Effect of mischmetal substitution on the glass-forming ability of Mg–Ni–La bulk metallic glasses

The effect of La substitution by LaMM (lanthanum mischmetal) on the glass-forming ability of a Mg–Ni–La metallic glass has been studied. For compositions close to the eutectic Mg₆₉Ni₁₈La₁₃, the LaMM substitution improved the glass-forming ability, for instance up to a critical amorphous diameter of 2 mm for the Mg₆₅Ni₂₀LaMM₁₅ alloy. However, of all the alloys studied, it has been observed that La-containing alloys have higher GFA for compositions further from the eutectic and a maximum critical amorphous diameter of 2.5 mm was obtained for the Mg₆₀Ni_23.6La_16.4 alloy.     

The effects of lanthanum on microstructure and electrochemical properties of Al–Zn–In based sacrificial anode alloys

In order to improve the non-uniform corrosion of Al–0.5Zn–0.03In–1Mg–0.05Ti alloys, Al–5Zn–0.03In–1Mg–0.05Ti–xLa (x = 0.3, 0.5 and 0.7 wt.%) alloys were developed. Microstructures and electrochemical properties of the alloys were investigated. The results show that the optimal microstructures and electrochemical properties are obtained in Al–5Zn–0.03In–1Mg–0.05Ti–0.5La alloy. The main precipitate phase is Al₂LaZn₂ particles. The excellent electrochemical properties of Al–5Zn–0.03In–1Mg–0.05Ti–0.5La alloy is mainly attributed to fine grains and grain boundaries containing fine Al₂LaZn₂ precipitates. At the same time the fine grains can improve the non-uniform corrosion of Al–0.5Zn–0.03In–1Mg–0.05Ti alloy.     

Thermodynamic and kinetic studies of Mg–Fe–H after mechanical milling followed by sintering

The transition metal complex hydride Mg₂FeH₆ has been successfully synthesized utilizing mechanical milling of a 2Mg–Fe mixture followed by heating at 673 K under 6 MPa of hydrogen pressure, without pressing step. The obtained yield of Mg₂FeH₆ was about 50%. Hydrogen storage properties of the Mg–Fe–H system, i.e. capacities, absorption/desorption kinetics and thermodynamic parameters, were examined. The pressure-composition isotherm (PCI) measurements of the samples at 548–673 K showed that the alloys possessed good cyclic stability and reversibility. Enthalpies and entropies of decomposition of the Mg–Fe–H system were evaluated by van’t Hoff plots. The absorption/desorption rates at 573 K were very fast in comparison with the reported data. The non-isothermal desorption of hydrogen was found greatly dependent on the thermal history of the sample.     

Investigation on the structures and electrochemical performances of La0.75−xZrxMg0.25Ni3.2Co0.2Al0.1 (x = 0–0.2) electrode alloys prepared by melt spinning

In order to improve the electrochemical cycle stability of the La–Mg–Ni system A₂B₇-type electrode alloys, La in the alloy was partially substituted by Zr and the melt-spinning technology was used for preparing La_0.75−xZr_xMg_0.25Ni_3.2Co_0.2Al_0.1 (x = 0, 0.05, 0.1, 0.15, 0.2) electrode alloys. The microstructures and electrochemical performances of the as-cast and quenched alloys were investigated in detail. The results obtained by XRD, SEM and TEM showed that the as-cast and quenched alloys have a multiphase structure which is composed of two main phases (La, Mg)Ni₃ and LaNi₅ as well as a residual phase LaNi₂. The substitution of Zr for La leads to an obvious increase of the LaNi₅ phase in the alloys, and it also helps the formation of a like amorphous structure in the as-quenched alloy. The results of the electrochemical measurement indicated that the substitution of Zr for La obviously decreased the discharge capacity of the as-cast and quenched alloys, but it significantly improved their cycle stability. The discharge capacity of the alloys (x ≤ 0.1) first increased and then decreased with the variety of the quenching rate. The cycle stability of the alloys monotonously rose with increasing quenching rate.     

Influences of the substitution of Fe for Ni on structures and electrochemical performances of the as-cast and quenched La0.7Mg0.3Co0.45Ni2.55−xFex (x = 0–0.4) electrode alloys

In order to improve the cycle stability of the La–Mg–Ni system PuNi₃-type hydrogen storage electrode alloys, Ni in the alloy was partially substituted by Fe. The La_0.7Mg_0.3Co_0.45Ni_2.55−xFe_x (x = 0, 0.1, 0.2, 0.3, 0.4) hydrogen storage alloys were prepared by casting and rapid quenching. The effects of the substitution of Fe for Ni on the structures and electrochemical performances of the as-cast and quenched alloys were investigated in detail. The results of the electrochemical measurement indicate that the substitution of Fe for Ni obviously decreases the discharge capacity, high rate discharge capability (HRD) and discharge potential of the as-cast and quenched alloys, but it significantly improves their cycle stabilities, and its positive impact on the cycle life of as-quenched alloy is much more significant than on that of the as-cast one. The microstructure of the alloys analyzed by XRD, SEM and TEM show that the as-cast and quenched alloys have a multiphase structure which is composed of two major phases (La, Mg)Ni₃ and LaNi₅ as well as a residual phase LaNi₂. The substitution of Fe for Ni helps the formation of a like amorphous structure in the as-quenched alloy. With the increase of Fe content, the grain sizes of the as-quenched alloys significantly reduce, and the lattice constants and cell volumes of the alloys obviously increase.     

Fabrication and characterization of monolithic nanoporous copper through chemical dealloying of Mg–Cu alloys

A new Mg–Cu system has been developed to fabricate monolithic nanoporous copper (NPC) ribbons and bulk NPC through chemical dealloying in a 5 wt.% HCl solution. The microstructures of the NPC ribbons were characterized using X-ray diffraction, scanning electron microscopy and energy dispersive X-ray analysis. The results show that the compositions of the melt-spun Mg–Cu alloys have an important effect on the dealloying process and microstructures of the NPC ribbons. Moreover, the synergetic dealloying of Mg₂Cu and MgCu₂ in two-phase Mg–Cu alloys results in the formation of NPC with a uniform porous structure.     

The third-element effect in the oxidation of Ni–xCr–7Al (x = 0, 5, 10, 15 at.%) alloys in 1 atm O2 at 900–1000 °C

The oxidation in 1 atm of pure oxygen of Ni–Cr–Al alloys with a constant aluminum content of 7 at.% and containing 5, 10 and 15 at.% Cr was studied at 900 and 1000 °C and compared to the behavior of the corresponding binary Ni–Al alloy (Ni–7Al). A dense external scale of NiO overlying a zone of internal oxide precipitates formed on Ni–7Al and Ni–5Cr–7Al at both temperatures. Conversely, an external Al₂O₃ layer formed on Ni–10Cr–7Al at both temperatures and on Ni–15Cr–7Al at 900 °C, while the scales grown initially on Ni–15Cr–7Al at 1000 °C were more complex, but eventually developed an innermost protective alumina layer. Thus, the addition of sufficient chromium levels to Ni–7Al produced a classical third-element effect, inducing the transition between internal and external oxidation of aluminum. This effect is interpreted on the basis of an extension to ternary alloys of a criterion first proposed by Wagner for the transition between internal and external oxidation of the most reactive component in binary alloys.     

Early oxidation behaviors of Mg–Y alloys at high temperatures

The early oxidation behaviors of Mg–Y alloys (Y = 0.82, 1.09, 4.31 and 25.00 wt.%) oxidized in pure O₂ have been investigated at high temperatures. The results showed that the oxidation behaviors of the Mg–Y alloys (Y = 4.31 and 25.00 wt.%) obeyed a parabolic law, while that of the Mg–Y (Y = 0.82 and 1.09 wt.%) exhibited both parabolic and linear kinetics depending on the oxidation temperature. Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and X-ray diffraction (XRD) analyses indicated that an oxide film with a single structure composed of MgO and Y₂O₃ had formed. Moreover, the higher the oxidation temperature was, the thicker the oxide film was. Finally, the corresponding oxidation mechanism has been discussed, and the improved oxidation resistance of the Mg–Y alloys can be due to the formation of a continuous Mg-dissolving Y₂O₃ protective film.     

The precipitation process in Mg–Ca–(Zn) alloys investigated by positron annihilation spectroscopy

Coincidence doppler broadening (CDB) spectroscopy has been applied to study the precipitation process induced by aging in Mg–1.0 wt.% Ca and Mg–1.0 wt.% Ca–1.0 wt.% Zn alloys. In addition positron lifetime experiments and microhardness measurements have been performed. A peak centered at 11.5 × 10⁻³m₀c is found in the CDB ratio spectra of the alloys aged at 473 K. It is attributed to annihilations with the core electrons of Ca. The results indicate the formation of a particle dispersion that hardens the alloys. This dispersion is correlated with the appearance of the peak attributed to Ca atoms. Zn atoms in the Mg matrix inhibit the formation of quenched-in vacancies bound to Ca atoms in the aged ternary alloy producing the dispersion refinement.     

Synthesis of FCC Mg–Ta hydrides using GPa hydrogen pressure method and their hydrogen-desorption properties

Magnesium–tantalum ternary hydrides with an FCC structure were prepared by an ultra high-pressure technique. The FCC Mg–Ta hydride phases with the Ca₇Ge-type super-lattice structure were formed at 4 and 8 GPa. Another new phase, Mg₃TaH_y, was also verified by XRD and SEM in the specimen prepared at 8 GPa. From the temperature-programmed desorption (TPD) measurements with a heating rate of 10 K/min under vacuum, the FCC hydride exhibited hydrogen desorption of ca. 3.1 mass% at an onset temperature of 583 K. When the FCC hydride phase coexisted with Mg₃TaH_y, simultaneous decomposition occurred and the hydrogen-desorption temperature was lowered to 543 K. The hydrogen-desorption temperatures of the Mg–Ta FCC hydrides were 130–170 K lower than that of MgH₂.     

Microstructural evolution behavior of Mg–5Si–1Al alloy modified with Sr–Sb during isothermal heat treatment

The microstructural evolution behavior of Mg–5Si–1Al alloys modified with Sr–Sb during isothermal heat treatment was investigated in the present study. Although the morphology of eutectic Mg₂Si phase varied with isothermal holding temperature increasing from 620 to 670 °C, no spheridization occurred for primary Mg₂Si polyhedrons in Sr–Sb-modified alloy even when the temperature reaches 660 or 670 °C. Such an abnormal phenomenon of primary Mg₂Si, during partial remelting isothermal treatment, might be ascribed to both the spheridization restriction effect caused by incorporation of Sb in Mg₂Si and stability of octahedral primary Mg₂Si crystals faced by {1 1 1} planes.     

New dielectric material system of La(Mg1/2Ti1/2)O3–Ca0.6La0.8/3TiO3 for microwave applications

The microstructure and microwave dielectric properties of xLa(Mg_1/2Ti_1/2)O₃–(1 − x)Ca_0.6La_0.8/3TiO₃ ceramics system with ZnO additions (0.5 wt.%) investigated by the conventional solid-state route have been studied. Doping with ZnO (0.5 wt.%) can effectively promote the densification and the dielectric properties of xLa(Mg_1/2Ti_1/2)O₃–(1 − x)Ca_0.6La_0.8/3TiO₃ ceramics. 0.6La(Mg_1/2Ti_1/2)O₃–0.4Ca_0.6La_0.8/3TiO₃ ceramics with 0.5 wt.% ZnO addition possess a dielectric constant (_r) of 43.6, a Q × f value of 48,000 (at 8 GHz) and a temperature coefficient of resonant frequency (τ_f) of −1 ppm/°C sintering at 1475 °C. As the content of La(Mg_1/2Ti_1/2)O₃ increases, the highest Q × f value of 62,900 (GHz) for x = 0.8 is achieved at the sintering temperature 1475 °C. A parallel-coupled line band-pass filter is designed and simulated using the proposed dielectric to study its performance.     

Amorphous and nanocrystalline sputtered Mg–Cu thin films

Binary Mg–Cu amorphous alloys were first fabricated in 1980s via liquid quenching. In this study, the Mg_1−xCu_x (x varying from 38 at.% to 82 at.%) partially amorphous thin films are prepared via co-sputtering. Upon thermal annealing, the Mg₂Cu or MgCu₂ nanocrystalline phases are induced in the Mg-rich or Cu-rich thin films, respectively. Due to the presence of fine nanocrystalline Mg₂Cu or MgCu₂ particles in the Mg–Cu amorphous matrix, the as-sputtered thin films show satisfactory Young's modulus 100 GPa and hardness 4 GPa.     

The microstructures and mechanical properties of cast Mg–Zn–Al–RE alloys

The microstructures and mechanical properties of cast Mg–Zn–Al–RE alloys with 4 wt.% RE and variable Zn and Al contents were investigated. The results show that the alloys mainly consist of α-Mg, Al₂REZn₂, Al₄RE and τ-Mg₃₂(Al,Zn)₄₉ phases, and a little amount of the β-Mg₁₇Al₁₂ phase will also be formed with certain Zn and Al contents. When increasing the Zn or Al content, the distribution of the Al₂REZn₂ and Al₄RE phases will be changed from cluster to dispersed, and the content of τ-Mg₃₂(Al,Zn)₄₉ phase increased gradually. The distribution of the Al₂REZn₂ and Al₄RE phases, and the content of β- or τ-phase are critical to the mechanical properties of Mg–Zn–Al–RE alloys. The Mg–6Zn–5Al–4RE alloy with cluster Al₂REZn₂ phase and low content of β-phase, exhibits the optimal mechanical properties, and the ultimate tensile strength, yield strength and elongation are 242 MPa, 140 MPa and 6.4% at room temperature, respectively.     

Microstructure and martensitic transformation of Ni–Fe–Ga–Si ferromagnetic shape memory alloys

The effects of the fourth element Si on the martensitic transformation and magnetic properties of Ni–Fe–Ga magnetic shape memory alloys were investigated. A complete thermoelastic martensitic transformation in Ni–Fe–Ga–Si alloys was observed in the temperature range of 218–285 K. The martensitic transformation temperatures of Ni–Fe–Ga alloys are obviously decreased by the substitution of Si for Ga element, that is, the substitution of 1 at.% Si for Ga leads to a decrease of martensitic transformation temperature of about 39.6 K. Moreover, the substitution of Si for Ga leads to a decrease of the saturation magnetic field and the magnetic anisotropy constant K₁ obviously.     

Phase equilibria on the ternary Mg–Mn–Ce system at the Mg-rich corner

Three isopleths at the Mg-rich corner of Mg–Mn–Ce ternary system were investigated via thermal analysis, SEM/EPMA and XRD. A ternary eutectic reaction was observed at 1 wt.% Mn and 23 wt.% Ce and 592 °C. A solid-solution type ternary intermetallic compound, (Mg,Mn)₁₂Ce, was observed with 0.5 at% solid solubility of Mn in the tetragonal Mg₁₂Ce. With the aid of thermodynamic modeling and experiments, a revised phase diagram for the binary Mg–Ce system and the isopleths of 0.6, 1.8 and 2.5 wt.% Mn were proposed up to 25 wt.% Ce.     

Synthesis of FCC Mg–Zr and Mg–Hf hydrides using GPa hydrogen pressure method and their hydrogen-desorption properties

Magnesium-based hydrides with Zr or Hf have been synthesized by means of an ultra-high pressure technique. Powder mixtures of MgH₂ and ZrH₂ or HfH₂ have been heated up to 873 K under 4–8 GPa in a multi-anvil cell. New ternary phases (Mg–Zr–H and Mg–Hf–H) with a face centered cubic (FCC) structure have been formed. In the Mg–Zr hydride, the FCC phase with disordered metal–atom occupancy was observed, while a Ca₇Ge-type super-lattice structure was observed in the Mg–Hf hydride. By the temperature programmed desorption (TPD) measurements, these new hydrides exhibit the hydrogen-desorption at around 543–583 K, which were 130–70 K lower than that of MgH₂ at a heating rate of 10 K/min under vacuum. Desorbed hydrogen contents were estimated to be 4.2 and 3.0 mass% for Mg–Zr and Mg–Hf hydrides, respectively.     

Effect of manganese on the microstructure of Mg–3Al alloy

The effect of manganese on the microstructure of Mg–3Al alloy, especially the nucleation efficiency of Al–Mn particles on primary Mg, has been investigated in this paper. Mg–0.72Mn was used to fabricate Mg–3Al–xMn (x = 0, 0.1, 0.2, 0.3, 0.4 and 0.5) alloys, and the grain sizes of these alloys fluctuate at 390 μm indicating addition of manganese does not evidently influence the grain size of Mg–3Al alloy. Through XRD, FESEM and TEM detection, it is found that Al_0.89Mn_1.11 compound is the dominant Al–Mn phase in Mg–3Al–0.3Mn, Mg–3Al–0.4Mn and Mg–3Al–0.5Mn, and distributes in primary Mg matrix and interdendritic regions with an angular blocky morphology. The number of Al_0.89Mn_1.11 increases gradually with increasing manganese content while the grain sizes of primary Mg are nearly the same in Mg–3Al, Mg–3Al–0.3Mn, Mg–3Al–0.4Mn and Mg–3Al–0.5Mn, indicating Al_0.89Mn_1.11 has low nucleation efficiency on primary Mg.     

Improvement of the hydrogen-storage kinetics of Mg by reactive mechanical grinding with 10 wt.% Fe2O3 and 5 wt.% Ni

The addition of Fe₂O₃ to Mg is believed to be able to increase the hydriding rate of Mg, and the addition of Ni is thought to be able to increase the hydriding and dehydriding rates of Mg. A sample Mg-(10wt.%Fe₂O₃, 5 wt.%Ni) was prepared by mechanical grinding under H₂ (reactive mechanical grinding). The as-milled sample absorbed 4.61 wt.% of hydrogen at 593 K under 12 bar H₂ for 60 min. Its activation was accomplished after two hydriding-dehydriding cycles. The activated sample absorbed 4.59 wt.% of hydrogen at 593 K under 12 bar H₂ for 60 min, and desorbed 3.83 wt.% hydrogen at 593 K under 1.0 bar H₂ for 60 min. The activated Mg-(10wt.%Fe₂O₃, 5 wt.%Ni) had a slightly higher hydriding rate at the beginning of the hydriding reaction but a much higher dehydriding rate compared with the activated Mg-10 wt.%Fe₂O₃. prepared via spray conversion. After hydriding-dehydriding cycling, Fe₂O₃ was reduced, Mg₂Ni was formed by the reaction of Mg with Ni, and a small fraction of Mg was oxidized.     

Thermal stability and primary phase of Al–Ni(Cu)–La amorphous alloys

Thermal stability and primary phase of Al_85+xNi_9−xLa₆ (x = 0–6) and Al₈₅Ni_9−xCu_xLa₆ (x = 0–9) amorphous alloys were investigated by X-ray diffraction and differential scanning calorimeter. It is revealed that replacing Ni in the Al₈₅Ni₉La₆ alloy by Cu decreases the thermal stability and makes the primary phase change from intermetallic compounds to single fcc-Al as the Cu content reaches and exceeds 4 at.%. When the Ni and La contents are fixed, replacing Al by Cu increases the thermal stability but also promotes the precipitation of single fcc-Al as the primary phase.