Thermodynamic analysis of processability of Mg–Al–Zn–Mn alloys for rheocasting

A two-stage thermodynamic calculation procedure was developed to analyse alloy compositions for rheocasting. Based on Kazakov's criteria, the processability of AZ91, AZ61 and AM60B for rheocasting was investigated. The results show that these alloys do not satisfy selected criteria fully, and only AZ91 is possible to be used for rheocasting with semisolid slurry having lower fraction solid (0.2–0.4). In microstructure produced by rheocasting, the β-Mg₁₇Al₁₂ phase forms continuous network along primary α-Mg gain boundary and is concentrated in this limited contiguous space. The routes to modify and optimise alloy composition were proposed.     

Deformation-driven formation of equilibrium phases in the Cu–Ni alloys

The homogeneous coarse-grained (CG) Cu–Ni alloys with nickel concentrations of 9, 26, 42, and 77 wt% were produced from as-cast ingots by homogenization at 850 °C followed by quenching. The subsequent high-pressure torsion (5 torsions at 5 GPa) leads to the grain refinement (grain size about 100 nm) and to the decomposition of the supersaturated solid solution in the alloys containing 42 and 77 wt% Ni. The lattice spacing of the fine Cu-rich regions in the Cu–77 wt% Ni alloy was measured by the X-ray diffraction (XRD). They contain 28 ± 5 wt% Ni. The amount of the fine Ni-rich ferromagnetic regions in the paramagnetic Cu–42 wt% Ni alloy was estimated by comparing its magnetization with that of fully ferromagnetic Cu–77 wt% Ni alloy. According to the lever rule, these Ni-rich ferromagnetic regions contain about 88 wt% Ni. It means that the high-pressure torsion of the supersaturated Cu–Ni solid solutions produces phases which correspond to the equilibrium solubility limit at 200 ± 40 °C (Cu–77 wt% Ni alloy) and 270 ± 20 °C (Cu–42 wt% Ni alloy). To explain this phenomenon, the concept of the effective temperature proposed by Martin (Phys Rev B 30:1424, 1984) for the irradiation-driven decomposition of supersaturated solid solutions was employed. It follows from this concept that the deformation-driven decomposition of supersaturated Cu–Ni solid solutions proceeds at the mean effective temperature T _eff = 235 ± 30 °C. The elevated effective temperature for the high-pressure torsion-driven decomposition of a supersaturated solid solution has been observed for the first time. Previously, only the T _eff equal to the room temperature was observed in the Al–Zn alloys.     

Newly observed prismatic Mg2Sn laths in a Mg–Sn–Zn–Mn alloy

Lath-shaped Mg₂Sn precipitates with their habit planes parallel to the prismatic planes of the Mg matrix are characterized in a Mg–Sn–Zn–Mn alloy. The orientation relationships (ORs) between these β-Mg₂Sn precipitates and α-Mg matrix are [0 1 1]_β//[0 1 ?1 0]_α and (0 1 ?1)_β deviating 0.36° to 1.20° from (0 0 0 1)_α, in which the deviation angle of 0.39° is most frequently observed. Although the ORs vary, the laths always exhibit four side facets bearing fixed relationships with g vectors in reciprocal space. Their major side facets incline to the basal plane of Mg matrix from 4.3° to 14.3°.     

Effect of silver addition on formation of secondary phases in squeeze cast Al–Cu–Mg alloys

Abstract

The effect of silver addition on the formation of secondary phases in squeeze cast Al–4.0Cu–1.5Mg and Al–4.0Cu–1.5Mg–0.7Ag (all wt-%) alloys has been investigated using optical microscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffractometry, and transmission electron microscopy. The as cast microstructure of both alloys consists of primary dendritic α-Al and various types of secondary solidification phase, e.g. Al₂Cu, Al₂CuMg, Al(Cu,Ag)Mg, and icosahedral (I) and decagonal (D) quasicrystalline phases. However, the solidification path in the interdendritic region during squeeze casting is different for each alloy, i.e. L→ternary α-Al–Al₂Cu–Al₂CuMg eutectic in Al–4.0Cu–1.5Mg and L→L′+Al₂Cu→α-Al–Al₂Cu–Al(Cu_0.75Ag_0.25)Mg eutectic in Al–4.0Cu–1.5Mg–0.7Ag. This indicates that silver acts as an alloying element stabilising the formation of Al(Cu,Ag)Mg Laves phase. The remaining copper and iron rich liquid in the interdendritic region at the final stage of solidification solidifies into a mixed structure of α-Al, Al₂Cu, and AlCuFe I (or D) phases. The composition of the I and D phases, measured by energy dispersive X-ray spectroscopy, is in the range Al–(27～28)Cu–(9～10)Fe and Al–(26～27)Cu–(7～9)Fe (all at.-%) respectively.     

Influence of second phases on mechanical properties of spray-deposited Al–Zn–Mg–Cu alloy

Al–10.66Zn–2.48Mg–1.41Cu–0.17Zr–0.17Sc (wt.%) alloy prepared by spray deposition was processed with different hot deformation followed by heat treatment. The mechanical properties and microstructure evolution were investigated. The results indicate that uniform ultimate tensile strength of 774 MPa, yield strength of 734 MPa and elongation of 13.7% are obtained with two-step hot deformation, which increase by 2.7%, 3.82% and 95% compared with one-step hot deformation. Microstructural observations show that increase of elongation is mainly ascribed to high volume fraction of smaller precipitates and reduction of stress concentration areas as a result of disappearance of the coarse second phases. The fractured tensile specimens with two-step hot deformation exhibit dimple fractographic features. Improvement of strength is attributed to the precipitation strengthening and dispersed strengthening.     

Optimization of composition and heat treatment design of Mg–Sn–Zn alloys via the CALPHAD method

This work is focused on the application of the calculation of phase diagrams method for alloy and heat treatment design. We analyzed the influence of Zn content on the precipitation of Mg₂Sn in Mg–Sn–Zn alloys. A comparison with previous studies in the Mg–Sn–Zn system was made according to the published results and computational thermochemistry simulations. The phase evolution in the Mg–Sn–Zn system was evaluated for the different compositions, and the simulations were used for precise alloy and heat treatment design. The composition of the ternary alloy was set as Mg–8wt%Sn–1.25wt%Zn. The Sn and Zn content was designed and confirmed to be within the α-Mg solubility limit at the solution treatment temperature. The addition of Zn and the heat treatment applied resulted in the enhancement and refinement of the Mg₂Sn precipitation. Three Vickers micro-hardness maxima were detected: precipitation of metastable Mg–Zn phases, heterogeneous precipitation of Mg₂Sn on the Mg–Zn precipitates, and Mg₂Sn precipitation in the α-Mg matrix. The CT simulations were found to be a valuable alloy design tool.     

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.     

Constitutive analysis of Mg–Al–Zn magnesium alloys during hot deformation

The constitutive behaviors of Mg–Al–Zn magnesium alloys during hot deformation were studied over a wide range of Zener–Hollomon parameters by consideration of physically-based material’s parameters. It was demonstrated that the theoretical exponent of 5 and the lattice self-diffusion activation energy of magnesium (135 kJ/mol) can be used in the hyperbolic sine law to describe the flow stress of AZ31, AZ61, AZ80, and AZ91 alloys. The apparent hyperbolic sine exponents of 5.18, 5.06, 5.17, and 5.12, respectively for the AZ31, AZ61, AZ80, and AZ91 alloys by consideration of deformation activation energy of 135 kJ/mol were consistent with the considered theoretical exponent of 5. The influence of Al upon the hot flow stress of Mg–Al–Zn alloys was characterized by the proposed approach, which can be considered as a versatile tool in comparative hot working and alloy development studies. It was also shown that while the consideration of the apparent material’s parameters may result in a better fit to experimental data, but the possibility of elucidating the effects of alloying elements on the hot working behavior based on the constitutive equations will be lost.     

Microstructure and mechanical property of high strength Mg–Sn–Zn–Al alloys

This paper aims to reveal the microstructure and mechanical properties of as-cast and hot-rolled Mg–Sn–Zn–Al based alloys. Three alloys, Mg–5Sn–2Zn (TZ52), Mg–5Sn–2Zn–2Al (TAZ522) and Mg–5Sn–5Al–1Zn–0.2Mn (TAZM5510) alloys were studied. The results revealed that the as-cast alloys showed fine dendritic structures. The TAZM5510 alloys exhibited moderate yield strength of 98?MPa with good elongation of ～15%, which was comparable to several commercially used Mg die-castings. Mechanical properties were significantly improved after multi-pass rolling. The TZ52 sheet showed a high yield strength of 277?MPa with excellent ductility exceeding 30%, and the TAZM5510 sheet exhibited the highest tensile strength of 386?MPa while keeping desirable elongation of 16.6%. These sheets are termed as strong and ductile Mg–Sn–Zn–Al wrought alloys.     

Stability of metastable phases and microstructures in the ageing process of Al–Mg–Si ternary alloys

Precipitation behaviour of Al–Mg–Si alloys, with balanced (Mg/Si=2), excess silicon (Mg/Si<2) and excess magnesium (Mg/Si>2) compositions, were studied by differential scanning calorimetry (DSC), transmission electron microscopy (TEM), and Vickers hardness tests. Four significant exothermic peaks were observed in DSC curves which were attributed to metastable clusters, , and stable phases. The peaks corresponding to and were formed closely in the DSC curves but showed different behaviour in isothermal annealing. The additional peak verifying the precipitation of phases, which has recently been proposed by some workers, was not detected. Transmission electron microscope observations and Vickers microhardness tests showed that precipitates played a major role in improving the hardness, but not precipitates. © 1998 Chapman & Hall     

Forgeability test of extruded Mg–Sn–Al–Zn alloys under warm forming conditions

Magnesium (Mg) alloys have been thoroughly researched to replace steel or aluminum parts in automotives for reducing weight without sacrificing their strength. The widespread use of Mg alloys has been limited by its insufficient formability, which results from a lack of active slip systems at room temperature. It leads to a hot forming process for Mg alloys to enhance the formability and plastic workability. In addition, forged or formed parts of Mg alloys should have the reliable initial yield and ultimate tensile strength after hot working processes since its material properties should be compatible with other parts thereby guaranteeing structural safety against external load and crash. In this research, an optimal warm forming condition for applying extruded Mg–Sn–Al–Zn (TAZ) Mg alloys into automotive parts is proposed based on T-shape forging tests and the feasibility of forged parts is evaluated by measuring the initial yield strength and investigating the grain size in orientation imaging microscopy (OIM) maps.     

Comparison of biodegradable behaviors of AZ31 and Mg–Nd–Zn–Zr alloys in Hank's physiological solution

The main challenge for the application of magnesium and its alloy as degradable biomaterials lies in their high degradation rates in physiological environment. In the present work, the biodegradable behavior of a patent magnesium alloy Mg–Nd–Zn–Zr (JDBM) and a reference alloy AZ31 was systematically investigated in Hank's physiological solution. The corrosion rate of JDBM (0.28 mm/year) was much slower than that of AZ31 (1.02 mm/year) in Hank's solution for 240 h. After corrosion products were removed, smooth surface of the JDBM was observed by SEM observation compared to many deep pits on the surface of AZ31. Open-circuit potential and potentiodynamic polarization results manifested that pitting corrosion did not occurred on the surface of JDBM at the early period of immersion time due to the formation of a more protective and compact film layer suggested by electrochemical impedance spectroscopy study. The corrosion rate of magnesium alloys was found to slow down in dynamic corrosion in comparison with that in the static corrosion. This provided the basis for scientific evaluation of in vitro and in vivo corrosion behavior for degradable biomagnesium alloy. The present results suggest that the new patent magnesium alloy JDBM is a promising candidate as degradable biomaterials and is worthwhile for further investigation in vivo corrosive environment.     

Enhancing mechanical properties of Mg–Sn alloys by combining addition of Ca and Zn

We developed new wrought Mg–2Sn–1Ca wt.% (TX21) and Mg–2Sn–1Ca–2Zn wt.% (TXZ212) alloys with high strength and ductility simultaneously, produced by conventional casting, homogenization and indirect extrusion. A partial dynamically recrystallized microstructure, with the micron-/nano-MgSnCa particles and G.P. zones dispersing, was obtained in TX21 alloy extruded at 260 °C (TX21-260). The TX21-260 alloy exhibited yield strength (YS) of 269 MPa, ultimate tensile strength (UTS) of 305 MPa, while those of the TX21 alloy extruded at 300 °C decreased to be 207 MPa and 230 MPa respectively. For TXZ212-260 alloy, on the other hand, MgSnCa, MgZnCa and MgZn₂ phases were observed, and the average grain size increased to be ∼5 μm. The YS and UTS of TXZ212-260 alloy evolved to be 218 MPa and 285 MPa, and the elongation (EL) reached as high as 23%. The high strengths of TX21-260 alloy were expected due to the high number density of nano-MgSnCa phases, G.P. zones and ultra-fine grain size (∼0.8 μm). The high EL of 23% in TXZ212-260 alloy was consistent with the high work-hardening rate, which was attributed to the larger grain size, more high angular grain boundaries, presence of more nano-particles and the weaker texture.     

Structure and thermodynamics of the key precipitated phases in the Al–Mg–Si alloys from first-principles calculations

First-principles calculations have been carried out to investigate the structure, stability, and finite-temperature thermodynamic properties of the key precipitates in the Al–Mg–Si alloys including β″-Mg₅Si₆, U1-Al₂MgSi₂, U2-Al₄Mg₄Si₄, β′-Mg₉Si₅, and β-Mg₂Si. The calculated phonon densities of states indicate that these precipitated phases are vibrationally stable. Within the framework of the quasiharmonic approach, the finite-temperature thermodynamic properties of these precipitated phases including entropy, enthalpy, and Gibbs free energy have been calculated. The heat capacities at constant pressure for these precipitates are predicted. The finite-temperature entropies of formation, enthalpies of formation, and Gibbs free energy of formation for these precipitates are also computed. The acquired thermodynamic properties are expected to be utilized for the prediction of the metastable equilibria in the Al–Mg–Si alloys.     

Creep deformation behavior of Sn–Zn solder alloys

Creep properties of three Sn–Zn solder alloys (Sn–9Zn, Sn–20Zn, and Sn–25Zn, wt%) were studied using the impression creep technique. Microstructural characteristics were examined using a scanning electron microscope. The alloys exhibited stress exponents of about 5.0. The activation energy for creep was calculated to be ~50–75 kJ/mol with a mean value of 66.3 kJ/mol. The likely creep mechanism was identified to be the low temperature viscous glide of dislocations.     

Effect of the Zn content on the microstructure and mechanical properties of indirect-extruded Mg–5Sn–xZn alloys

Mg–5Sn–xZn alloys with varying Zn contents were subjected to indirect extrusion and the effects of the Zn content on the microstructure and mechanical properties of the as-extruded alloys were investigated. It was found that, the grain size and the basal texture are basically similar, however, the amount of fine particles consisting of Mg₂Sn and MgZn phases increases markedly as the Zn content increases. A higher number of these particles would be responsible for the better comprehensive mechanical properties as well as a lower degree of yield asymmetry.     

Prediction and characterization of growth temperatures in Al–Zn–Mg alloys

Growth temperatures of α-Al, intermetallic τ and eutectic α + τ phases in Al-12 wt.% Zn 6 wt.% Mg alloy has been determined as a function of growth velocity in the range of 3 × 10^? 5 to 1 × 10^? 3 m/s at a temperature gradient of 2500 K/m, using a directional solidification technique. The experimental results are found to be in good agreement with predictions of growth temperatures of competing constituents for multicomponent systems.     

Effect of Al on the microstructure and mechanical properties of Mg–6Zn–2Sn–0.5Mn alloy

The microstructure and mechanical properties of Mg–6Zn–2Sn–0.5Mn–xAl (x?=?0, 1, 2, 3) alloy are investigated. The addition of Al leads to the refinement of grain size and the formation of Al₆Mn, Mg₃₂(Al,Zn)₄₉ also forms when the amount of Al is higher than 2?wt-%. Because of the addition of Al, the precipitates in the alloy after ageing treatment are refined. The alloy containing 1?wt-% Al shows good mechanical properties in the as-cast state which is attributed to the refined grains and low volume fraction of large second phases, it also shows high strength after ageing treatment resulted mainly from the homogeneously distributed fine precipitates, the yield strength, ultimate tensile strength and elongation are 183, 310?MPa and 11%, respectively.     

Geometrical compatibility factor analysis of paired extension twins in extruded Mg–3Al–1Zn alloys

Recently, geometrical compatibility factor (m′) has been used to characterize local strain compatibility between paired twins formed in rolled Mg alloys with basal texture. High m′ and m′ rank were present in most cases, suggesting that m′ plays an important role in twin pair formation. The present study aims to extend the understanding of the effects of m′ and grain boundary (GB) misorientation angle on twin pair formation in an extruded Mg alloy with basal fiber texture. 106 sets of paired twins were extracted from electron backscatter diffraction (EBSD) data and were analyzed. The results show that m′ of paired twins distributes in a wide range (− 0.5 to 1) in extruded Mg alloys due to the presence of a large fraction of high angle GBs. About 60% of twin pairs have the first m′ rank, implying that m′ is still an important factor for variant selection of paired twins in extruded Mg alloys. The distribution of m′ with SF rank was also analyzed, showing that more than half of twin pairs are located in the left-top corner with m′ > 0.6 and SF either rank one or two, which confirms that simultaneously high SF and high m′ is favorable for twin pair formation in extruded Mg alloys.