Rare Earth Alloys Research Articles

Numerical simulation on metallurgical transport phenomena during DC casting of large-size Mg-Gd-Y alloy billet under various magnetic fields

The manufacture of large-size rare-earth Magnesium alloy billets by direct-chill (DC) casting process is now facing great technical challenges, mainly due to the high cost of casting experiments, and such casting defects like severe cracking, macrosegregation, and non-homogenized solidified structure. Based on the low-cost and high-efficiency numerical simulation method, the present study systematically explores the effects of single pulsed and alternating magnetic fields (PMF and AMF), differential-phase pulsed and alternating magnetic fields (DPMF and DAMF) on DC casting metallurgical transport phenomena of Φ750mm large-size Mg-Gd-Y magnesium alloy billet. The electromagnetic characteristics, flow behavior, and temperature distribution during casting process are clearly visualized. The results demonstrate that traditional DC casting process is optimized by applying magnetic fields. For one thing, pulsed magnetic fields (PMF and DPMF) generate larger and faster changing instantaneous Lorentz forces, which induce huge transient impact and oscillation effects on the melt. For another, alternating magnetic fields (AMF and DAMF) have greater time-average Lorentz forces, which can force the melt to flow continuously and steadily. Additionally, differential-phase magnetic fields (DPMF and DAMF) enhance the melt’s axial flow strength while reducing the small vortex generated at the edges, resulting in improved heat transfer efficiency and uniform temperature field. Among those magnetic fields, DPMF shows dual advantages of transient oscillation and homogenized temperature distribution. Based on the present simulated research, the Φ750mm large-sized rare earth Mg-Gd-Y alloy billet with high-quality and non-cracking has been manufactured during DC casting process under DPMF.

Study on the hydrogen absorption properties of a YGdTbDyHo rare-earth high-entropy alloy

Study on the hydrogen absorption properties of a YGdTbDyHo rare-earth high-entropy alloy

Research on the Hierarchical Separation of Rare Earths and Lithium from Rare Earth Molten Salt Slag

Lithium is an important non-renewable resource, and the study of the tiered separation of rare earths and lithium from rare earth molten salt slag is an important approach to solving the current global resource shortage. This article adopts a sulfuric acid leaching process and a lithium-containing solution iron lithium extraction separation process to recover lithium from rare earth molten salt slag. The method systematically investigates the impact of sulfuric acid concentration, liquid-to-solid ratio, leaching temperature, leaching time, pH, P507 concentration, phase ratio, extraction temperature, and extraction time on the lithium extraction effect and iron lithium separation effect in rare earth molten salt slag. The results show that under the conditions of a sulfuric acid concentration of 0.9 mol/L, a liquid-to-solid ratio of 8:1 mL/g, a leaching temperature of 70 °C, a leaching time of 90 min, a pH of 0.9, a P507 concentration of 50%, a phase ratio of 5:3, an extraction temperature of 30 °C, and an extraction time of 20 min, the lithium leaching rate reaches 97.8%, and the separation of iron and lithium is fully achieved. This method can efficiently recover the valuable element lithium from rare earth molten salt slag, which is of great significance for the subsequent preparation of lithium products and the realization of a closed-loop production of rare earth alloys by molten salt electrolysis.

Superplastic deformation mechanisms of coarse-grained rolled Mg-4Y-3RE magnesium alloy

The Mg-4Y-3RE (WE43) magnesium alloy possesses significant advantages such as high specific strength, excellent shock absorption, strong electromagnetic shielding capabilities and recyclability. However, its close-packed hexagonal structure leads to poor plasticity at room temperature, which limits its broader engineering applications. Therefore, superplastic forming at high temperatures is used to manufacture the components from this alloy. This study conducted tensile tests on hot-rolled WE43 rare-earth magnesium alloy with coarse grains at various temperatures and strain rates. The high-temperature superplastic properties were characterized, revealing the intrinsic mechanisms of thermal deformation behavior. The results indicate that the best superplasticity is achieved at 460 °C. This is attributed to the smallest grain size, the weakest texture, and the relatively uniform distribution of the second phase at this temperature. The influence of strain rate on elongation at temperatures among 440 °C∼500 °C is not significant as the impact of strain rate is multifaceted. Meanwhile, the elongation can reach up to 367.7 ± 3.7 % at a strain rate of 0.0 1s−1, which exhibits the high strain rate superplasticity (HSRS). Under these conditions, the deformation of coarse-grained WE43 rare-earth magnesium alloy is controlled by grain boundary sliding (GBS) and solute drag dislocation creep. Furthermore, the GBS involves deformation coordination mechanisms such as grain boundary diffusion, lattice diffusion, dislocation climbing, and dynamic recrystallization accommodation mechanisms.

Topological signatures of triply degenerate fermions in Heusler alloys: an ab initio study

Triply degenerate nodal point (TP) fermions, lacking elementary particle counterparts, have been theoretically anticipated as quasiparticle excitations near specific band crossing points constrained by distinct space-group symmetries instead of Lorentz invariance. Here, based onfirst-principlescalculations and symmetry analysis, we demonstrate the presence of TP fermions in Heusler alloys. Furthermore, we predict that these Heusler alloys are dynamically stable, exhibiting TP fermions along four distinctC3axes in the F-43m space group. We show thatα-LiCaPdSb harbours peculiar Fermi arcs and surface states on the (111) and (001) crystal facets, owing to the coexistence of threefold rotational and time reversal symmetry. More interestingly, a modest tensile strain can increase the distance of fermions along the Γ-Lhigh symmetric line by as much as 21.10%, which give rise to measurable Fermi arcs. Furthermore, we investigate non-trivial topological insulator phase inβ-LiCaPdSb, by changing the chemical environment through placing transition metal atoms at various Wyckoff positions. Theβ-LiCaPdSb harbour a semi-metallic nature, and by breaking cubic symmetry, it undergoes a transition from semi-metal to a non-trivial topological insulator. In addition, for the first time, rare-earth LaPtBi half-Heusler alloy is examined under strain to uncover multiple band inversions associated with the TP fermionic phase. The observed multiple band inversion is entirely unaffected by spin-orbit coupling. We show that the LaPtBi compound hosts TP fermions, which are linked to aZ2topological invariant. Remarkably, with clear band crossings and multiple band inversion, we point out the possibilities of the LaPtBi for displaying a rich topological phase diagram. Our work provides a prototype material platform for experimental detection through angle-resolved photoemission spectroscopy or scanning tunnelling spectroscopy and practical spintronic applications.

Quasi-isothermal magnetocaloric effect in the DyAl2 alloy in magnetic field up to 14 T

Experimental and analytical studies were carried out on the magnetocaloric effect (MCE) in the rare-earth alloy of the Laves phase DyAl2, which has the second-order magnetic phase transition (PT) in the region of cryogenic temperatures. The measurements are carried out using an extraction magnetic calorimeter with a Bitter electromagnet. A polycrystalline DyAl2 sample was synthesized followed by heat treatment. X-ray diffraction and elemental chemical analyzes are provided. The magnetization of the sample was measured in magnetic fields up to 13.5T. Calculations of the entropy changes of the magnetic subsystem ΔSmag are provided. Measurements of the MCEs ΔT − effect in adiabatic and ΔQ − effect in quasi-isothermal conditions were carried out. The MCE investigated by direct method in the temperature range of 15–110 K and magnetic field up to 14 T. It was found that the maximum of the adiabatic MCE in the region of the Curie temperature of the DyAl2 alloy under adiabatic magnetization in a magnetic field of 14T is ΔT = 12.94K. The obtained values are well approximated by the ΔT∼ΔH2/3, The maximum value of the quasi-isothermal MCE is ΔQ = 3.1kJ/kg. The value corresponds to the maximum of the entropy change of the magnetic subsystem ΔSmag = 32.3J/(kg*K). The influence of thermal contact resistance (TCR) on the results of measuring the MCE under quasi-isothermal conditions is assessed.

Corrosion and wear mechanisms of rare earth (Gd, Sc, Y)-doped Zr-based amorphous alloys

Rare-earth elements have been utilized in the design and development of new amorphous alloys to improve the corrosion and wear resistance of Zr-based amorphous alloys. In this study, a rare-earth doped Zr-based amorphous alloy (Zr-BMG(RE)) was prepared by the copper mold casting method, which was investigated by corrosion and wear experiments. The results show that Zr-BMG(RE) has a completely amorphous structure, and the doping of rare earths Gd and Y raises the crystallization transition temperature of the amorphous. The addition of rare earth elements Gd and Sc increases the microhardness of Zr-based amorphous alloys, while rare earth element Y causes a slight decrease in microhardness. Gd and Sc will make Zr-based amorphous materials corrosion current density increases, the material pitting and localized corrosion, acid corrosion resistance is reduced. Y doping improves the self-corrosion potential of Zr-based amorphous alloys, reduces the corrosion current density, the surface passivation film is the densest, and the degree of charge transfer on the metal surface is the most difficult, Zr-BMG(Y) has a better corrosion resistance compared with other alloy materials. Zr-BMG(Gd) has the smallest friction rate (1.72 × 10−7mm3N−1mm−1), and the wear rates of the rare earth doped Zr-based amorphous alloys are all smaller than that of Zr-BMG, and the main loss mechanism of Zr-based amorphous alloys is the interaction of adhesive wear, abrasive wear, oxidative wear and fatigue wear. The mechanism of corrosion and wear resistance of rare earth to Zr-based amorphous alloys is discussed, which provides a new idea for the design of amorphous alloys.

Prediction of Mechanical Properties of Rare-Earth Magnesium Alloys Based on Convolutional Neural Networks.

Rare-earth magnesium alloys exhibit higher comprehensive mechanical properties compared to other series of magnesium alloys, effectively expanding their applications in aerospace, weapons, and other fields. In this work, the tensile strength, yield strength, and elongation of a Mg-Gd-Y-Zn-Zr rare-earth magnesium alloy under different process conditions were determined, and a large number of microstructure observations and analyses were carried out for the tensile specimens; a prediction model of the corresponding mechanical properties was established by using a convolutional neural network (CNN), in which the metallographic diagram of the rare-earth magnesium alloy was taken as the input, and the corresponding tensile strength, yield strength, elongation, and three mechanical properties were taken as the output. The stochastic gradient descent (SGD) algorithm was used for parameter optimization and experimental validation, and the results showed that the average relative errors of the tensile strength and yield strength prediction results were 1.90% and 3.14%, respectively, which were smaller than the expected error of 5%.

The Inclusion Characteristics and Mechanical Properties of M2 High-Speed Steel Treated with a Vacuum Carbon Deoxidation Process

The oxygen content of M2 high-speed steel has not been intentionally controlled in industrial production through secondary refinement in vacuum furnaces. However, a lower oxygen content has a significant effect on the cleanliness, toughness, and addition of rare-earth elements to M2 high-speed steel. The changes in total oxygen content controlled by vacuum carbon deoxidation (VCD) treatment and inclusion evolution were investigated in M2 high-speed steel to understand the effects of carbon on dissolved oxygen and oxides in the carbon–oxygen (C-O) reaction process. Furthermore, the microstructure and properties of M2 high-speed steel caused by vacuum insulation and the role of reducing oxygen content in rare-earth alloying were briefly demonstrated. The results showed that the [O%] decreased from 30 ppm to 3 ppm in a vacuum at holding times above 25 min through the C-O reaction, leading to an inclusion reduction of approximately 70%. In the case of [O%] = 3 ppm in M2 high-speed steel, the addition of rare-earth elements has a greater effect on the inclusion characteristics. Lowering the oxygen content of M2 high-speed steel improves cleanliness and plays a significant role in rare-earth alloying.

An investigation on tool performances in milling rare-earth magnesium alloys

An investigation on tool performances in milling rare-earth magnesium alloys

Fieldlike torque driven switching in rare-earth transition-metal alloys

Fieldlike torque driven switching in rare-earth transition-metal alloys

A novel shell-like structure Zn-5Mn alloy with high strength and high plasticity for degradable oil fracturing tools

Fracturing tools for oil and gas exploitation require high mechanical properties and degradability. Zn alloys are possible to have good mechanical properties and much lower cost than widely used rare-earth Mg alloys, so it is worthy to develop Zn alloys as alternative materials. In this paper, a novel shell-like microstructure of Zn-5Mn alloy has been realized by bottom circulating water cooling. MnZn9 phase appears by the first time in Zn-Mn alloys with Mn < 6.4 wt%. This phase leads to the formation of hard MnZn9/MnZn13 core/shell structure with a high volume fraction of 76 %, dispersed uniformly in soft Zn phase. The alloy has excellent compressive properties without fracture even when stress and strain reach 2776 MPa and 80 %, respectively. Its ultimate uniform compressive stress and strain are 865 MPa and 56 % respectively, beyond widely used dissoluble Mg alloys. Weight loss rate of the Zn-5Mn alloy is two times that of pure Zn, immersed in 3 wt% KCl solution at 93°C. The shell-like Zn-5Mn alloy provides guiding significance of applying Zn alloys in fracturing tools for oil and gas exploitation.

Highly Efficient and Precise Rare-Earth Elements Separation and Recycling Process in Molten Salt

Owing to the worldwide trend towards carbon neutrality, the number of Dy-containing heat-resistant Nd magnets used for wind power generation and electric vehicles is expected to increase exponentially. However, rare earth (RE) elements (especially Dy) are unevenly distributed globally. Therefore, an environmental-friendly recycling method for RE elements with a highly precise separation of Dy and Nd from end-of-life magnets is required to realize a carbon-neutral society. As an alternative to traditional hydrometallurgical RE separation techniques with a high environmental load, we designed a novel, highly efficient, and precise process for the separation and recycling of RE elements from magnet scrap. As a result, over 90% of the RE elements were efficiently extracted from the magnets using MgCl2 and evaporation loss was selectively suppressed by adding CaF2. The extracted RE elements were electrolytically separated based on the formation potential differences of the RE alloys. Nd and Dy metals with purities greater than 90% were estimated to be recovered at rates of 96% and 91%, respectively. Almost all the RE in the scraps could be separated and recycled as RE metals, and the byproducts were easily removed. Thus, this process is expected to be used on an industrial scale to realize a carbon-neutral society.

Pulsed laser surface texturing enhancing corrosion resistance of rare-earth WE43 magnesium alloys in simulated body fluid environment

The addition of rare earth (RE) elements in Magnesium (Mg) alloys could optimize alloy microstructures and improve the mechanical property. The corrosion resistance however is a tough issue that limits its application as biomedical materials in human bodies. In this work, a green, fast and economical method of pulsed laser surface texturing (PLST) was employed to modify the RE WE43 Mg alloys and the corresponding corrosion resistance after the PLST treatment in simulated body fluid (SBF) was further examined. The microstructural results show that the surface exhibits petal-like microstructures and an oxide film composed of various oxides with remelting particles are also generated on laser-processed areas after PLST treatment. The electrochemical results reveal that the WE43 sample treated by PLST exhibits a superior corrosion resistance in SBF compared with the as-cast one. As for the PLST treated sample with 24 W, the corrosion potential (Ecorr) positively shifts from −1.788 V to −1.556 V after being immersed in SBF for 7 days, which is also nobler than that of the as-cast one, −1.915 V. While the corrosion current density (icorr) drops to the value of 8.3 μA/cm2, considerably lower than that of the as-cast sample, 1380 μA/cm2. The enhancement of corrosion resistance in the early stage is mainly due to the protective oxide film induced by PLST. Furthermore, long-term immersion in SBF further accelerates the formation of deposited hydroxyapatite (HA) products layer on petal-like microstructures, which would further contribute to its enhancement in corrosion resistance in the long-term service in human bodies.

Structural, morphological, and magnetic properties of carbon-modified nanocrystalline Pr5Co19 alloys

Nanocrystalline rare-earth (R) and transition metal (T) alloys are known for their outstanding magnetic properties, which are driven by the combination of (R) and (T) magnetic moments. Adding carbon (C) has been proven to alter these magnetic properties. In the present work, we use X-ray diffraction, transmission electron microscopy, and atom probe tomography to investigate and characterize the impact of carbon addition on the crystalline structure, morphology, and chemical distribution of Pr5Co19 and its carbides Pr5Co19Cx. The nanocrystalline Pr5Co19 compound was synthesized by high-energy ball milling and the addition of carbon was performed by a solid-solid reaction between Pr5Co19 and C10H14. TEM study revealed that after carbonation the microstructure is refined, and the mean grain size decreases from 126 nm in Pr5Co19 to 65 nm with a carbon of content 1.5. Three-dimensional APT was performed to characterize the chemical composition of Pr-Co binary systems. The analyzed Pr5Co19C1.5 sample reveals an irregular nano-lamella structure decorated by carbon atoms, the distance between the lamellas varying from 8 to 20 nm. An under-stoichiometry of Co was found in the C-rich lamellas. Fundamental magnetic properties such as saturation magnetization Ms, exchange field Hex and magnetic susceptibility χ of the Pr5Co19 and its carbides were calculated using the random magnetic anisotropy (RMA) method.

The role of zinc addition on the microstructural evolution and mechanical properties of wire-arc directed energy deposited Mg-Gd-Y-(Zn)-Zr alloys

Wire-arc directed energy deposition (WA-DED) demonstrates significant potential in the rapid and free forming of high-strength magnesium rare-earth (Mg-RE) alloys. This highlights a growing demand for tailored wire alloy compositions to promote engineering applications of this technology. In this work, the role of zinc addition on WA-DED processed Mg-Gd-Y based alloys has been thoroughly investigated by utilizing Mg-6Gd-3Y-0.5Zr (wt%, GW63K) and Mg-6Gd-3Y-0.5Zn-0.5Zr (wt%, GWZ631K) alloy wires as model materials. The microstructure evolution of these two alloys during deposition and heat treatment is revealed by multi-scale microstructure characterization techniques. The influences of Zn addition on mechanical properties of these deposited alloys are investigated comparatively. Obtained results indicate that addition of Zn element into Mg-Gd-Y based alloys promotes phase transformation between eutectic phases and long period stacking order (LPSO) phases during the WA-DED deposition process owing to the multiple thermal cycling. More importantly, the addition of Zn element increases the tendency of solidification shrinkage of the deposited metal. During high-temperature solid solution treatment, the presence of Zn is conducive to improving the thermal stability of the as-deposited grain boundaries and thus suppressing grain coarsening. After optimized T6 treatments, the strength of GW63K alloys increases to 374 ± 7 MPa, and is obviously higher than that (315 ± 6 MPa) of GWZ631K alloys. The addition of Zn element weakens the precipitation strengthening effect. This can be attributed to the formation of LPSO phases, which consumes a substantial amount of RE elements, and in turn decreases the density of aging precipitated nanoscale β´ phases. This work promotes the understanding of the non-equilibrium solidified microstructure evolution of multi-component Mg-RE alloys and guides the optimization of alloy composition of WA-DED specific wire materials.

Summary of the Research Progress on Advanced Engineering, Processes, and Process Parameters of Rare Earth Green Metallurgy.

The addition of rare earth metals to aluminum alloys can effectively improve their corrosion resistance and has been widely used in the aerospace and military industries. However, the current methods for the preparation of rare earth metals involve long processing steps, high energy consumption, and high carbon emissions, which severely constrains the development of aluminum alloys. Its output is further developed. To this end, this paper reviews mainstream rare earth production processes (precipitation methods, microemulsion methods, roasting-sulfuric acid leaching methods, electrochemical methods, solvent extraction methods, and ion exchange methods) to provide basic information for the green smelting of rare earth metals and help promote the development of green rare earth smelting. Based on the advantages and disadvantages of each process as well as recent research results, the optimal process parameters and production efficiency were summarized. Studies have concluded that the precipitation method is mostly used for the recovery of rare earth elements and related valuable metals from solid waste; the microemulsion method is mostly used for the preparation of nanosized rare earth alloys by doping; the roasting-sulfuric acid leaching method is mostly used for the treatment of raw rare earth ores; and the molten salt electrolysis method is a more specific method. This is a green and environmentally friendly production process. The results of this study can provide direction for the realization of green rare earth smelting and provide a reference for improving the existing rare earth smelting process.

Regulating the grain refinement and rolling properties of coarse-crystalline Mg-Zn-Gd-Ca-Mn alloy through multi-pass cold rolling and annealing

The newly developed Mg–Zn-RE (rare earth) alloy sheet shows significant prospects for 3C applications due to its superior room-temperature malleability compared to the commercial AZ31 alloy. However, the casting ingots of these alloys often exhibit coarse grains due to low alloying element content and the absence of the grain-refining element Zr, making them susceptible to significant cracking while hot-rolling. This study applies a multi-pass cold rolling technique with minimal reduction to a cast Mg–Zn-Gd-system alloy characterized by coarse grains, followed by a static annealing process to enhance its rolling capability. The impact of cold rolling and annealing temperatures on microstructure, plastic deformation mechanism, and static recrystallization (SRX) behavior were studied. It was found that multi-pass cold rolling with minimal decrease promoted the generation of more twins and slip lines, resulting in more uniform deformation and a substantial accumulated rolling strain of 10 %. Consequently, the significant accumulated strain, coupled with stress concentration at positions such as grain boundaries, twin boundaries, and dislocation tangles, acted as nucleation sites for complete static recrystallization at a specific annealing temperature of 375 °C. As a result, the coarse cast grains were successfully refined from 400 μm to 37 μm. Fortunately, this improvement has significantly enhanced the hot-rolling qualities, removing fractures throughout the process. This advancement not only enables industrial-scale rolling but also enhances production efficiency.

Mechanical properties, corrosion behavior, and in vitro and in vivo biocompatibility of hot-extruded Zn-5RE (RE = Y, Ho, and Er) alloys for biodegradable bone-fixation applications

Biodegradable Zn alloys have significant application potential for hard-tissue implantation devices owing to their suitable degradation behavior and favorable biocompatibility. Nonetheless, pure Zn and its alloys in the as-cast state are mechanically instable and low in strength, which restricts their clinical applicability. Here, we report the exceptional mechanical, corrosion, and biocompatibility properties of hot-extruded Zn-5RE (wt.%, RE = rare earth of Y; or Ho; or Er) alloys intended for use in biodegradable bone substitutes. The microstructural characteristics, mechanical behavior, corrosion resistance, cytocompatibility, osteogenic differentiation, and capacity of osteogenesis in vivo of the Zn-5RE alloys are comparatively investigated. The Zn-5Y alloy demonstrates the best tensile properties, encompassing a 138 MPa tensile yield strength, a 302 MPa ultimate tensile strength, and 63% elongation, while the Zn-5Ho alloy shows the highest compression yield strength of 260 MPa and Vickers hardness of 104 HV. The Zn-5Er alloy shows a 126 MPa tensile yield strength, a 279 MPa ultimate tensile strength, 52% elongation, a 196 MPa compression yield strength, and a 101 HV Vickers microhardness. Further, the Zn-5Er alloy has a 130 µm per year corrosion rate in electrochemical tests and a 26 µm per year degradation rate in immersion tests, which is the lowest among the tested alloys. It also has the best in vitro osteogenic differentiation ability and capacity for osteogenesis and osteointegration in vivo after implantation in rat femurs among the Zn-5RE alloys, indicating promising potential in load-bearing biodegradable internal bone-fixation applications. Statement of significanceThis work reports the exceptional mechanical, corrosion, and biocompatibility properties of hot-extruded (HE) Zn-5 wt.%–rare earth (Zn-5RE) alloys using single yttrium (Y), holmium (Ho), and erbium (Er) alloying for biodegradable bone-implant applications. Our findings demonstrate that the HE Zn-5Er alloy showed σuts of 279 MPa, tensile yield strength of 126 MPa, elongation of 51.6%, compression yield strength of 196 MPa, and microhardness of 101.2 HV. Further, HE Zn-5Er showed the lowest electrochemical corrosion rate of 130 µm/y and lowest degradation rate of 26 µm/y, and the highest in vitro osteogenic differentiation ability, in vivo osteogenesis, and osteointegration ability after implantation in rat femurs among the Zn-5RE alloys, indicating promising potential in load-bearing biodegradable internal bone-fixation applications.

Unveiling synergistic strength and plasticity enhancement of Mg–Zn–Mn alloy via closed forging extrusion

A cost-effective, high-performance Mg-2.0Zn-1.5Mn alloy was fabricated using closed forging extrusion (CFE). The results reveal that CFE can promote a dynamic recrystallization (DRX) ratio and enhance the residual dislocation density in deformed grains and subgrains. Grain refinement is achieved through multiple DRX mechanisms, particle-stimulated nucleation, and pinning effects. In addition, the basal texture and precipitation behavior are significantly influenced by pre-forging in CFE. Finally, grain refinement and substantial residual dislocations result in a good combination of strength and plasticity, with the ultimate tensile strength of 400 MPa and elongation of 22.1%, respectively. A novel strategy for regulating the bimodal grain structure is proposed to guide the optimization of the mechanical performance of rare-earth free Mg alloys.