Role of CO2 in the initial stage of atmospheric corrosion of AZ91 magnesium alloy in the presence of NaCl

The effect of CO2 and NaCl on the initial stage of atmospheric corrosion of AZ91 magnesium alloy was studied. The observation of surface morphology by optical microscopy （OM）, scanning electron microscopy （SEM） and the analysis of corrosion products by X-ray diffraction （XRD） were integrated to investigate corrosion evolution. The results showed that NaCl stimulated the corrosion by promoting the formation of thin electrolyte film, increasing the conductivity and breaking the protective film in the absence of CO2. The morphology of the corroded samples with deposited NaCl was more homogenous in the presence of CO2. It was suggested that NaCl-induced corrosion was inhibited in the presence of CO2 by the formation of slightly soluble corrosion products containing hydroxy carbonates and hydroxy chlorides that provided a partly protective layer on the surface of the magnesium alloy.     

The influence of NaCl and CO2 on the atmospheric corrosion of magnesium alloy AZ91

The influence of NaCl and CO₂ on the atmospheric corrosion of magnesium alloy AZ91 is studied in the laboratory. Samples were exposed under carefully controlled air and flow conditions; the relative humidity was 95%, the temperature was 22.0°C and the concentration of CO₂ was < 1 ppm or 350 ppm. Different amounts of sodium chloride (0–70 μg/cm²) were added before exposure. The corrosion products were analyzed by gravimetry, ion chromatography, X‐ray diffraction and scanning electron microscopy. Mass gain and metal loss results are reported. The combination of high humidity and NaCl is very corrosive towards AZ91. However, the NaCl‐induced corrosion is inhibited by ambient concentrations of CO₂. Exposure in the absence of CO₂ gives rise to heavy pitting, with brucite, Mg(OH)₂, being the dominant corrosion product. In the presence of CO₂ a layer of hydrated magnesium hydroxy carbonate, Mg₅(CO₃)₄(OH)₂ · 5 H₂O forms. A tentative corrosion mechanism is presented that explains the behavior in the two environments.     

Corrosion behaviour of magnesium/aluminium alloys in 3.5 wt.% NaCl

Corrosion behaviour of commercial magnesium/aluminium alloys (AZ31, AZ80 and AZ91D) was investigated by electrochemical and gravimetric tests in 3.5 wt.% NaCl at 25 °C. Corrosion products were analysed by scanning electron microscopy, energy dispersive X-ray analysis and low-angle X-ray diffraction. Corrosion damage was mainly caused by formation of a Mg(OH)₂ corrosion layer. AZ80 and AZ91D alloys revealed the highest corrosion resistance. The relatively fine β-phase (Mg₁₇Al₁₂) network and the aluminium enrichment produced on the corroded surface were the key factors limiting progression of the corrosion attack. Preferential attack was located at the matrix/β-phase and matrix/MnAl intermetallic compounds interfaces.     

Influences of NH4 + ions and thin electrolyte layers (TEL) thickness on the corrosion behavior of AZ91D magnesium alloy

In this study, the influences of NH₄ ⁺ ions and the thin electrolyte layer (TEL) thickness on the corrosion behavior of the AZ9D magnesium alloy in NH₄⁺‐containing environments were investigated by electrochemical measurements and surface characterization. The experimental results indicate that NH₄⁺ greatly accelerates the corrosion of AZ91D magnesium alloy whether in a bulk solution or in a TEL. As the TEL thickness decreasing, the corrosion resistance of the AZ91D magnesium alloy is strengthened. According to the corrosion morphology, electrochemical analysis, and characterization analysis of corrosion products, the corrosion mechanism of AZ91D under TELs with different thicknesses is divided into three stages: (a) uniformly distributed corrosion pits with deep depth and large size when TEL thickness is higher than or equal to 500 μm; (b) slightly corrosion with randomly distributed corrosion pits and the accumulation of small amount of corrosion product when TEL thickness is between 100 μm and 200 μm; (c) no corrosion pit with only deposition of corrosion product when TEL thickness is lower than or equal to 100 μm. Among which, the roles of NH₄⁺, TEL thickness, and corrosion product are emphasized and discussed in the corrosion process of AZ91D magnesium alloy under TEL with different thicknesses.     

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.     

Corrosion behaviour of silicon-carbide-particle reinforced AZ92 magnesium alloy

The corrosion behaviour of silicon-carbide-particle (SiCp) reinforced AZ92 magnesium alloy manufactured by a powder metallurgy process was evaluated in 3.5 wt.% NaCl solution, neutral salt fog (ASTM B 117) and high relative humidity (98% RH, 50 °C) environments. The findings revealed severe corrosion of AZ92/SiC/0-10p materials in salt fog environment with formation of corrosion products consisting of Mg(OH)₂ and (Mg,Al)_x(OH)_y. The addition of SiCp increased the corrosion rate and promoted cracking and spalling of the corrosion layer for increasing exposure times. Composite materials revealed higher corrosion resistance in high humidity atmosphere with almost no influence of SiCp on the corrosion behaviour.     

Effect of Gd on microstructure and stress corrosion cracking of the AZ91-extruded magnesium alloy

AZ91 and AZ91–xGd (x = 0.5, 1.0, 1.5 wt%) magnesium alloys are extruded into plates. The addition of Gd promotes the formation of Al₂Gd, effectively reducing the volume fraction of the β-Mg₁₇Al₁₂ phase and making the banded structures of the extruded magnesium alloys thinner. The corrosion weight loss tests and electrochemistry analyses demonstrate that Gd significantly improves the pitting resistance of the AZ91 in 3.5-wt% NaCl solution saturated with Mg(OH)₂. Slow strain rate tensile tests show that in a corrosive environment, compared with AZ91, the elongation to failure of the AZ91–1.0Gd alloy is increased by 47%, and the alloy exhibits excellent stress corrosion resistance in this study. The fracture mode of AZ91 is changed from typical intergranular fracture to a mixture of transgranular and intergranular fracture in the corrosion solution by adding Gd. The mechanism of Gd to improve the stress corrosion resistance of the AZ91 magnesium alloy is that Gd increases the corrosion resistance, especially the pitting of AZ91.     

Corrosion resistance of WE43 and AZ91D magnesium alloys with phosphate PEO coatings

The corrosion performance of WE43-T6 and AZ91D magnesium alloys with and without treatment by plasma electrolytic oxidation (PEO) was investigated by electrochemical measurements in 3.5 wt.% NaCl solution. For untreated WE43-T6 alloy, formation of a uniform corrosion layer (Mg(OH)₂) was accompanied by initial pits around magnesium-rare earth intermetallic compounds. The AZ91D alloy disclosed increased corrosion susceptibility, with localized corrosion around the β-phase, though the β-phase network phase acted as a barrier for corrosion progression. PEO treatment in alkaline phosphate electrolyte improved the corrosion resistance of WE43-T6 alloy only at the initial stages of immersion in the test solution. However, PEO-treated AZ91D alloy revealed a relatively high corrosion resistance for much increased immersion times, contrary to the relative corrosion resistances of the untreated alloys. The improved performance of the PEO-treated AZ91D alloy appears to be related to the formation of a more compact coating.     

Corrosion behavior of Cr/Cu-coated Mg alloy (AZ91D) in 0.1 M H2SO4 with different concentrations of NaCl

An electroplating process was proposed for obtaining a protective Cr/Cu deposit on the two-phase Mg alloy AZ91D. The corrosion behavior of Cu-covered and Cr/Cu-covered AZ91D specimens was studied electrochemically in 0.1 M H₂SO₄ with different NaCl concentrations. Experimental results showed that the corrosion resistance of an AZ91D specimen improved significantly after Cr/Cu electrodeposition. The corrosion resistance of Cr/Cu-covered AZ91D decreased with increasing NaCl concentration in 0.1 M H₂SO₄ solution. After immersion in a 0.1 M H₂SO₄ with a NaCl-content above 3.5 wt.%, the surface of Cr/Cu-covered AZ91D suffered a few blisters. Cracks through the Cr deposit provided active pathways for corrosion of the Cu and the AZ91D substrate. Formation of blisters on the Cr/Cu-covered AZ91D surface was confirmed based on the results of an open-circuit potential test, which detected an obvious potential drop from noble to active potentials.     

Effect of antimony, bismuth and calcium addition on corrosion and electrochemical behaviour of AZ91 magnesium alloy

This study investigated the effect of antimony, bismuth and calcium addition on the corrosion and electrochemical behaviour of AZ91 magnesium alloy in 3.5% NaCl solution. Techniques including constant immersion, electrochemical potentiodynamic polarisation, scanning electron microscopy (SEM), energy dispersed spectroscopy (EDS) and X-ray diffraction (XRD) were used to characterise electrochemical and corrosion properties and surface topography. It was found that corrosion attack occurred preferentially on Mg₃Bi₂ and Mg₃Sb₂ particles while Mg₁₇Al₈Ca_0.5 and Mg₂Ca phases showed no detrimental effect on corrosion. Combined addition of small amounts of bismuth and antimony to the AZ91 alloy resulted in significant increase in corrosion rate.     

AZ91D镁合金电偶腐蚀的研究

在自来水和3.5%NaCl溶液中测试了铸造AZ91D镁合金与铝合金、锌合金、Q235碳钢和Cu偶合后的电偶腐蚀行为,研究了腐蚀环境、偶接材料和阴阳极面积比(CAAR)对铸造AZ91D镁合金电偶腐蚀行为的影响。在电偶腐蚀过程中测量溶液的pH值以及电偶腐蚀电流;用失重法计算了铸造AZ91D镁合金的电偶腐蚀速率,利用SEM观察了AZ91D镁合金的腐蚀形貌,并对腐蚀产物进行XRD分析。结果表明,AZ91D镁合金在电偶腐蚀过程中会使溶液的pH值升高,并伴有以Mg(OH)₂为主的腐蚀产物的生成;溶液中Cl^-的存在会加速AZ91D镁合金的电偶腐蚀速率;低氢过电位金属Q235碳钢和Cu对AZ91D镁合金的电偶腐蚀加速效果明显高于中氢过电位金属铝合金和锌合金,偶接材料的极化性能对AZ91D镁合金的电偶腐蚀速率有较大影响。同时,大的阴阳极面积比会加速AZ91D镁合金的电偶腐蚀速率,且AZ91D镁合金的电偶腐蚀电流随阴阳极面积比的增大而呈线性增长趋势。     

Corrosion behaviour of AZ31B magnesium alloy in NaCl solutions saturated with CO2

Corrosion behaviour of AZ31B magnesium alloy in different concentrations of NaCl solution saturated with CO₂ was studied by electrochemical techniques, Fourier transform infrared spectroscopy, scanning electron microscopy and energy dispersive X-ray. The corrosion rate increases with increasing NaCl concentration both in the presence and absence of CO₂. The corrosion rate in NaCl solution saturated with CO₂ is bigger than that in single NaCl solution. The inhibitive effect of CO₂ is also observed with immersion time increased in NaCl solution saturated with CO₂, showing that CO₂ reduces the average corrosion rate due to the formation of insoluble products.     

The effects of 8-hydroxyquinoline on corrosion performance of a Mg-rich coating on AZ91D magnesium alloy

A Mg-HQ-rich primer was prepared by adding 45% pure magnesium particles and 5% 8-hydroxyquinoline in epoxy coating. The Mg-HQ-rich primer showed obviously better protection for AZ91D alloy than 50% Mg-rich primer. The additive 8-HQ combines with Mg²⁺ in the coating, forming a insoluble complex, MgQ₂, instead of Mg(OH)₂ on Mg particles. The MgQ₂ layer may retard dissolution of magnesium particles and prolong the cathodic protection effect of Mg-HQ-rich primer. Additionally, the corrosion products may also block the defects in the primer and the active sites on the substrate surface, thereby further increase the corrosion resistance of the Mg-HQ-rich primer.     

An exploratory study of the corrosion of Mg alloys during interrupted salt spray testing

A first systematic investigation was carried out to understand the corrosion of common Mg alloys (Pure Mg, AZ31, AZ91, AM30, AM60, ZE41) exposed to interrupted salt spray. The corrosion rates were also evaluated for these alloys immersed in 3 wt.% NaCl by measuring hydrogen evolution and an attempt was made to estimate the corrosion rate using Tafel extrapolation of the cathodic branch of the polarisation curve. The corrosion of these alloys immersed in the 3 wt.% NaCl solution was controlled by the following factors: (i) the composition of the alpha-Mg matrix, (ii) the volume fraction of second phase and (iii) the electrochemical properties of the second phase. The Mg(OH)₂ surface film on Mg alloys is probably formed by a precipitation reaction when the Mg²⁺ ion concentration at the corroding surface exceeds the solubility limit. Improvements are suggested to the interrupted salt spray testing; the ideal test cycle would be a salt spray of duration X min followed by a drying period of (120-X) min. Appropriate apparatus changes are suggested to achieve 20% RH rapidly within several minutes after the end of the salt spray and to maintain the RH at this level during the non-spray part of the cycle. The electrochemical measurements of the corrosion rate, based on the “corrosion current” at the free corrosion potential, did not agree with direct measurements evaluated from the evolved hydrogen, in agreement with other observations for Mg.     

Corrosion behaviour of Mg/Al alloys in high humidity atmospheres

The influence of relative humidity (80–90–98% RH) and temperature (25 and 50 °C) on the corrosion behaviour of AZ31, AZ80 and AZ91D magnesium alloys was evaluated using gravimetric measurements. The results were compared with the data obtained for the same alloys immersed in Madrid tap water. The corrosion rates of AZ alloys increased with the RH and temperature and were influenced by the aluminium content and alloy microstructure for RH values above 90%. The initiation of corrosion was localised around the Al–Mn inclusions in the AZ31 alloy and at the centre of the α‐Mg phase in the AZ80 and AZ91D alloys. The β‐Mg₁₇Al₁₂ phase acted as a barrier against corrosion.     

Effect of cerium addition on microstructure and corrosion resistance of die cast AZ91 magnesium alloy

A novel AZ91 Ce containing magnesium alloy characterized by excellent corrosion resistance is fabricated by adding rare earth Ce (cerium) in the form of a Mg‐Ce master alloy. The metallographic investigation shows that Ce added to AZ91 can obviously decrease the size of β‐Mg₁₇Al₁₂ and forms Al₁₁Ce₃ intermetallic compounds in the shape of fine needles. The corrosion tests and electrochemical measurements indicate that the corrosion resistance of AZ91 Ce containing magnesium alloy is obviously higher than that of AZ91. Furthermore, increasing the content of Ce in the magnesium alloy can further enhance the corrosion resistance. X‐ray photoelectron spectroscopy (XPS) reveals that Ce can be incorporated into corrosion products in the form of CeO₂ in the course of corrosion. Based on the preliminary analysis, the addition of Ce can improve the corrosion resistance of AZ91 by decreasing the size of β‐Mg₁₇Al₁₂ and enhancing the protective effectiveness of corrosion products.     

Electrophoretic deposition of 3YSZ coating on AZ91D using an aluminum interlayer

The zirconia stabilized by 3 mol % Y₂O₃ (3YSZ) was applied onto the surface of the magnesium alloy AZ91D using electrophoretic deposition (EPD) from a non- aqueous solvent. An interlayer of aluminum between the substrate and YSZ coating was also prepared by EPD. The preparation, microstructure and corrosion resistance of the coatings were investigated. The surface morphologies of the coatings were studied by scanning electron microscopy (SEM) and their compositions were determined by X-ray diffraction (XRD). The corrosion resistance of the coatings was evaluated by electrochemical impedance spectroscopy (EIS) in 3.5% NaCl solution. The results indicate that the aluminum interlayer has a favorable effect on the densification of the coating by formation of aluminum oxide. In addition, the corrosion resistance of coated AZ91D alloy in chloride solution is significantly improved because of the aluminum interlayer and an increase in charge-transfer resistance of the AZ91D surface in chloride solution was observed which was attributed to YSZ.     

压铸镁合金AZ91D在酸性NaCl溶液中的腐蚀行为

采用电化学方法研究了压铸镁合金AZ91D在酸性NaCl溶液中的腐蚀行为,并用扫描电镜观察了腐蚀形貌,对腐蚀产物进行了能谱分析.研究结果表明:在酸性溶液环境下,随着Cl-浓度的升高,镁合金的平衡腐蚀电位降低,线性阻抗减小,腐蚀电流增大;随着pH值的减小,晶界出现腐蚀开裂现象;富Al相的耐蚀性高于基体相,在酸性环境中,腐蚀产物主要为MgO和Mg(OH)2     

Characterization and corrosion studies of ceria thin film based on fluorinated AZ91D magnesium alloy

The CeO₂ thin film was prepared via sol-gel method on fluorinated AZ91D magnesium alloy surfaces. The surface morphology, composition and the corrosion resistance of the film were investigated in details using scanning electron microscope, X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy as well as potentiodynamic polarization tests. It was found that small amount of MgO and MgF₂ were encapsulated in CeO₂ thin film. The electrochemical measurement results demonstrated that the CeO₂ thin film on fluorinated AZ91D magnesium alloy could improve the corrosion resistance approximately by two orders of magnitude compared with that of the bare substrate.     

Investigations on the corrosion behaviour and biocompatibility of magnesium alloy surface composites AZ91D-ZrO2 fabricated by friction stir processing

In the current study, friction stir processing was applied as a methodology to produce surface composites of AZ91D magnesium alloy with ZrO₂ particles. Microstructural evolution, microhardness profile and corrosion behaviour of the developed surface composite were analysed. The results indicate that the combined effect of friction stir processing and reinforcement of ZrO₂ reduced the grain size, and fragmented and dispersed the secondary phases. The fine dispersion of ZrO₂ particles contributed to the enhancement of cumulative surface potential, and hence the corrosion resistance of the developed surface composite. The analysis of post-corrosion test specimens revealed the formation of corrosion products that had similar composition to that of hydroxyapatite. The formation of such corrosion products is beneficial, as it contributes to corrosion resistance (stable and adherent layer) and biocompatibility.