2加速镁合金的腐蚀,随着SO2含量增加,镁的腐蚀速率加快。镁合金的初期腐蚀具有局部腐蚀的特征。腐蚀优先从α相基体开始,腐蚀初期在材料表面生成一层保护性的含有MgO和Mg(OH)2的薄膜。SO2降低了薄液层的pH值,增强溶解过程,促进可溶性MgSO3·6H2O和MgSO4·6H2O腐蚀产物的生成,使表面膜失去保护作用,加速镁合金的后期腐蚀。     

Effect of surface nanocrystallization on the microstructural and corrosion characteristics of AZ91D magnesium alloy

Surface distinct deformed layers with thicknesses up to 150 μm, with grain size in the top most surface is in the nanometer scale, were produced on AZ91D magnesium alloy using surface mechanical attrition treatment (SMAT). Effects of different ball size on the properties of the SMATed samples were investigated. The microstructural, grain size, hardness and roughness features of the treated surfaces were characterized using optical microscopy (OM), scanning electron microscopy (SEM), X-ray diffraction (XRD), micro-indenter and digital roughness meter, respectively. Corrosion behavior of the samples was evaluated using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. It is found that the ball diameter does not have a significant effect on the top surface grain size, but the thickness of the deformed layer increases with increase of ball size, from 50 μm for 2 mm balls to 150 μm for 5 mm balls. For all of the SMATed samples, the top surface microhardness value increased significantly and did not show any obvious change for samples treated with different balls. Corrosion studies show that the corrosion resistance of the sample treated with 2 mm balls is higher than that of those treated with 3 mm and 5 mm balls. This can be mainly attributed to the surface roughness and defects density of the samples, which are higher for the SMATed samples with 3 mm and 5 mm balls compared with that of sample SMATed with 2 mm balls.     

States and transport of hydrogen in the corrosion process of an AZ91 magnesium alloy in aqueous solution

Mott–Schottky measurement and secondary ion mass spectroscopy (SIMS) were used to investigate the states and transport of hydrogen during the corrosion behavior of an AZ91 magnesium alloy in 0.1 M sodium sulfate solution. The results showed that when samples were immersed or charged in solution, hydrogen atoms diffused into the film and reacted with vacancy to cause the increases of the carrier concentration (excess electron or hole carrier) and diffusion rate of hydrogen. Some hydrogen atoms diffused to interior of matrix and enriched in β phase while others resorted in the corrosive film. With the increase of immersion or charging time, magnesium hydride would be brittle fractured when the inner stress caused by hydrogen pressure and expansion stress of formation of magnesium hydride was above the fracture strength, which provided the direct experimental evidence of the hydrogen embrittlement (HE) mechanism of magnesium and its alloys. After immersion in solution, the transfer of excess electrons to the interfaces of corrosion film and solution would destroy the charge equilibrium in the film and stimulate the adsorption of , which resulted in the initiation of localized corrosion; after cathodic charging and then immersion, the enrichment of hydrogen atoms at interior of corrosion film would combine into hydrogen gas to form high pressure and result in the rupture of corrosion film, and localized corrosion initiated and developed at surface. Therefore, localized corrosion nucleated earlier on the charged samples than on the uncharged samples. Hydrogen invasion accelerated the corrosion of matrix.     

Improvement of corrosion resistance of AZ91D magnesium alloy by gadolinium addition

Based on the previous investigation on beneficial introduction of holmium into magnesium alloy, the effect of gadolinium, an adjacent rare earth element, on corrosion resistance was examined. The corrosion behavior of two Mg-9Al-Gd alloys （Mg-9Al-0.45Gd and Mg-9Al-l.43Gd） was evaluated and compared with that of Mg-9Al alloy without Gd by means of specimen mass loss and hydrogen evolution in 3.5% NaCl solution saturated with Mg（OH）2. The Gd-containing alloys exhibit enhanced corrosion resistance with respect to the plain Mg-9Al alloy. The microstructures of Mg-9Al alloy and Mg-9Al-0.45 Gd alloy were observed by electron probe microanalysis （EPMA） and energy dispersion spectroscopy （EDS）. The alloys with Gd addition show a microstructure characterized by a phase solid solution, surrounded by minor amount of β phase and more grain-like Gd-containing phase. To illustrate the involved mechanism their polarization curves were recorded. The electrochemical investigations reveal that Gd addition shifts the corrosion potential of the alloy towards active, as Gd containing phase is more active and hence less cathodic. As a result, the micro-galvanic corrosion is suppressed. Moreover corrosion product films formed on the Gd containing alloys are more compact and provide a better protective effectiveness than that on the alloy without Gd against corrosion. Repassivation measurements in mixture solution of 0.21 mol/L K2CrO4＋0.6 mol/L NaCI also verify the beneficial role of Gd addition. Based on the present preliminary analysis, both the deposited Gd-containing phases and corrosion product films are believed to be responsible for the improved corrosion behaviour due to Gd addition.     

Gas-tungsten arc welding of AZ91 magnesium alloy

The gas-tungsten arc (GTA) welding behaviors of the commercial AZ91 magnesium alloy were examined in terms of process efficiencies and microstructure characteristics. This study focused on the effects of GTA welding process parameters (like welding current in the range of 100/300 A and welding speed in the range of 3.33/13.33 mm/s) on energy absorption by the substrate material. The dependences of arc and welding efficiency on the used process parameters were presented. The measurements revealed that the arc efficiency values ranged from 0.63 to 0.88. Melting efficiency was found to rise with both increasing welding current and speed. The analyses revealed a strong influence of the GTA welding process on the width and depth of the fusion zone and also on the refinement of the microstructure in the fusion zone. The results of dendrite arm size (DAS) measurements were presented. Additionally, the presence of a partially melted zone (PMZ) was disclosed.     

Electrolytic MgO/ZrO2 duplex-layer coating on AZ91D magnesium alloy for corrosion resistance

By a two-step fabrication process of electrolytic deposition and annealing treatment, an MgO/ZrO₂ duplex-layer coating has been prepared on AZ91D magnesium alloy as a protective film against corrosion. Owing to the chemical bonding formed after the condensation of precursory hydroxides, the adhesion strength, thickness and compactness of MgO coating on the substrate are significantly enhanced by the intermediate ZrO₂ layer which prevents the formation of corrosion product Mg₂(OH)₃Cl·4H₂O. As a result, the MgO/ZrO₂ duplex-layer coated specimen reveals relatively high corrosion resistance and superior stability in 3.5 wt% NaCl solution with respect to the MgO single-layer coated specimen.     

Corrosion product formation during NaCl induced atmospheric corrosion of magnesium alloy AZ91D

Magnesium alloy AZ91D was exposed in humid air at 95% relative humidity (RH) with a deposition of 70 μg/cm⁻² NaCl. The corrosion products formed and the surface electrolyte were analysed after different exposure times using ex situ and in situ FTIR spectroscopy, X-ray diffraction and Ion Chromatography. The results show that magnesium carbonates are the main solid corrosion products formed under these conditions. The corrosion products identified were the magnesium carbonates hydromagnesite (Mg₅ (CO₃)₄ (OH)₂4H₂O) and nesquehonite (MgCO₃ 3H₂O). The corrosion attack starts with the formation of magnesite at locations with higher NaCl contents. At 95% RH, a sequence of reactions was observed with the initial formation of magnesite, which transformed into nesquehonite after 2-3 days. Long exposures result in the formation of pits containing brucite (Mg(OH₂)) covered with hydromagnesite crusts. The hydromagnesite crusts restrict the transport of CO₂ and O₂ to the magnesium surface and thereby favour the formation of brucite. Analysis of the surface electrolyte showed that the NaCl applied on the surface at the beginning was essentially preserved during the initial corrosion process. Since the applied salt was not bound in sparingly soluble corrosion products a layer of NaCl electrolyte was present on the surface during the whole exposure. Thus, Na⁺ and Cl⁻ ions can participate in the corrosion process during the whole time and the availability of these species will not restrict the atmospheric corrosion of AZ91D under these conditions. It is suggested that the corrosion behaviour of AZ91D is rather controlled by factors related to the microstructure of the alloy and formation of solid carbonate containing corrosion products blocking active corrosion sites on the surface.     

Oxidation behaviour of molten magnesium and AZ91D magnesium alloy in 1,1,1,2-tetrafluoroethane/air atmospheres

The oxidation rates, the morphologies and compositions of the surface films on molten magnesium and AZ91D alloy in covering gas of 1,1,1,2-tetrafluoroethane/air at 760 °C were investigated using thermogravimetric techniques, SEM, XRD and XPS. The oxidation rates of the two melts followed parabolic law in the atmosphere of high concentrate 1,1,1,2-tetrafluoroethane, and obeyed linear law in the atmosphere of low concentrate 1,1,1,2-tetrafluoroethane. But the oxidation rates of molten magnesium and AZ91D alloy presented a certain difference. The oxidation products on its surface films were composed of MgF₂ which played an import role to prevent the molten oxidation and other compounds.