New Al–Mg–Li–C dispersion strengthened alloy Part 1 – Composition and process development

Abstract

New fine grained aluminium–magnesium–lithium–carbon alloys, produced by mechanical alloying/powder metallurgy techniques, have been developed. The alloys are suitable for use in the as forged (T1) condition. A preferred chemistry (Al–5.2Mg–1.3Li–0.35%C, wt-%) has been defined, and methods for production of bulk (50 kg) billets and open die uniaxial forgings have been examined. These have produced attractive mechanical properties (0.2%PS=441 MPa, UTS=501 MPa and K_1C=23 MPa m^1/2) without recourse to cold compression. The new alloy is differentiated from AA 5091 by its much lower C content, and by being enriched in magnesium, which provides improved fracture toughness and superior powder handling ability. The balance of properties, achievable in a lightweight, non-heat-treatable alloy, make the alloy a candidate for aerospace, and other applications.     

Development of corrosion resistant magnesium alloys Part 1 Characterisation of splat quenched Mg–10Al and Mg–16Al alloys

Abstract

The surfaces and bulk of splat quenched Mg–10Al and Mg–16Al (wt-%) alloys were investigated. The surfaces were studied using X-ray photoelectron spectroscopy (XPS) , X-ray excited Auger electron spectroscopy (X-AES), Rutherford backscattering spectrometry (RBS) , scanning electron microscopy (SEM), and electron probe microanalysis (EPMA) and the bulk using X-ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. The solid solubility of Al in Mg was extended to at least 16 wt-%. The quantity of Al ions present on the surfaces of the alloys increased with Al content. Contrary to the suggested layered MgO/Mg–Al–oxide/alloy structure, the surfaces of the alloys consisted of an admixture of magnesium spinel (MgAl₂O₄) in periclase (MgO) and brucite (Mg(OH)₂) of non-uniform thickness varying between 10 and 50 nm, determined via RBS, X-AES, and depth profiling using XPS.

MST/1714a     

Interfacial reactions between AZ91D magnesium alloy and plaster mould material during investment casting

Abstract

Reactions at the mould/metal interface play an important role in determining the quality of investment castings. They are particularly critical in the case of magnesium alloys cast in industrial plaster moulds. In this work, reactions of molten magnesium alloy with plaster mould were studied. First the potential interactions with mould materials (including gases) were examined using thermodynamic considerations. Then thin sheets of AZ91D magnesium alloy were cast in industrial plaster moulds using vacuum assistance: the surface of sheets and plaster mould were characterised. The analysis of reaction products indicates that magnesium vapours diffuse through the plaster and reduce the silica present in the investment material according to the following reaction: 4Mg + SiO₂=2MgO + Mg₂Si. The extent of reactions is controlled by mould temperature and thickness of castings.     

Laser–tungsten inert gas hybrid welding of dissimilar AZ based magnesium alloys

Abstract

The microstructure and mechanical properties of dissimilar AZ based magnesium alloys subjected to laser–tungsten inert gas (TIG) hybrid welding have been investigated. The results show that magnesium alloys can be readily welded as dissimilar joints using this process. The microstructure of the dissimilar magnesium alloy joints is composed of primary α phase (Mg) and β phase (Mg₁₇Al₁₂), based on electron probe microanalysis (EPMA) and X-ray diffraction (XRD) data. In addition, the tensile strength of AZ31B–AZ61 and –AZ91 joints is equal to that of AZ31B base metal. It has also been found that the presence of β phase has a severe influence on the tensile strength and mirohardness of dissimilar magnesium alloy joints.     

Effect of Y on the bio-corrosion behavior of extruded Mg–Zn–Mn alloy in Hank's solution

The bio-corrosion properties of Mg–Zn–Mn alloys with and without Y in Hank's solution at 37 °C were investigated by using electrochemical test and electrochemical impedance spectra (EIS). The results of open circuit potential (OCP) and polarization tests indicated that Y could reduce the cathodic current density. A passivative stage appeared in the Tafel curve of the Y containing magnesium alloy, indicating that a passivative film was formed on the surface of the Y containing magnesium alloy. EIS results showed that the Y containing alloy had higher charge transfer resistance and film resistance, but lower double layer capacity than the alloy without the Y element. The surface reaction product identification by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) showed that the surface corrosion products were hydroxide and phosphate (Mg₃Ca₃(PO₄)₄) for Mg–Zn–Mn alloy and phosphate (MgNaPO₄) for the Y containing Mg–Zn–Mn alloys. The XPS results also showed that a Y₂O₃ protective film was formed on the surface of the Y containing magnesium alloy which contributed mainly to the low cathodic current density and the high resistance.     

Effect of Mg content and solution treatment on the microstructure of Al-Si-Cu-Mg alloys

Three different quaternary alloys Al-6Si-3Cu-xMg (x = 0.59, 3.80 and 6.78 wt.%) were produced using conventional ingot casting metallurgy. The study was focused to investigate the effect of magnesium and solution heat treatment on the microstructure. Results shown variations in composition and morphology for the silicon-rich phases as well as a change of the predominant copper-rich phase Al₂Cu (θ) to Al₅Cu₂Mg₈Si₆ (Q phase) when magnesium content is increased. The amount of Mg in solid solution was constant for the three different cast-alloys, increasing considerably after solution heat treatment to 2.7 at.% for the alloy with higher Mg content This fact allowed to obtain Cu:Mg ratios (in at.%) in solid solution lower than 1.0 for the alloys with 3.80 and 6.78 Mg wt.%, impossible to reach for the alloy with low Mg content. During dissolution process, Al₂Cu phase was observed to be more suitable to dissolve than Q phase. Fragmentation, spheroidization and coarsening of Q and silicon-rich phases were observed. Solution time required for these processes occurrence was longer for Q phase. Solution heat treatments at 480°C for 12 h were found to be appropriate for the studied alloys.     

Mechanical and bio-corrosion properties of quaternary Mg–Ca–Mn–Zn alloys compared with binary Mg–Ca alloys

Binary Mg–xCa alloys and the quaternary Mg–Ca–Mn–xZn were studied to investigate their bio-corrosion and mechanical properties. The surface morphology of specimens was characterized by X-ray diffraction (XRD), Fourier-transformed infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). The results of mechanical properties show that the yield strength (YS), ultimate tensile strength (UTS) and elongation of quaternary alloy increased significantly with the addition of zinc (Zn) up to 4 wt.%. However, further addition of Zn content beyond 4 wt.% did not improve yield strength and ultimate tensile strength. In contrast, increasing calcium (Ca) content has a deleterious effect on binary Mg–Ca alloys. Compression tests of the magnesium (Mg) alloys revealed that the compression strength of quaternary alloy was higher than that of binary alloy. However, binary Mg–Ca alloy showed higher reduction in compression strength after immersion in simulated body fluid. The bio-corrosion behaviour of the binary and quaternary Mg alloys were investigated using immersion tests and electrochemical tests. Electrochemical tests shows that the corrosion potential (E_corr) of binary Mg–2Ca significantly shifted toward nobeler direction from −1996.8 to −1616.6 mV_SCE with the addition of 0.5 wt.% manganese (Mn) and 2 wt.% Zn content. However, further addition of Zn to 7 wt.% into quaternary alloy has the reverse effect. Immersion tests show that the quaternary alloy accompanied by two secondary phases presented higher corrosion resistance compared to binary alloys with single secondary phase. The degradation behaviour demonstrates that Mg–2Ca–0.5Mn–2Zn alloy had the lowest degradation rate among quaternary alloys. In contrast, the binary Mg–2Ca alloy demonstrated higher corrosion rates, with Mg–4Ca alloy having the highest rating. Our analysis showed the Mg–2Ca–0.5Mn–2Zn alloy with suitable mechanical properties and excellent corrosion resistance can be used as biodegradable implants.     

Structural refinement of cast magnesium alloys

Abstract

The structure of cast magnesium alloys (grain size and precipitate morphology and size) affects the properties of the products and the scope for use of the alloys. The structure can be controlled by minor additions of inoculants, which are largely determined on the basis of the composition of the alloy concerned. The present paper reviews the scientific background of structural refinement by inoculation and its application to Mg–Zn, Mg–Al, and Mg–Al–Si alloys.     

Microstructure characterisation and mechanical properties of rapidly solidified Mg–Zn–Ca alloys with Ce addition

Abstract

The rapidly solidified (RS) Mg–Zn–Ca based alloys with Ce addition were produced via atomising the alloy melt and subsequently splat quenching the atomised droplets on the water cooled copper twin rollers in the form of flakes. The alloys were characterised by XRD, SEM, HRTEM, DSC and microhardness. All the alloys are characteristic of fine grains in the size of 1–5 μm. The RS Mg–6Zn–5Ca ternary alloy is composed of α–Mg, Mg₂Ca, Ca₂Mg₆Zn₃ and a small quantity of Mg₅₁Zn₂₀, Mg₂Zn₃ and MgZn₂. With the increment of Ce, the Mg₁₂Ce phase in the alloy increases and the Mg₅₁Zn₂₀, Mg₂Zn₃ and Ca₂Mg₆Zn₃ phases decrease, seemly indicating that the proper Ce content is beneficial to the suppression of the latter phases. Moreover, the addition of Ce to the Mg–Zn–Ca alloy contributes to the enhanced thermal stability of the phases in the alloys, especially for the Mg–6Zn–5Ca–3Ce alloy. The microhardness of the RS alloys increases with the increment of Ce, and the strengthening mechanism is discussed.     

Micromorphological effect of calcium phosphate coating on compatibility of magnesium alloy with osteoblast

Abstract

Octacalcium phosphate (OCP) and hydroxyapatite (HAp) coatings were developed to control the degradation speed and to improve the biocompatibility of biodegradable magnesium alloys. Osteoblast MG-63 was cultured directly on OCP- and HAp-coated Mg-3Al-1Zn (wt%, AZ31) alloy (OCP- and HAp-AZ31) to evaluate cell compatibility. Cell proliferation was remarkably improved with OCP and HAp coatings which reduced the corrosion and prevented the H₂O₂ generation on Mg alloy substrate. OCP-AZ31 showed sparse distribution of living cell colonies and dead cells. HAp-AZ31 showed dense and homogeneous distribution of living cells, with dead cells localized over and around corrosion pits, some of which were formed underneath the coating. These results demonstrated that cells were dead due to changes in the local environment, and it is necessary to evaluate the local biocompatibility of magnesium alloys. Cell density on HAp-AZ31 was higher than that on OCP-AZ31 although there was not a significant difference in the amount of Mg ions released in medium between OCP- and HAp-AZ31. The outer layer of OCP and HAp coatings consisted of plate-like crystal with a thickness of around 0.1 μm and rod-like crystals with a diameter of around 0.1 μm, respectively, which grew from a continuous inner layer. Osteoblasts formed focal contacts on the tips of plate-like OCP and rod-like HAp crystals, with heights of 2–5 μm. The spacing between OCP tips of 0.8–1.1 μm was wider than that between HAp tips of 0.2–0.3 μm. These results demonstrated that cell proliferation depended on the micromorphology of the coatings which governed spacing of focal contacts. Consequently, HAp coating is suitable for improving cell compatibility and bone-forming ability of the Mg alloy.     

Bio-corrosion characterization of Mg–Zn–X (X = Ca, Mn, Si) alloys for biomedical applications

The successful applications of magnesium-based alloys as biodegradable orthopedic implants are mainly inhibited due to their high degradation rates in physiological environment. This study examines the bio-corrosion behaviour of Mg–2Zn–0.2X (X = Ca, Mn, Si) alloys in Ringer’s physiological solution that simulates bodily fluids, and compares it with that of AZ91 magnesium alloy. Potentiodynamic polarization and electrochemical impedance spectroscopy results showed a better corrosion behaviour of AZ91 alloy with respect to Mg–2Zn–0.2Ca and Mg–2Zn–0.2Si alloys. On the contrary, enhanced corrosion resistance was observed for Mg–2Zn–0.2Mn alloy compared to the AZ91 one: Mg–2Zn–0.2Mn alloy exhibited a four-fold increase in the polarization resistance than AZ91 alloy after 168 h exposure to the Ringer’s physiological solution. The improved corrosion behaviour of the Mg–2Zn–0.2Mn alloy with respect to the AZ91 one can be ascribed to enhanced protective properties of the Mg(OH)₂ surface layer. The present study suggests the Mg–2Zn–0.2Mn alloy as a promising candidate for its applications in degradable orthopedic implants, and is worthwhile to further investigate the in vivo corrosion behaviour as well as assessed the mechanical properties of this alloy.     

Effect of some alloying elements on boiling point of magnesium

Abstract

The evaporation capacity of alloys differs with temperature, and this is the basis of a new experimental method to measure the boiling points of various kinds of alloys. In the present work, the effects of Al, Zn, Mn and La additions on the boiling point of magnesium have been studied. It is shown that various elemental additions and their varying contents in magnesium alloys have different influences on the boiling point of the alloys. Among these additions, Zn affected the boiling point of magnesium alloys most obviously, followed by Mn, Al and La. The boiling point of Mg–6 wt-%Zn alloy was the highest in the present study, up to 1715 K.     

Microstructural evaluation of dross formation on Mg- and non-Mg-containing Al alloys from industrial furnaces

Abstract

The microstructural aspects of dross formation in industrial Al re-melt furnaces for several different alloy compositions have been evaluated. The Al alloys used in this study included 1350 (no Mg), 3004 (low Mg), and 5182 (high Mg). Dross specimens were collected directly from the different Al alloy melts in industrial furnaces using a consistent sampling protocol in order to compare the microstructure and phase development of the dross as a function of melt temperature and composition. The results showed that the sequence of phases formed during the re-melt process was the same for all the alloys examined; amorphous-Al₂O₃ forms first followed by either α-Al₂O₃+AlN (for non-Mg-containing alloys) or cubic MgO, then MgAl₂O₄, and lastly α-Al₂O₃ (for low- or high-Mg content). The formation of MgAl₂O₄ is associated with accelerated oxidation rates (known as breakaway oxidation) and this reaction proceeds until the Mg is depleted at the molten surface. At this point, aluminum oxidation is predominant and occurs at a significantly lower oxidation rate. The results obtained in this study are consistent with models developed for dross grown on similar Al alloys in laboratory environments and show that Mg oxidation (and the accelerated formation of MgAl₂O₄) dominates the oxidation process during Al melting, whether the Al contains low or high Mg contents. The oxide morphology within the dross layer differed according to the particular alloy being melted and thus the amount of Al recovery from dross can vary with composition.     

Quasicrystal-reinforced Mg alloys

The formation of the icosahedral phase (I-phase) as a secondary solidification phase in Mg–Zn–Y and Mg–Zn–Al base systems provides useful advantages in designing high performance wrought magnesium alloys. The strengthening in two-phase composites (I-phase + α-Mg) can be explained by dispersion hardening due to the presence of I-phase particles and by the strong bonding property at the I-phase/matrix interface. The presence of an additional secondary solidification phase can further enhance formability and mechanical properties. In Mg–Zn–Y alloys, the co-presence of I and Ca₂Mg₆Zn₃ phases by addition of Ca can significantly enhance formability, while in Mg–Zn–Al alloys, the co-presence of the I-phase and Mg₂Sn phase leads to the enhancement of mechanical properties. Dynamic and static recrystallization are significantly accelerated by addition of Ca in Mg–Zn–Y alloy, resulting in much smaller grain size and more random texture. The high strength of Mg–Zn–Al–Sn alloys is attributed to the presence of finely distributed Mg₂Sn and I-phase particles embedded in the α-Mg matrix.     

Effects of Mg content on aging behavior of Al4CuXMg PM alloy

Starting with elemental (pre-mixed) powders for producing shaped powder metallurgy alloys provides some advantages over a pre-alloyed system. The premixed powders are softer than prealloyed powders and therefore by using premixed powders it is possible to have higher compact densities and within a longer die life. In this research work, elemental aluminum powder was mixed with copper and magnesium in various ratios. They were compacted, sintered and heat treated in order to produce light but strong Al-based powder metallurgy alloys. The main focus of this paper is on the effects of micro to macro scale addition of magnesium on the aging response of Al4Cu alloys. Four per cent Cu gives Al powder metallurgy alloy a good control of sintering and a large space for solution treatment. Minor addition of Mg with little amount of Fe, comes from the based Al and Cu powders, enhances the hardness values of Al4Cu powder metallurgy alloys. Highest hardness value was 118 HB obtained from 24 h aged Al4Cu2Mg alloy.     

The influence of HF treatment on corrosion resistance and in vitro biocompatibility of Mg-Zn-Zr alloy

The samples made of a Mg-2.5wt.%Zn-0.5wt.%Zr alloy were immersed in the 20% hydrofluoric acid (HF) solution at room temperature for different time, with the aim of improving the properties of magnesium (Mg) alloy in applications as biomaterials. The corrosion resistance and in vitro biocompatibility of untreated and fluoride-coated samples were investigated. The results show that the optimum process is to immerse Mg alloys in the 20% HF solution for 6 h. After the immersion, a dense magnesium fluoride (MgF₂) coating of 0.5 μm was synthesized on the surface of Mg-Zn-Zr alloy. Polarization tests recorded a reduction in the corrosion current density from 2.10 to 0.05 μA/cm² due to the MgF₂ protective coating. Immersion tests in the simulated body fluid (SBF) also reveal a much milder corrosion on the fluoride-coated samples, and its corrosion rate was calculated to be 0.05 mm/yr. Hemolysis test suggests that the conversion coated Mg alloy has no obvious hemolysis reaction. The hemolysis ratio (HR) of the samples decreases from 11.34% to 1.86% with the HF treatment, which meets the requirements of biomaterials (HR < 5%). The coculture of 3T3 fibroblasts with Mg alloy results in the adhesion and proliferation of cells on the surface of fluoride-coated samples. All the results show that the MgF₂ conversion coating would markedly improve the corrosion resistance and in vitro biocompatibility of Mg-Zn-Zr alloy.     

The influence of HF treatment on corrosion resistance and <Emphasis Type="Italic">in vitro</Emphasis> biocompatibility of Mg-Zn-Zr alloy

The samples made of a Mg-2.5wt.%Zn-0.5wt.%Zr alloy were immersed in the 20% hydrofluoric acid (HF) solution at room temperature for different time, with the aim of improving the properties of magnesium (Mg) alloy in applications as biomaterials. The corrosion resistance and in vitro biocompatibility of untreated and fluoride-coated samples were investigated. The results show that the optimum process is to immerse Mg alloys in the 20% HF solution for 6 h. After the immersion, a dense magnesium fluoride (MgF₂) coating of 0.5 μm was synthesized on the surface of Mg-Zn-Zr alloy. Polarization tests recorded a reduction in the corrosion current density from 2.10 to 0.05 μA/cm² due to the MgF₂ protective coating. Immersion tests in the simulated body fluid (SBF) also reveal a much milder corrosion on the fluoride-coated samples, and its corrosion rate was calculated to be 0.05 mm/yr. Hemolysis test suggests that the conversion coated Mg alloy has no obvious hemolysis reaction. The hemolysis ratio (HR) of the samples decreases from 11.34% to 1.86% with the HF treatment, which meets the requirements of biomaterials (HR < 5%). The coculture of 3T3 fibroblasts with Mg alloy results in the adhesion and proliferation of cells on the surface of fluoride-coated samples. All the results show that the MgF₂ conversion coating would markedly improve the corrosion resistance and in vitro biocompatibility of Mg-Zn-Zr alloy.     

Wetting of (0001) α-alumina single crystals by molten Mg–Al alloys in the presence of evaporation

The wetting of (0001) α-alumina single crystals by Mg–Al alloys over a wide composition range at 1073?K was investigated using an improved sessile drop method in a flowing argon atmosphere. The initial contact angles are between 103° and 84°, almost linearly decreasing with increasing nominal Mg concentration, suggesting that the addition of Mg to Al improves the initial wettability. According to the evolution of contact angle and contact diameter, representative stages were identified to characterize the complex wetting behavior in the presence of evaporation. The wetting kinetics was dependent on the nominal Mg concentration in the alloy. Two patterns of “stick–slip” behavior were observed in the wetting process and interpreted by combining the effects of interfacial reaction and evaporation of magnesium. In addition, the dependence of the interfacial reaction on the Mg–Al alloy concentration was thermodynamically analyzed. The dominant reaction product at 1073?K should be MgO when x _Mg?>?9?mol%, while MgAl₂O₄ when x _Mg?<?9?mol%. However, because of the continuous consumption of Mg due to the evaporation and reaction, its concentration in the alloy progressively decreased with time. As a result, MgO formed usually earlier while MgAl₂O₄ later even for the alloys with higher than 9?mol% Mg.     

Effect of Ce on microstructures and mechanical properties of rapidly solidified Mg–Zn alloy

Abstract

The rapidly solidified (RS) Mg–Zn based alloys with Ce addition were produced via atomising the alloy melt and subsequent splat quenching on the water cooled copper twin rollers in the form of flakes. The effects of Ce additions on the microstructures, phase compositions, thermal stability and isochronal age hardening behaviour of the RS Mg–Zn alloy were systematically investigated. The RS Mg–6Zn alloy is characterised by fine grains in the size of 6–10 μm and is composed of α-Mg, Mg₅₁Zn₂₀ and a small quantity of MgZn₂ and Mg₂Zn₃ phases. With the increment of Ce, the microstructures of the alloys are refined, and the volume fractions of dispersions are increased remarkably. The stable intermetallic compounds, i.e. the Mg_xZn_yCe_z ternary phases, are formed in the RS Mg–Zn–Ce alloys at the expense of the Mg₅₁Zn₂₀ phases, which leads to the enhanced thermal stability of the alloys, especially for the Mg–6Zn–5Ce alloy. In the alloy, the atomic percentage ratio of Zn/Ce in the Mg_xZn_yCe_z phase is close to two, and the maximum hardness is 91·5±7 HV after annealing at 200°C for 1 h. However, the age hardening behaviour of the alloys decreases with the increment of Ce, and the main reason is discussed.