Search

In this investigation, we report the cyclic performance, microstructure and thermal properties of near eutectic Mg–Ni alloys with different Ni contents (4.4, 11.3 and 16.3 at%). The starting cast ingots are mechanically chipped to flakes of about 400 μm, all displaying composite structures characterized by a typical eutectic microstructure with rather coarse features (1–5 μm). The flakes are cycled 1000 times at 330 °C under 30/1 bar H2 for the absorption/desorption processes. The hydrogen storage capacity is maintained throughout the cycling: 5.09, 4.46 and 3.49 wt% H2 for Ni16.3, Ni11.3 and Ni4.4 (at%), respectively. No significant microstructural change is observed, indicating the excellent stability of the alloys at elevated temperatures. Nevertheless, a marked porosity, and spheroidal Mg2Ni clusters can be noted after cycling, however their exact contribution to reaction kinetics has yet to be fully elucidated. An attempt is made to estimate the dehydrogenation activation energy of Ni16.3, and the calculated value seems comparable to that obtained for an early cycling stage (10 cycles). In the light of the superior stability under cyclic service and the low decomposition temperature, the Mg–Mg2Ni system is shown to possess an excellent potential for long-term hydrogen and heat storage applications.

This article reports the hydrogenation properties of several Mg–Mg2Ni composite specimens with increasing Ni content: 4.4, 11.3 (eutectic), and 16.3 (in at%). Mg–Mg2Ni composites were prepared by means of induction melting, followed by simple mechanical chipping of the casts. The hydrogenation and dehydrogenation reaction kinetics were studied, and reaction mechanisms were described by means of solid-gas reaction modeling. Absorption and desorption properties were evidenced to be diffusion controlled, with hydrogen diffusion through hydrided/dehydrided phases being the rate limiting step in most cases (the migration of metal/hydride interface at a constant velocity being rate-limiting in only few of them). The kinetics study was supported by a thorough thermal analysis to provide in-depth insights of the decomposition reaction. Hence, thermogravimetry (TG) and pressurized differential scanning calorimeter (PDSC) were combined to investigate the dehydrogenation properties such as hydrogen gravimetric density, reaction onset temperature, enthalpy and activation energy as a function of Ni content. Structural analysis included X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM, TEM) to discuss the structural stability and microstructural evolution as a function of cycles, notably during the activation procedure. Finally, cyclic performance was evaluated for 100 cycles, using a custom-made large-scale reactor to demonstrate scale-up feasibility.

This study investigated the corrosion protection by electrodeposited copper layer on AZ31 Mg alloy with and without additional silver layer. The single copper layer electrodeposited on AZ31 from copper pyrophosphate bath exhibited nodular structure and crevices between the nodules which resulted in the rapid initiation of pitting corrosion. Employing an additional electrodeposited silver layer onto the copper deposited AZ31 alloy decreased the number of imperfections and changed structure of electrodeposited copper from nodular to fine particle type resulting in improved corrosion resistance. This study further revealed that triple-layer coating of Cu/Ag/Cu exhibited the most efficient corrosion protection of AZ31 Mg alloy.

We report that alloying with Y remarkably enhances the corrosion resistance of extruded Mg–Al–Ca-based alloy. The corrosion rates, measured by immersion tests in 0.6 M NaCl solution at 25 °C, were 0.31 and 1.84 mm y −1 for the Mg–6Al–1Zn–0.5Ca–0.3Mn (wt.%) alloys with and without 0.25 wt.% Y, respectively. The improved corrosion resistance is mainly attributed to a change in the type of Al-containing intermetallic particles toward reducing their electrochemical nobility, resulting in reduced H 2 evolution rate during corrosion.

We report that twin-roll cast and subsequently heat-treated Mg–6Zn–1Mn–1Al alloy sheets with a thin thickness of 1 mm were successfully joined by surface-friction welding process. The welded sheet revealed several distinct weld zones, which are closely related to plastic flow and frictional heat generation during welding. Although large microstructural differences were found among the welded zones, the presence of thermally stable Al 8 Mn 5 particles pre-existing in the sheet appeared uninfluenced by the welding process. The role of the microstructural changes induced by the welding process in the hardness variation and tensile properties of the welded sheet is discussed.

This study paid attention to the big difference between the corrosion rates of permanent mold cast and hot-extruded pure Mg. Fe existed as different state according to process history, which affected the corrosion behavior of pure Mg largely. The corrosion rate of high purity Mg was measured extremely low when Fe was dissolved into the matrix as a solid solution while it increased dramatically when Fe was precipitated as a second phase. The precipitation behavior of the second phase containing Fe was affected by other impurities as much as thermal history, which affected the corrosion behavior of high purity Mg. It is suggested from this study that the tolerance limit of Fe is strongly dependent on the content of Fe, the sort and content of other impurities and process history, which should be considered to design the composition and processing route of high corrosion-resistant Mg alloy.

In this study, the effects of processing history on corrosion behaviours of pure Mg with controlled impurity content, were analysed systematically. Results revealed that impurity Fe and Si were precipitated into the Fe-Si phase by heat treatment prior to extrusion, leading to severe micro-galvanic corrosion of as-extruded pure Mg despite the same impurity contents with as-cast pure Mg. This result suggests that control of the actual tolerance limit, considering not only the impurity content but also the processing history, is required in designing alloys.

In this study, the tensile deformation behavior of as-extruded AZ91 magnesium alloy under pulsed electric current has been investigated based on microstructural observations. The flow stress decreased and the elongation increased remarkably on applying electric current in comparison with non-pulsed tensile test at both room temperature and at 70 °C. The results of EBSD and EDS analysis showed that dissolution of the Mg17Al12 phase obviously occurs during pulsed tensile test due to thermal effect caused by Joule heating and athermal effect of electric current. To distinguish the athermal and thermal effects of electric current, the induction heat treatment (IHT) that follows the temperature cycle measured during pulsed tensile test was carried out using a dilatometer, which could control the temperature of specimen by an induction heater in a vacuum. Additionally, electropulsing treatment (EPT) was conducted and compared with the conventional heat treatment (CHT) under the same condition. The fraction of Mg17Al12 phase after pulsed tensile test and EPT was obviously lower in comparison with IHT and CHT, respectively. The results prove that applying electric current accelerates dissolution of Mg17Al12 phase in as-extruded AZ91 alloy with a distinct effect from Joule heating during deformation. It is proposed that electrically-assisted manufacturing (EAM) technique can improve the efficiency of forming process for as-extruded AZ91 alloy.

Microstructure and corrosion properties of extruded AZ61 Mg alloys with varying Ca contents were investigated. Microstructure of the extruded AZ61 alloy consisted of α-Mg grains and Al 8 Mn 5 particles. Alloying with 0.1–0.5 wt% Ca to the AZ61 alloy resulted in the additional presence of (Mg,Al) 2 Ca particles in the extruded microstructure. In 0.6 M NaCl solution at 25 °C, the extruded AZ61 alloys with 0.1–0.5 wt% Ca showed corrosion rates over 2 times faster than that of the AZ61 alloy without Ca addition. Such deteriorated corrosion resistance due to Ca addition is discussed in terms of passivation and microgalvanic corrosion.

In this work, effect of zincate treatment of AZ91 Mg alloy on the following electrodeposition of copper was examined in a non-cyanide bath containing pyrophosphate ions in view of surface morphology and adhesion of the electrodeposited copper layer. Without zincate treatment, the electrodeposited copper layer showed very porous structure and poor adhesion. On the other hand, the copper layer electrodeposited on the zincate-treated surface showed dense structure and good adhesion. The dissolution rate of AZ91 Mg alloy after the zincate treatment appeared to decrease about 40 times in the copper pyrophosphate bath, as compared to that of the surface without zincate treatment. The porous morphology and poor adhesion of a copper layer on the AZ91 Mg alloy surface without zincate treatment were attributed to small number of nucleation sites of copper because of rapid dissolution of the magnesium substrate in the pyrophosphate bath. Based on the experimental results, it is concluded that the zincate treatment to form a conducting and protecting layer on the AZ91 Mg alloy surface is essential for successful electrodeposition of a copper layer on AZ91 Mg alloy with good adhesion and dense structure in the copper pyrophosphate bath.

The effects of microstructural factors, including the fraction of second phase particles and solute content in the matrix, on the corrosion behavior of as-extruded Mg-Sn-Zn alloys were evaluated by immersion and salt spray testing. After immersion testing, the average corrosion rate increased with the increase in Sn content and decrease in Sn:Zn ratio. On the other hand, after salt spray testing, the average corrosion rate increased with the increase in Sn content, but it was minimized at the Sn:Zn ratio of 5:2. Hydrogen evolution appeared to be the dominant controlling factor of corrosion during immersion, while the partial protectiveness of the film also contributed to the corrosion during salt spray testing.

Copper electrodeposition on AZ91 Mg alloy was studied in views of preferential deposition on α- or β-phases and how to achieve uniform deposition over the entire surface on α- and β-phases in a cyanide solution. The inhomogeneous microstructure of AZ91 Mg alloy, particularly α- and β-phases, was found to result in non-uniform deposition of zincate layer, preferential deposition of zincate on β-phases, which leads to non-uniform growth of copper layer during the following electrodeposition process. The preferential depositions of zincate can be attributed to higher cathodic polarizations on the β-phases. Pin-hole defects in the copper electrodeposit were observed at the center of large size β-phase particles which is ascribed to gas bubbles formed at the β-phases. The activation of AZ91 Mg alloy in hydrofluoric acid solution was used to obtain uniform growth of zincate layer on both the α- and β-phases. By choosing an optimum activation time, a uniform zincate layer was obtained on the AZ91 Mg alloy surface and thereby uniform growth of copper was obtained in a cyanide copper electroplating solution.

The corrosion behaviours of commercial AZ91D alloy and Ca–Y-containing AZ91 alloy, fabricated by casting, were evaluated, and their microstructural changes and surface properties were analysed. The Ca–Y-containing AZ91 alloy showed superior corrosion resistance compared with the AZ91D alloy mainly because of the decrease in the Volta potential difference between the matrix and the secondary phases formed in the Ca–Y-containing alloy, such that micro-galvanic corrosion was significantly suppressed. Furthermore, passivity and stability of the surface film improved with the addition of Y to the AZ91 alloy. Thus, the overall corrosion resistance was significantly improved in the Ca–Y-containing AZ91 alloy.

Corrosion behavior of extruded Mg and Mg5Sn (in wt%) alloy was investigated, and a passivated surface of the Mg5Sn was examined. Immersion test in a 0.6 M NaCl solution revealed that corrosion of the Mg was significantly faster than the Mg5Sn alloy, and vigorous H2 evolution was accompanied with the severe corrosion of Mg. Polarization tests confirmed that cathodic reaction was inhibited in the Mg5Sn alloy. It was considered that the decreased H2 evolution of the Mg5Sn alloy was attributed to the formation of Sn-accumulated layer between the passive film and matrix, which was examined by an XPS analysis.

In this study, the effects of solid tin dissolved in the α-magnesium matrix of magnesium-tin alloys on the characteristics of surface films of the alloys were investigated using immersion and electrochemical tests, which were performed in a sodium chloride solution. The macroscopic in-situ and anodic potentiostatic tests showed that the breakdown resistance of the surface films could be arranged in the following order: pure magnesium

Microstructure and corrosion properties of extruded Mg–8Sn–1Zn alloys with varying Al contents were investigated. Microstructures of the extruded alloys mainly consisted of α-Mg grains and Mg2Sn particles in common. Addition of Al to the ternary alloy resulted in the formation of different types of Al–Fe-based intermetallic particles depending on Al contents. In 0.6 M NaCl solution, the extruded alloys with 1–3 wt% Al showed over 30 times higher corrosion rates than those containing less than 0.3 wt% Al; this discrepancy was attributed to the presence of Al5Fe2 particles acting as strong cathodic sites for H2 evolution during corrosion.

We present simulations of the nucleation and equiaxed dendritic growth of the primary hexagonal close-packed $$\mathrm{\alpha} $$ -Mg phase followed by the nucleation of the $$\mathrm{\beta} $$ -phase in interdendritic regions. A zoomed-in region of a melt channel under eutectic conditions is investigated and compared with experiments. The presented simulations allow prediction of the final properties of an alloy based on process parameters. The obtained results give insight into the solidification processes governing the microstructure formation of Mg-Al alloys, allowing their targeted design for different applications.

The effects of microstructural factors, including fraction of second phase particles and solute content in a matrix, on the corrosion behaviour of Mg–5Sn–xZn (x = 1, 3 wt%) alloys were evaluated by using potentiodynamic polarisation and immersion tests. The hydrogen evolution rate and the corrosion potential increased with increasing Zn content, while the passive current density decreased. The average corrosion rate measured by immersion test increased with increasing Zn content, and was consistent with the hydrogen evolution rate. The increase of the corrosion rate with increasing Zn content resulted from increasing fraction of Mg2Sn particles and Zn content dissolved in the matrix.

The corrosion behavior of as-extruded Mg–5Sn–(1–4)Zn (in wt%) alloys in a 0.6 M NaCl solution were investigated using an immersion test, a polarization test, and a zero resistance ammeter technique, and the corrosion properties of the alloys were discussed in consideration of the microstructure. The immersion test showed that the Mg–5Sn–2Zn alloy exhibited the lowest dissolution rate among the alloys, and further addition of Zn increased the corrosion rate. The electrochemical test results revealed that the overall corrosion rate of the passivated Mg–5Sn–(1–4)Zn alloys showed a strong correlation with the H2 evolution rate rather than the stability of the passivity.

The corrosion product films formed on the surface of Mg–2Zn and Mg–5Zn alloys in NaCl solution were investigated by electrochemical measurement, scanning electron microscopy (SEM) observation and X-ray photoelectron spectroscopy (XPS) analysis. It is found that a compact corrosion product film is formed in the initial stage of immersion, and then the film gradually degrades due to dissolution reaction. The product film formed on Mg–2Zn alloy presents better protection property than that on Mg–5Zn alloy, which can be attributed to the different chemical composition and microstructure of the both alloys.

Microstructural characterization and mechanical properties of as-cast Mg-8Sn-1Al-1Zn-xCu (x=0wt%, 1wt%, 1.5wt% and 2.0wt%) alloys were studied by OM, Pandat software, XRD, SEM, DSC and a standard universal testing machine. The experimental results indicate that adding Cu to TAZ811 alloy leads to the formation of the AlMgCu and Cu3Sn phases. Tensile tests indicate that yield strength increases firstly and then decreases with increasing Cu content. The alloy with the addition of 1.5wt% Cu exhibits optimal mechanical properties among the studied alloys. The improved mechanical properties can be ascribed to the second phase strengthening and fine-grain strengthening mechanisms resulting from the more dispersed second phases and smaller grain size, respectively. The decrease in ultimate tensile strength and elongation of TAZ811-2.0wt% Cu alloy at room temperature is ascribed to the formation of continuous AlMgCu and coarse Mg2Sn phases in the liquid state.

The corrosion behaviour of extruded Mg–(2–8 wt%)Sn alloys was investigated in aqueous chloride solutions, and the influences of the volume fraction of Mg 2 Sn intermetallics, solutionised Sn, and area fraction of grain boundaries on the corrosion behaviour were discussed. The Sn addition to α-Mg increased the solutionised Sn content in the matrix, increased the volume fraction of Mg 2 Sn intermetallics to 7.3%, and changed the grain size distribution. Regarding the corrosion behaviour, the Sn addition up to 8 wt% increased the overall dissolution rate of the alloys, although it promoted the passivity, which resulted from the increased H 2 evolution rate and increased numbers of initiation sites for pitting corrosion. The overall corrosion behaviour primarily depended on the amount of Mg 2 Sn intermetallics, which promoted passivity and notably increased the H 2 evolution rate, and functioned as pitting corrosion initiation sites. As the area fraction of grain boundaries increased, the H 2 evolution rate was also accelerated. In contrast, the solutionised Sn decreased the H 2 evolution rate.

A hot rolled magnesium alloy sheet embedded in a steel block was rolled together with 3% thickness reduction at room temperature, 373 K, and 673 K. Tensile twins were observed after the rolling, which could not be found when the magnesium alloy sheet was rolled without the steel block. The twin fraction was the highest at 373 K because of thermal expansion and activating non-basal slip systems at high temperature. Electron back-scattered diffraction analysis and finite element simulations confirmed that the steel block with higher strength played an important role in generating compressive stress along the transverse direction in the magnesium alloy sheet. The compressive stress could increase owing to suppression of thermal expansion in the magnesium alloy sheet at 373 K. The yield stress and the tensile stress became higher in the rolled specimen with the steel block at 373 K than in the specimen without it owing to grain refinement caused by tensile twins.

The effects of Zn on corrosion behaviour of as-extruded Mg-(1-4)Zn alloys were investigated using an immersion test, a zero resistance ammeter technique, and a potentiodynamic polarisation test. As a result, it was revealed that the solutionised Zn enhanced protectiveness of the passive film, and accelerated the H2 evolution rate of the Mg–Zn binary alloys. The acceleration of the H2 evolution rate by addition of Zn leads to an increase in the net corrosion rate of the Mg–Zn alloy. In this research, the polarisation test was found to have some limitations for evaluating the true corrosion behaviour of passive Mg–Zn alloy.

This study demonstrates that cold pre-forging (CPF) conducted before extrusion is a promising means for improving the mechanical properties of extruded magnesium alloys. The CPF process induces numerous twins in the billet, which in turn provides nucleation sites for dynamic recrystallization during extrusion, leading to an increase in the dynamically recrystallized (DRXed) fraction of the extruded alloy. This process increases the uniformity of the DRXed grain structure, thereby improving the strength and ductility of the extruded alloy.

The naturally formed oxide films on Mg–2Zn and Mg–5Zn alloys were investigated by atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and electrochemical measurements. The oxide films on the both alloys present a similar chemical composition, consisting of surface layer of basic magnesium carbonate and MgO following with MgO and ZnO, but the oxide film on Mg–5Zn is thicker and contains more defects. The protection performance of the oxide film on Mg–5Zn is worse under open circuit potential but better in a suitable anodic potential scope compared with that on Mg–2Zn alloy.

The effect of addition of Sn and/or Zn on corrosion properties of Mg–6Al–0.3Mn alloy was investigated systematically by immersion and salt spray tests. In case of immersion test, average corrosion rate increased by addition of 1 wt% Sn but it decreased by addition of 1 wt% Zn. When the half of the amount of Sn addition was replaced by Zn, the average corrosion rate decreased in comparison with the average corrosion rate of Mg–6Al–0.3Mn–1Sn alloy. In case of salt spray test, the change of average corrosion rate according to composition of the alloy was similar to the result of immersion test. It seemed that the change of corrosion properties according to composition of the alloy was strongly related to the microstructural changes including the sort, fraction and morphology of second phase.

The effect of Zn concentration on the corrosion behavior of Mg-xZn alloys is investigated. The microstructure is observed by scanning electron microscopy (SEM). The corrosion resistance is evaluated by electrochemical and immersion tests. The initiation and propagation of corrosion are analyzed based on the electrochemical measurements and corrosion morphologies observation. It is found that the MgxZny second phases are precipitated on the boundaries and their volume fractions rise with increasing Zn concentration. As a result, the corrosion resistance of Mg-xZn alloys reduces with increasing Zn concentration, which is greatly associated with the micro-cathodic effect of the MgxZny second phases. (C) 2012 Elsevier Ltd. All rights reserved.

The MgxZny second phases in Mg-5Zn alloy were adjusted by T4 and T6 treatment, and then the role of second phases in the corrosion behavior of Mg-5Zn alloy was investigated. The dimension of the MgxZny second phases is only some hundred nanometers. They present discrete distribution on the boundaries of the as-received sample and continuous distribution in the T6 sample. The T4 sample in absence of second phases exhibits the best corrosion resistance while the T6 sample with the largest volume fraction of second phases exhibits the worst one, which can be attributed to the micro-cathodic effect of second phases. (c) 2012 Elsevier Ltd. All rights reserved.

Magnesium alloys exhibit poor ignition resistance after the addition of elements whose solubility limit in the matrix is extremely low, although these elements can thermodynamically bring about the formation of an additional protective oxide layer by alloying. The solute concentration of the alloying elements dissolved in a matrix, in conjunction with conventionally used factors such as the Pilling–Bedworth ratio and the Gibbs free energy change for oxidation, should be considered as an important factor influencing the ignition resistance of magnesium.

Microstructural changes with varying amounts of Ca in cast AZ31-xCa (x: 0.7 wt.%, 2.0 wt.%, 5.0 wt.%) alloys were investigated. According to transmission electron microscopy (TEM) analyses, it was experimentally confirmed that the C36-(Mg,Al)2Ca phase with a di-hexagonal structure formed at interdendritic regions in as-cast AZ31 alloys with no more than 2 wt.% Ca. On the other hand, as the Ca content exceeded 2 wt.%, the lamellar structure consisting of the α-Mg phase and the Mg2Ca phase with a C14 structure formed at interdendritic regions instead of C36 phase. Plate-like Al2Ca precipitates with a C15 structure also formed on the basal plane inside the α-Mg grains.

Impurities such as Fe, Ni and Cu and non-metallic inclusions such as oxides, nitrides, carbides, sulfides and fluorides are harmful to the quality and various properties of magnesium alloy sheets produced by twin-roll casting. In this study, the changes of the content of Fe and non-metallic inclusions in AZ31B magnesium alloys with melt temperature and isothermal holding time were quantitatively evaluated using EPMA and the metallographic method. The Fe content did not increase above the Fe content in the raw material, which implies that the dissolution of Fe from a steel crucible was suppressed effectively. The content of non-metallic inclusions, mainly consisting of oxide, fluoride and Fe-rich intermetallic compounds, did not change remarkably with the melt temperature but it increased with the isothermal holding time due to the continuous oxidation of the magnesium alloy melt on the melt surface.

The effect of Ca element on the hot workability and microstructure evolution of AZ31 magnesium alloy was investigated. Conventional AZ31, AZ31 + 0.7 wt.%Ca, and AZ31 + 2.0 wt.%Ca alloys were tested. Electron back scattered diffraction microscopy revealed that the alloys containing Ca exhibited much finer and more homogeneous microstructure than the conventional AZ31 alloy. Hot compression and tensile tests showed that the Ca element generally increased flow strength and decreased ductility at low temperature. High temperature elongation was considerably improved by the operation of the thermally activated process. TEM work suggested that the large volume fraction of fine (Mg, Al)2Ca particles played an important role in preventing significant grain growth of the AZ31 + 2.0Ca alloy.

The effect of the reduction ratio per pass on the microstructural evolution of an AZ31 gravity cast plate during hot rolling was evaluated systematically. {10\( \bar 1 \)2} extension twinning was observed in large grains after an earlier rolling pass, but it disappeared upon a subsequent rolling pass due to the reorientation of the grains in an unfavorable direction caused by repetitive rolling. The finer grains were newly formed at the boundaries of the original large grains and twin boundaries by dynamic recrystallization. The grain size distribution was changed from a bimodal distribution upon a small total reduction to a homogeneous distribution upon a large total reduction due to the formation of finer grains that continued at the grain boundaries of large grains by repetitive hot rolling. The size and distribution of the grains were affected not only by the reduction ratio per pass but also by the total reduction (number of rolling passes).

Mg–23.5 wt.%Ni–(5, 10 and 15 wt.%)La alloys were prepared by gravity casting and their hydrogen-storage properties were examined after pulverizing. The gravity cast Mg–23.5Ni–(5, 10 and 15)La alloys consist of α-Mg, Mg2Ni and Mg17La2 phases. The activated Mg–23.5Ni–10La alloy has the highest hydrogen-storage capacity of 4.96 wt.%H (from P–C–T curve) and the highest initial hydriding rate (hydrogen content 3.83 wt.%H at 10 min) with an initial hydrogen pressure in the channel of 11 bar H2 at 573 K. This is attributed to its containing the largest amount of the Mg17La2 phase, which is easily dissociable during the hydriding reaction.

ZrCl4 was added into Mg-0.3Al model alloy in order to reduce the Al content in the castings below 0.005 mass%. Amount of ZrCl4 was determined by thermodynamic calculation. Various Al-Zr intermetallic compounds were formed in the melt at 1013 K. Large intermetallic compounds would be floated to melt surface by Ar bubbling and then removed by skimming before pouring. Smaller ones remained after Ar bubbling and isothermal holding would be partially removed by filter inserted into a mold during pouring. The Al content in the castings was higher than that predicted by thermodynamic calculation due to incomplete removal of Al-Zr intermetallic compounds from the melt. [doi:10.2320/matertrans.MRP2008246]