Evaluation of corrosion resistance of magnesium alloys in radiator coolants

Abstract

Coolant corrosion is a major drawback for the use of magnesium alloys in engine and cooling system, but the coolant is not normally intended to prevent corrosion of magnesium alloys. This research assessed the corrosion performance of two magnesium alloys, AZ91D and AM50A, in two newly formulated radiator coolants using immersion test, potentiodynamic polarisation test, and corroded surface analysis. Two coolants were named as Irgacool Plus L and Irgacool Plus S. C7, C8-organic acids and polycarboxylic acid were the main inhibitor species in Irgacool Plus L while Irgacool Plus S was formulated with C7, C8-organic acids and sebacic acid inhibitors. Corrosion rates of magnesium alloys decreased twice in Irgacool Plus L compared with Irgacool Plus S. AZ91D alloy had better corrosion resistance than AM50A alloy in both radiator coolants. Both alloys suffered corrosion due to microgalvanic coupling between cathodic β-Mg₁₇Al₁₂ intermetallic and anodic α-Mg matrix, and the presence of Al₈Mn₅ and Al₁₁Mn₄ intermetallics in AM50A led to further microgalvanic corrosion. A continuous network of β-Mg₁₇Al₁₂ phase and higher Al content α-Mg matrix accounted for better corrosion resistance of AZ91D alloy.     

Oxidation Behavior of AZ91D Magnesium Alloy Containing Nd or Gd

The influence of Nd and Gd additions on the evolution of microstructure, surface hardness and oxidation behavior of the extruded AZ91D magnesium alloy exposed to air was investigated in the temperature range from 290 to 410???C. The kinetics of the oxidation process was obtained from gravimetric measurements performed during 28?days. Nd and Gd formed Al-rich intermetallic compounds (Al₂Gd, Al₂Nd, Al?CMn?CGd and Al?CMn?CNd) and reduced the volume fraction of ??-Mg₁₇Al₁₂ phase. Surface degradation of the AZ91D alloy, with and without Gd or Nd, was negligible for temperatures below 370???C. At 410???C, the grain size and oxidation rate significantly increased, although lanthanide-containing alloys revealed lower degradation compared with the unmodified AZ91D alloy.     

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.     

Effect of heat treatment on corrosion behaviour of magnesium alloy AZ91D in simulated body fluid

The research explored ways of improving corrosion behaviour of AZ91D magnesium alloy through heat treatment for degradable biocompatible implant application. Corrosion resistance of heat-treated samples is studied in simulated body fluid at 37 °C using immersion and electrochemical testing. Heat treatment significantly affected microgalvanic corrosion behaviour between cathodic β-Mg₁₇Al₁₂ phase and anodic α-Mg matrix. In T4 microstructure, dissolution of the β-Mg₁₇Al₁₂ phase decreased the cathode-to-anode area ratio, leading to accelerated corrosion of α-Mg matrix. Fine β-Mg₁₇Al₁₂ precipitates in T6 microstructure facilitated intergranular corrosion and pitting, but the rate of corrosion was less than those of as-cast and T4 microstructures.     

Corrosion of hot extrusion AZ91 magnesium alloy. Part II: Effect of rare earth element neodymium (Nd) on the corrosion behavior of extruded alloy

The corrosion behavior of extruded Nd-free AZ91 and extruded AZ91 + 1.5Nd alloy was investigated by weight loss and electrochemical measurements. The results showed that the extruded AZ91 + 1.5Nd alloy had higher corrosion resistance compared to the extruded Nd-free AZ91 alloy, which could been explained from point of view of microstructure changes: (1) the significant decrease of twins and dislocation decreased the anodic dissolution rate; (2) the micro-galvanic corrosion was inhibited by the formation of Al₃Nd phase; and (3) Nd not only increased the percent of Non-Faraday process, but also led to anisotropic feature on the corrosion mechanism.     

Corrosion behaviour of AZ91D and AM50 magnesium alloys with Nd and Gd additions in humid environments

AM50 and AZ91D alloys modified with rare earths (RE) were evaluated under atmospheric conditions. Nd and Gd additions resulted in formation of Al₂RE and Al–Mn–RE compounds and reduction of the fraction of β-phase. According to surface potential maps, RE-containing intermetallics were more noble than the β-phase, but less than Al–Mn inclusions. As a result, the action of micro-galvanic couples depended on the added amount of RE and the initial alloy microstructure. Nd or Gd additions improved the corrosion resistance of the AM50 alloy by up to 43%, but had no significant effect on the corrosion resistance of the AZ91D alloy.     

AZ91镁合金的挤压和析出硬化行为(英文)

挤压比为4:1,将铸态AZ91镁合金分别在250,300和350℃下进行挤压,随后进行析出硬化处理(T6)。经过热挤压和析出硬化处理后,铸态AZ91镁合金中粗大的和偏析Mg17Al12析出相被细化并均匀分布在α-镁基体中。在不同的挤压温度下合金中发生了部分或全部动态再结晶。经挤压后,该合金的极限抗拉强度从铸态的190MPa增加到570MPa。AZ91镁合金的时效硬化特征与晶粒尺寸有关。在250、300和350℃下以4:1的挤压比挤压该合金后,获得峰值硬度的时效时间分别为35、30和20h。SEM观察到在AZ91基体中存在均匀细小的Mg17Al12析出相。     

Microstructure and corrosion behavior of plasma electrolytic oxidation coated magnesium alloy pre-treated by laser surface melting

An AZ91D magnesium alloy was treated using duplex techniques of laser surface melting (LSM) and plasma electrolytic oxidation (PEO). The microstructure, composition and corrosion behavior of the laser melted surface, PEO coatings, LSM–PEO duplex coatings as well as the as-received specimen were characterized by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD) and electrochemical corrosion tests, respectively. Especially, the effect of LSM pre-treatment on the microstructure, composition and corrosion resistance of the PEO coatings was investigated. Results showed that the corrosion resistance of AZ91D alloy was marginally improved by LSM due to the refinement of grains, redistribution of β-phase (Mg₁₇Al₁₂) and increase of Al on the surface. Both the PEO and duplex (LSM–PEO) coatings improved significantly the corrosion resistance of the AZ91D alloys, while the duplex (LSM–PEO) coating exhibited better corrosion resistance compared with the PEO coating.     

Gd对镁合金AZ81耐腐蚀性能的影响

为了改善镁合金的耐腐蚀性能,进一步拓宽镁合金的应用范围,利用静态腐蚀试验,辅以腐蚀速率计算和腐蚀形貌观察,研究了稀土元素Gd对镁合金AZ81在0.5%NaCl溶液中耐腐蚀性能的影响作用。结果表明,随着Gd含量的增加,镁合金AZ81的腐蚀速率总体上表现出先增加后降低的变化趋势;加入适量的Gd,可改善镁合金AZ81的耐腐蚀性能。     

Corrosion behavior of 3C magnesium alloys in simulated sweat solution

AZ series Mg alloys AZ31, AZ61, and AZ80 are widely applied in 3C (computer, communication, and consumer electronic) industry. Their corrosion characters in simulated sweat solution have been investigated by electrochemical technology, surface analysis, and pH measurements. Electrochemical test results showed that the three magnesium alloys revealed different corrosion resistance (R_t) in simulated sweat solution, R_t(AZ31) < R_t(AZ61) < R_t(AZ80). Three major components of simulated sweat solution played different roles during corrosion processes. Lactic acid was a kind of strong erosive medium for the magnesium alloys, and NaCl can induce pitting corrosion on alloys surface, while urea acted as a corrosion inhibitor. The corroded surface morphology of the three magnesium alloys was observed using scanning electron microscopy (SEM) and corrosion products were analyzed by X‐ray diffraction (XRD). Result of pH measurement tests showed that there were differences in climbing speed and final values of pH for the three magnesium alloys in simulated sweat solution.     

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.     

Corrosion performance of magnesium alloys MEZ and AZ91

The corrosion performance of sand cast MEZ_S, zirconium-grain-refined MEZ_R, sand cast AZ91_S, and high pressure diecast AZ91_D magnesium alloys were evaluated by means of salt spray testing, optical metallography, hydrogen evolution, polarisation curve measurement and AC impedance spectroscopy. The results show that the corrosion resistance of the four alloys can be ranked in decreasing order as AZ91_D > AZ91_S ≈ MEZ_R > MEZ_S and that the intergranular phases and chemical composition of the matrix phase have a significant influence on the corrosion performance. Alloys with a finer grain size and higher aluminum or zirconium contents exhibit better corrosion resistance.     

Corrosion behaviour of Sn-containing oxide layer on AZ91D alloy formed by plasma electrolytic oxidation

Corrosion phenomenon of magnesium alloys is one of the limits for using magnesium alloys in automotive and aerospace industries. The aim of this study is the development of Sn-containing protective oxide coating by a simple plasma electrolytic oxidation in KOH/KF/Na₃PO₄ electrolyte on AZ91D magnesium alloy in galvanostatic mode. The film morphology and composition were analysed by SEM coupled with EDS, XRD and Raman spectroscopy. In the oxide, tin is mainly incorporated as crystallised MgSn(OH)₆ compound in the layer. The main properties of Sn-containing oxide coating on AZ91D are both keeping the corrosion rate at open-circuit conditions at an acceptable value, and providing a sufficient passivation plateau to reduce the pitting sensibility. The lather characteristic, revealed by pitting tests, addresses the major drawback of magnesium alloys which often undergo important galvanic coupling in service. Consequently, the addition of low stannate concentration in the electrolyte to form Sn-rich anodic oxide on magnesium alloys represents an interesting way to synthesize protective coatings by PEO in a short time of anodization.     

Corrosion and self‐healing behaviour of AZ91D magnesium alloy in ethylene glycol/water solutions

Corrosion behaviour of magnesium alloy‐based engine parts in cooling system is an urgent fundamental issue in automotive field where magnesium alloys are increasingly used. In the present work, the corrosion behaviour of AZ91D magnesium alloys in various ethylene glycol/water solutions was studied by electrochemical measurements and immersion tests at room temperature. The surfaces of the samples after immersion tests were examined using scanning electron microscope (SEM) and X‐ray diffraction (XRD). The results showed that the corrosion rates of AZ91D magnesium alloys decreased with the increase of ethylene glycol concentration in ethylene glycol/water solutions and the corrosion process was dominated by pitting corrosion. A continuous protective film transferred from corrosion products was formed on the corroded surface after sufficient immersion duration in ethylene glycol/water solutions, which is able to heal the corrosion pits. The self‐healing behaviour inhibited the further corrosion of AZ91D magnesium alloy.     

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.     

Enhanced corrosioon resistance by sol‐gel‐based ZrO2‐CeO2 coatings on magnesium alloys

The physical, chemical and mechanical properties of magnesium alloys make them attractive materials for automotive and aerospace applications. However, these materials are susceptible to corrosion and wear. This work discusses the potential of using sol‐gel based coatings consisting of ZrO₂ and 15 wt.% of CeO₂. The CeO₂ component provides enhanced corrosion protection, while ZrO₂ impart corrosion as well as wear resistance. Coating deposition was performed by the dip coating technique on two magnesium alloy substrates with different surface finishes: AZ91D (as‐casted, sand‐blasted, and machined) and AZ31 (rolled and machined). All as‐deposited coatings (xerogel coatings) were then subjected to 10 h annealilng: a temperature of 180°C was applied to the AZ91D alloy and 140°C to the AZ31 alloy. Morphological and structural properties of the annealed coatings were investigated by scanning electron microscopy, atomic force microscopy and transmission electron microscopy. Coating composition was examined using energy dispersive X‐ray analysis. Adhesion of the annealed ZrO₂‐CeO₂ coatings on the substrates, assessed by scratch tests, showed critical loads indicative of coating perforation of up to 32 N. Hardness and elasticity, measured using depth‐sensing nanoindentation tests, gave a hardness and elastic modulus of 4.5 GPa and 98 GPa, respectively. Salt spray corrosion tests performed on these coatings showed superior corrosion resistance for AZ91D (as‐casted and machined) and AZ31 (machined), while severe corrosion was observed for the AZ31 (rolled) and AZ91D (sand‐blasted) magnesium alloy substrates.     

Ignition-proof performance and mechanism of AZ91D-3Nd-xDy magnesium alloys at high temperatures

This study focused on the synergistic effect of alloying elements neodymium(Nd) and dysprosium(Dy) on the ignition-proof performance of AZ91D alloy. The ignition-proof mechanism of AZ91D-3 Nd-x Dy(x = 0.5, 1.0, 1.5, 2.0 and 2.5 wt.%) alloy was discussed in depth through ignition-proof testing and microstructure observation. The results showed that the AZ91D-3 Nd-2 Dy alloy exhibited the highest ignition-point of 893 K, increased by 69 K as compared to the AZ91D alloy. The ignition-proof mechanism of Nd and Dy additions lay in three aspects:(1) the formation of denser oxide film consisting of Dy_2O_3 and MgO improves the oxidation resistance of the alloy,(2) the great reduction of the low melting-point phase β-Mg_(17)Al_(12), which leads to the decrease in the oxygen diffusion channels, and(3) the newly formed high melting-point phases(Al_2Nd and Al_2Dy), which block the oxygen diffusion channels and prevent the chemical reaction of Mg and oxygen.     

The use of Al-Al2O3 cold spray coatings to improve the surface properties of magnesium alloys

Pure Al and 6061 aluminium alloy based Al₂O₃ particle-reinforced composite coatings were produced on AZ91E substrates using cold spray. The strength of the coating/substrate interface in tension was found to be stronger than the coating itself. The coatings have corrosion resistance similar to that of bulk pure aluminium in both salt spray and electrochemical tests. The wear resistance of the coatings is significantly better than that of the AZ91 Mg substrate, but the significant result is that the wear rate of the coatings is several decades lower than that of various bulk Al alloys tested for comparison. The effect of post-spray heat treatment, the volume fraction of Al₂O₃ within the coating and of the type of Al powder used in the coatings on the corrosion and wear resistance was also discussed.     

Comparison of corrosion behaviors of AZ31, AZ91, AM60 and ZK60 magnesium alloys

The corrosion behaviours of four kinds of rolled magnesium alloys of AZ31, AZ91, AM60 and ZK60 were studied in 1 mol/L sodium chloride solution. The results of EIS and potentiodynamic polarization show that the corrosion resistance of the four materials is ranked as ZK60＞AM60＞AZ31＞AZ91. The corrosion processes of the four magnesium alloys were also analyzed by SEM and energy dispersive spectroscopy(EDS). The results show that the corrosion patterns of the four alloys are localized corrosion and the galvanic couples formed by the second phase particles and the matrix are the main source of the localized corrosion of magnesium alloys. The corrosion resistance of the different magnesium alloys has direct relationship with the concentration of alloying elements and microstructure of magnesium alloys. The ratio of the β phase in AZ91 is higher than that in AZ31 and the β phase can form micro-galvanic cell with the alloy matrix, as a result, the corrosion resistance of AZ31 will be higher than AZ91. The manganese element in AM60 magnesium alloy can form the second phase particle of AlMnFe, which can reduce the Fe content in magnesium alloy matrix, purifying the microstructure of alloy, as a result, the corrosion resistance of AM60 is improved. However, due to the more noble galvanic couples of AlMnFe and matrix, the microscopic corrosion morphology of AM60 is more localized. The zirconium element in ZK60 magnesium alloy can refine grain, form stable compounds with Fe and Si, and purify the composition of alloy, which results in the good corrosion resistance of ZK60 magnesium alloy.     

Influence of rare earth element Ce and La addition on corrosion behavior of AZ91 magnesium alloy

Two types of AZ91 magnesium alloys containing rare earth element Ce or La were fabricated. Hydrogen evolution and electrochemical tests were carried out to evaluate the corrosion behavior of new AZRE (RE = Ce or La) and AZ91 alloys in 3.5% NaCl solutions (pH 6.50). Various corrosion rate tests indicated that addition of RE obviously enhanced corrosion resistance of AZ91 magnesium alloy. The optimal content of RE was 0.92% for Ce and 0.66% for La. Scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), and low‐angle X‐ray diffraction (XRD) were used to characterize the effect of RE addition on microstructure and corrosion product film of AZ91 magnesium alloy. The refined β phase and formation of γ phase in AZRE alloy were observed by SEM, which resulted in the improvement of corrosion resistance due to the depression of microgalvanic couples. Moreover, the enhanced protective effectiveness of corrosion products was another reason for the improved corrosion resistance.