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.     

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 of magnesium alloys in commercial engine coolants

A number of magnesium alloys show promise as engine block materials. However, a critical issue for the automotive industry is corrosion of the engine block by the coolant and this could limit the use of magnesium engine blocks. This work assesses the corrosion performance of conventional magnesium alloy AZ91D and a recently developed engine block magnesium alloy AM‐SC1 in several commercial coolants. Immersion testing, hydrogen evolution measurement, galvanic current monitoring and the standard ASTM D1384 test were employed to reveal the corrosion performance of the magnesium alloys subjected to the coolants. The results show that the tested commercial coolants are corrosive to the magnesium alloys in terms of general and galvanic corrosion. The two magnesium alloys exhibited slightly different corrosion resistance to the coolants with AZ91D being more corrosion resistant than AM‐SC1. The corrosivity varied from coolant to coolant. Generally speaking, an organic‐acid based long life coolant was less corrosive to the magnesium alloys than a traditional coolant. Among the studied commercial coolants, Toyota long life coolant appeared to be the most promising one. In addition, it was found that potassium fluoride effectively inhibited corrosion of the magnesium alloys in the studied commercial coolants. Both general and galvanic corrosion rates were significantly decreased by addition of KF, and there were no evident side effects on the other engine block materials, such as copper, solder, brass, steel and aluminium alloys, in terms of their corrosion performance. The ASTM D 1384 test further confirmed these results and suggested that Toyota long life coolant with 1%wt KF addition is a promising coolant for magnesium engine blocks.     

Microstructure and mechanical properties of AZ91D magnesium alloy by expendable pattern shell casting with different mechanical vibration amplitudes and pouring temperatures

To refine the microstructure and improve the mechanical properties of AZ91 D alloy by expendable pattern shell casting(EPSC),the mechanical vibration method was applied in the solidification process of the alloy.The effects of amplitude and pouring temperature on microstructure and mechanical properties of AZ91 D magnesium alloy were studied.The results indicated that the mechanical vibration remarkably improved the sizes,morphologies and distributions of the primaryα-Mg phase andβ-Mg17 Al12 phase,and the densification and tensile properties of the AZ91 D alloy.With an increase in amplitude,the microstructures were gradually refined,resulting in a continuous increase in mechanical properties of the AZ91 D alloy.While,with the increase of pouring temperature,the microstructures were continuously coarsened,leading to an obvious decrease of the mechanical properties.The tensile strength and yield strength of the AZ91 D alloy with a vibration amplitude of 1.0 mm and a pouring temperature of 730℃were 60%and 38%higher than those of the alloy without vibration,respectively.     

Effects of Er on the microstructure and properties of AZ31 magnesium alloy prepared via the EMS process

The effects of small amounts of the rare-earth element erbium on the microstructure and the mechanical properties of AZ31 magnesium alloy via the electromagnetic stirring(EMS) process have been studied.It has been shown that AZ31-Er alloys are mainly composed of α-Mg solid solution and β-Mg17Al12 phases.When the Er content reaches 0.12 wt.%,the characteristic peaks of Al2Er can be observed.The micro-structure is obviously refined and the tensile strength of the AZ31-based alloy at ambient temperature is significantly improved by contents of 0.03 wt.% Er,especially the elongation(δ=19%).More addition of Er obviously decreases the tensile strength and elongation of the AZ31-based alloy because of the grain coarsening and the reduction of β-Mg17Al12 phases.     

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.     

Microstructure and Elevated Temperature Properties of Die-cast AZ91-<Emphasis Type="Italic">x</Emphasis>Nd Magnesium Alloys

The effect of Nd addition on the microstructure and mechanical properties of a die-cast AZ91 alloy was investigated in the present work. The results show that the die-cast AZ91 alloy is composed of α-Mg matrix and γ-Mg₁₇Al₁₂ phase. Nd addition into the AZ91 alloy leads to the formation of rare earth containing intermetallic phase. Al₄Nd phase forms when Nd content is less than or equal to 1.0 wt.%. Al₂Nd phase appears simultaneously when Nd content reaches to 3.0 wt.%. The size and volume fraction of γ-Mg₁₇Al₁₂ phase decrease, because of the newly formed Al-Nd phase. And the γ-Mg₁₇Al₁₂ phase distributes from reticular to dispersive. Nd addition has a little effect on the room temperature properties of the die-cast AZ91 alloy, but greatly improves the elevated temperature properties. The tensile strength of AZ91-0.5Nd and AZ91-1.0Nd alloy tested at 150 °C is even close to the room temperature strength. The AZ91-1.0Nd alloy has the optimal properties.     

The influence of microstructure on the corrosion behaviour of AZ91D studied by scanning Kelvin probe force microscopy and scanning Kelvin probe

β-Mg₁₇Al₁₂, η-Al₈Mn₅ and an α-magnesium phase have been synthesized from pure components by controlled solidification procedures. These phases have been studied using different electrochemical techniques including the scanning Kelvin probe (SKP). From the results, it was possible to determine the nobility and the rate of the cathodic reaction of the different phases. Measurements have also been made on an AZ91D Mg-alloy using scanning Kelvin probe force microscopy (SKPFM) and field emission gun scanning electron microscopy (FEG-SEM). The results show that the Volta potentials measured with the scanning Kelvin probe (SKP) on bulk intermetallics are comparable with those recorded with the SKPFM on the AZ91D alloy. It is shown that SKPFM provides information on the local nobility of the different intermetallic particles and phases on the submicron scale. Both the η-Al₈Mn₅ phase and the β-Mg₁₇Al₁₂ phase in AZ91D showed a more noble potential than the α-magnesium phase. It is also shown that the aluminium-rich coring along the grain boundaries results in measurable changes in the Volta potential. Finally, the role of the β-Mg₁₇Al₁₂ phase and the η-Al₈Mn₅ phase in the corrosion behaviour of AZ91D is discussed in term of local nobility, surface coverage of the cathode and the cathodic activity of the different phases.     

Broad-beam laser cladding of Al-Si alloy coating on AZ91HP magnesium alloy

In the present study, an attempt was made to improve the wear resistance and the corrosion resistance of AZ91HP magnesium alloy by laser cladding Al-Si eutectic alloy. The results showed that the clad layer mainly consisted of Mg₂Si, Mg₁₇Al₁₂ and Mg₂Al₃ phases. The microstructure of the bonding zone changed from columnar grains to equiaxial grains along the direction of heat-flow. The heat-affected zone consisted of α-Mg and α-Mg + β-Mg₁₇Al₁₂ eutectic. The formation of multiple Mg intermetallic compounds allowed the clad layer to exhibit higher hardness, better wear resistance and corrosion resistance.     

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.     

Enhanced heterogeneous nucleation in AZ91D alloy by intensive melt shearing

Intensive melt shearing was applied to the commercial AZ91D alloy melt to investigate its effects on grain refinement. Alloy melts with and without melt shearing were also filtered using a pressurized filtration technique to concentrate the potential nucleating particles for electron microscopic examination. The results showed that intensive melt shearing resulted in significant refinement of both the Al₈Mn₅ intermetallics and the primary α-Mg phase in the as-cast AZ91D alloy, and that this grain-refining effect is insensitive to the superheat and can persist even after prolonged isothermal holding. The pressurized filtration experiments showed for the first time that oxide films and skins consist of nano-sized MgO particles populated densely in a liquid matrix. Intensive melt shearing can effectively disperse such MgO particles throughout the alloy melt. The HRTEM investigation and detailed crystallographic analysis confirmed that dispersed MgO particles act as potent heterogeneous nucleation sites for both the Al₈Mn₅ and α-Mg phase.     

Effect of Nd on the corrosion behaviour of AM50 and AZ91D magnesium alloys in 3.5 wt.% NaCl solution

The corrosion performance of AM50 and AZ91D alloys containing up to 1.5 wt.% Nd was investigated by electrochemical and gravimetric measurements in 3.5 wt.% NaCl at 22 °C. The alloys were characterized by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD) and surface potential maps. In Nd-containing alloys, formation of Al₂Nd and Al–Mn–Nd intermetallic compounds reduced the volume fraction and modified the morphology of the β-Mg₁₇Al₁₂ phase. The addition of Nd improved the corrosion resistance of the alloys due to increased passivity of the surface film and suppression of micro-galvanic couples.     

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.     

Microstructure and mechanical properties of AZ91 magnesium alloy with minor additions of Sm,Si and Ca elements

The effects of Sm, Si and Ca on the microstructure and mechanical property of AZ91 magnesium alloy were investigated by means of optical microscopy(OM), differential scanning calorimetry(DSC), scanning electronic microscopy(SEM), X-ray diffraction(XRD) and tensile testing. The results indicated that the addition of 1.5 wt.% Sm with or without 0.8 Si/Ca led to a decrease in the volume fraction of the β-Mg17 Al12 phase and the formation of the intermetallic compounds of Al-Sm, Mg2 Si, Mg Al Ca and Al2 Ca. The microstructure of AZ91 alloy was significantly refined and distribution became discrete with additions of Sm and Ca; the average grain size of the α-Mg matrix was reduced from 239.7 ± 16.9 μm to 66.34 ± 5.10 μm. The AZ91-Sm-Ca alloy exhibited a good combination of yield strength at 135 MPa, ultimate tensile strength at 199 MPa and elongation at 4.32%, which was ascribed to grain refinement strengthening. Furthermore, the T6 treated AZ91-Sm-Ca alloy possessed yield strength of 154 MPa and elongation of 7.1%, which was due to grain refinement strengthening and reduction in discontinuous precipitates.     

Enhanced corrosion behavior and mechanical properties of AZ91 magnesium alloy developed by ultrasonic-assisted friction stir processing

In this study, ultrasonic-assisted friction stir processing (UaFSP) and friction stir processing (FSP) were conducted on AZ91 magnesium alloy sheets, and their microstructure, corrosion behavior, and mechanical properties were comparatively investigated. Scanning electron microscopy, open-circuit potential, and potentiodynamic polarization were used to study the corrosion behavior of the material. Electrochemical measurements reveal that employing UaFSP, the corrosion rate of the AZ91 magnesium alloy was significantly reduced where lower corrosion current density for UaFSP specimens was obtained (2.09 µA/cm²) compared with 3.42 µA/cm² for the FSP and 6.82 µA/cm² for the base metal. This is mainly attributed to the alteration of morphology and better distribution of the β-Mg₁₇Al₁₂ phase during UaFSP. By using ultrasonic vibration in FSP, a finer grain structure was obtained, which improved the tensile strength and hardness of the AZ91 Mg alloy.     

The corrosion performance of anodised magnesium alloys

The corrosion performance of anodised magnesium and its alloys, such as commercial purity magnesium (CP-Mg) and high-purity magnesium (HP-Mg) ingots, magnesium alloy ingots of MEZ, ZE41, AM60 and AZ91D and diecast AM60 (AM60-DC) and AZ91D (AZ91D-DC) plates, was evaluated by salt spray and salt immersion testing. The corrosion resistance was in the sequential order: AZ91D ≈ AM60 ≈ MEZ ? AZ91D-DC ? AM60-DC > HP-Mg > ZE41 > CP-Mg. It was concluded the corrosion resistance of an anodised magnesium alloy was determined by the corrosion performance of the substrate alloy due to the porous coating formed on the substrate alloy acting as a simple corrosion barrier.     

The use of microcapillary techniques to study the corrosion resistance of AZ91 magnesium alloy at the microscale

The AZ91 alloy is composed of Mg₁₇(Al, Zn)₁₂ precipitates, an eutectic phase around these precipitates, AlMn intermetallic particles and an α-Mg solid solution (matrix). The corrosion behaviour of AZ91 was investigated at the microscale by means of the electrochemical microcell technique, which uses extremely small capillaries (diameters between 5 and 10 μm). Experiments were conducted in 0.1 M NaClO₄ at 25 °C. The β-Mg₁₇(Al, Zn)₁₂ precipitates were found to have the highest corrosion resistance, whereas the eutectic phase was very active (pitting potential of approximately −1400 mV vs. Ag/AgCl). The α-Mg solid solution displayed better corrosion resistance than the eutectic phase.     

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.     

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.     

Peak temperatures and microstructures in aluminium and magnesium alloy friction stir spot welds

Abstract

The peak temperatures during friction stir spot welding of similar and dissimilar aluminium and magnesium alloys are investigated. The peak temperatures attained during friction stir spot welding of Al 6111, Al 2024, and AZ91 are within 6% of their solidus temperatures. In dissimilar AZ91/Al 6111 spot welds the peak temperature corresponds with the α-Mg solid solution and Mg₁₇Al₁₂ eutectic temperature of 437°C. An a-Mg plus Mg₁₇Al₁₂ eutectic microstructure is produced in dissimilar friction stir spot welds when material displaced during pin penetration into the lower sheet material contacts the upper sheet material at the eutectic temperature.