Biomedical rare-earth magnesium alloy:Current status and future prospects

Biomedical magnesium(Mg)alloys have garnered significant attention because of their unique biodegradability,favorable biocompatibility,and suitable mechanical properties.The incorporation of rare earth(RE)elements,with their distinct physical and chemical properties,has greatly contributed to enhancing the mechanical performance,degradation behavior,and biological performance of biomedical Mg alloys.Currently,a series of RE-Mg alloys are being designed and investigated for orthopedic implants and cardiovascular stents,achieving substantial and encouraging research progress.In this work,a comprehensive summary of the state-of-the-art in biomedical RE-Mg alloys is provided.The physiological effects and design standards of RE elements in biomedical Mg alloys are discussed.Particularly,the degradation behavior and mechanical properties,including their underlying action are studied in-depth.Furthermore,the preparation techniques and current application status of RE-Mg alloys are reviewed.Finally,we address the ongoing challenges and propose future prospects to guide the development of high-performance biomedical Mg-RE alloys.

Development and characteristics of a low rare-earth containing magnesium alloy with high strength-ductility synergy

In this study,we successfully developed a low RE containing Mg-3Y-2Gd-1Nd-0.5Zr(wt%)alloy with high strength-ductility synergy by combined processes of hot extrusion,hot rolling and ageing.This alloy exhibits an excellent strength-ductility balance(UTS of 345±2.0 MPa,TYS of 301±5.0 MPa and EL of 9.2±1.9%),which is better than that of many Mg-RE wrought alloys with higher RE concentration and even comparable to that of 6061 Al wrought alloy.A long-range chain-like structure consisting ofβphase,βH phase,βM phase and zig-zag atomic columns is observed for the first time in the studied alloy.The combined process of hot extrusion and hot rolling boosts the formation of deformed grains and low angle grain boundaries,and makes the deformed grains dominate in the alloy strengthening.Under this circumstance,the following ageing generates a novel heterogeneous structure comprising the long-range chain-like structure with broad interparticle spacing and the spacious precipitate-free zones in the deformed grains,which plays a key role in the concurrent strengthening and toughening of the alloy.The present study demonstrates that the deformed grains with long-range chain-like structures and precipitate-free zones is desirable microstructure for the low RE containing Mg alloys to achieve high strength-ductility synergy.

Recent advances on grain refinement of magnesium rare-earth alloys during the whole casting processes:A review

High-performance cast magnesium rare-earth(Mg-RE) alloys are one of the most important materials among all developed Mg alloy families, and have shown great potential in military and weapons, aerospace and aviation, orthopedic implants, etc. Controlling grain size and distribution of it is key to the promising mechanical performance of Mg-RE alloy casting components. During the casting of a real component, nearly every procedure in the fabrication process will influence the grain refinement effect. The procedure may include and may not be limited to the chemical inoculations, possibly applied physical fields, the interfere between grain refiner and purifications, and the casting techniques with different processing parameters. This paper reviews the recent advances and proposed future developments in these categories on grain refinement of cast Mg-RE alloys. The review will provide insights for the future design of grain refinement techniques,the choosing of processing parameters, and coping strategies for the failure of coarsening for cast Mg-RE components with high quality and good performance.

Microstructure and mechanical properties of a cast heat-resistant rare-earth magnesium alloy

Microstructure,mechanical properties and phase transformation of a heat-resistant rare-earth(RE)Mg-16.1Gd-3.5Nd-0.38Zn-0.26Zr-0.15Y(wt.%)alloy were investigated.The as-cast alloy is composed of equiaxedα-Mg matrix,net-shaped Mg5RE and Zr-rich phases.According to aging hardening curves and tensile properties variation,the optimized condition of solution treatment at 520℃for 8 h and subsequent aging at 204℃for 12 h was selected.The continuous secondary Mg5RE phase predominantly formed at grain boundaries during solidification transforms to residual discontinuousβ-Mg5RE phase and fine cuboid REH2particles after heat treatment.The annealed alloy exhibits good comprehensive tensile property at 350℃,with ultimate tensile strength of 153 MPa and elongation to fracture of 6.9%.Segregation of RE elements and eventually RE-rich precipitation at grain boundaries are responsible for the high strength at elevated temperature.

Rare earth alloy nanomaterials in electrocatalysis

With the rapid development of society and economy, the excessive consumption of fossil energy has led to the global energy and environment crisis. In order to explore the sustainable development of new energy, research based on electrocatalysis has attracted extensive attention in the academic circle. The main challenge in this field is to develop nano-catalysts with excellent electrocatalytic activity and selectivity for target products. The state of the active site in catalyst plays a decisive role in the activity and selectivity of the reaction. In order to design efficient and excellent catalysts, it is an effective means to adjust the electronic structure of catalysts. Electronic effects are also called ligand effects. By alloying with rare earth(RE) elements, electrons can be redistributed between RE elements and transition metal elements, achieving accurate design of the electronic structure of the active site in the alloy. Because of the unique electronic structure of RE, it has been paid attention in the field of catalysis. The outermost shell structure of RE elements is basically the same as that of the lower shell, except that the number of electrons in the 4f orbital is different, but the energy level is similar, so their properties are very similar. When RE elements form compounds, both the f electrons in the outermost shell and the d electrons in the lower outer shell can participate in bonding. In addition, part of the 4f electrons in the third outer shell can also participate in bonding.In order to improve the performance of metal catalysts, alloying provides an effective method to design advanced functional materials. RE alloys can integrate the unique electronic structure and catalytic behavior of RE elements into metal materials, which not only provides an opportunity to adjust the electronic structure and catalytic activity of the active component, but also enhances the structural stability of the alloy and is expected to significantly improve the catalytic performance of the catalyst. From the perspective of electronic and catalytic activity, RE elements have unique electronic configuration and lanthanide shrinkage effect. Alloying with RE elements will make the alloy have more abundant electronic structure, activity, and spatial arrangement, effectively adjusting the reaction kinetics of the electrochemical process of the catalyst. In this paper, the composition,structure, synthesis of RE alloys and their applications in the field of electrocatalysis are summarized, including the hydrogen evolution reaction, the oxygen evolution reaction, the oxygen reduction reaction, the methanol oxidation reaction, the ethanol oxidation reaction, and other catalytic reactions. At the same time, the present challenges of RE alloy electrocatalytic materials are summarized and their future development direction is pointed out. In the field of electrocatalysis, the cost of catalyst is too high and the stability is not strong. Therefore, the testing process should be related to the actual application, and the test method should be standardized, so as to carry forward the field of electrocatalysis.

Impact of scandium and terbium on the mechanical properties,corrosion behavior,and biocompatibility of biodegradable Mg-Zn-Zr-Mn alloys

Magnesium(Mg)-based bone implants degrade rapidly in the physiological environment of the human body which affects their structural integrity and biocompatibility before adequate bone repair.Rare earth elements(REEs)have demonstrated their effectiveness in tailoring the corrosion and mechanical behavior of Mg alloys.This study methodically investigated the impacts of scandium(Sc)and terbium(Tb)in tailoring the corrosion resistance,mechanical properties,and biocompatibility of Mg–0.5Zn–0.35Zr–0.15Mn(MZZM)alloys fabricated via casting and hot extrusion.Results indicate that addition of Sc and Tb improved the strength of MZZM alloys via grain size reduction and solid solution strengthening mechanisms.The extruded MZZM–(1–2)Sc–(1–2)Tb(wt.%)alloys exhibit compressive strengths within the range of 336–405 MPa,surpassing the minimum required strength of 200 MPa for bone implants by a significant margin.Potentiodynamic polarization tests revealed low corrosion rates of as–cast MZZM(0.25 mm/y),MZZM–2Tb(0.45 mm/y),MZZM–1Sc–1Tb(0.18 mm/y),and MZZM–1Sc–2Tb(0.64 mm/y),and extruded MZZM(0.17 mm/y),MZZM–1Sc(0.15 mm/y),MZZM-2Sc(0.45 mm/y),MZZM-1Tb(0.17 mm/y),MZZM-2Tb(0.10 mm/y),MZZM–1Sc-1Tb(0.14 mm/y),MZZM-1Sc-2Tb(0.40 mm/y),and MZZM–2Sc–2Tb(0.51 mm/y)alloys,which were found lower compared to corrosion rate of high-purity Mg(~1.0 mm/y)reported in the literature.Furthermore,addition of Sc,or Tb,or Sc and Tb to MZZM alloys did not adversely affect the viability of SaOS2 cells,but enhanced their initial cell attachment,proliferation,and spreading shown via polygonal shapes and filipodia.This study emphasizes the benefits of incorporating Sc and Tb elements in MZZM alloys,as they effectively enhance corrosion resistance,mechanical properties,and biocompatibility simultaneously.

Mechanism of Effects of Rare Earths on Microstructure and Properties at Elevated Temperatures of AZ91 Magnesium Alloy

By using real-space recursion method,the energetics of the undoped and Al and/or RE atoms doped 7（1450）〈0001〉 symmetric tilt grain boundaries（GBs）in AZ91 alloys were investigated.Similar calculations were performed on undoped and doped bulk α Mg for comparison.The results showed that Al atoms segregated at GBs in AZ91 alloys.When RE atoms were added,they also segregated at GBs,and their segregation is stronger than Al atoms＇.Therefore,RE atoms retard the segregation of Al atoms.Calculations of interaction energy indicated that Al atoms repelled each other,and could form ordered phase with host Mg atoms.On the contrary to the case of Al,RE atoms attracted each other,they could not form ordered phase with Mg,but could form clusters.Between RE and Al,there existed attractive interaction,and this attractive interaction was the origin of Al11RE3 precipitation.Precipitation of Al11RE3 particles with high melting point and high thermal stability along GB improves high temperature properties of AZ91 alloys.

Influence of Rare Earth Elements on Microstructure and Mechanical Properties of Mg-Li Alloys

A series of a-based Mg-Li-A1-Zn-xRE alloys were prepared. These alloys have low density ranging from 1.5 to 1.7 g·cm^-3 and high strength properties. The influence of RE element on the microstructure and the mechanical properties of these alloys were studied. The results indicate that the addition of RE （La, Pr, Ce） leads to the formation of rodshaped intermetallic compound Al2Zn2La distributed in the matrix. Al2Zn2La induces reduction of the laminar spacing and causes refinement of the microstructure. Therefore, this compound improves the strength of alloys at a high temperature.

CuZnAl Shape Memory Alloy Refined with Composite Rare Earths La+Ce

The effects of composite rare earths La+Ce on properties of CuZnAl shape memory alloys were studied bymetallograph examination, tensile and bending tests, electric resistivity measurements, EDS and SEM. The test resultsshow that the grain size of CuZnAl shape memory alloys could be diminished effectively and the mechanical propertiesimproved obviously by the addition of composite rare earths La+Ce (La: Ce=1: 1). Meanwhile, the excellent shapememory properties remained unchanged. The results of microanalyses indicate that the composite rare earths were segregated at grain boundaries and impeded the grain growth, leading to the improvement of the mechanical properties ofCuZnAl alloys. If the amount of composite rare earths La+Ce was greater than 0. 10%, the shape memorial propertiesbecame poor.

Preparation and Performance of Rare Earths Chemical Conversion Film on Magnesium Alloy

Golden yellow cerium conversion film was obtained on magnesium alloys surface by immersion method and the preparation parameters were established. The influence of different process parameters on the surface morphology and performance of the conversion film were analyzed by means of SEM and electrochemical method. Formation dynamics about cerium conversion film on magnesium alloy in solution containing cerium salt and the anti-corrosion behavior of the conversion film in 3.5% NaCl solution were studied by electrochemical method respectively. The results shows that the conversion film is more compact at room temperature when concentration of cerium sulfate is 10 g·L-1 in the solution; the open circuit potential of the magnesium sample moves up to positive direction about 100 mV, the surface of conversion film becomes even and lustrous, and the adhesion intensity of conversion film increases when adding aluminum nitrate into the solution containing cerium salt. The pH value of the solution and immersion time of the sample in the solution also affect the surface morphology and anti-corrosion property of the conversion film. After covered by rare earths conversion film, the anti-corrosion property of magnesium alloy is obviously improved. Rare earth conversion film has self-repairing capability in corrosion medium.

Effects of rare earths on the microarc oxidation of a magnesium alloy

The effects of rare earths on the properties of the microarc oxidation（MAO） coating on a magnesium alloy were investigated by means of scanning electron microscopy（SEM）,energy dispersive X-ray spectroscopy（EDS）,and electrochemistry methods.The results show that a nice and compact MAO coating was successfully obtained when the magnesium alloy was treated in nitrate solutions as the pre-treatment of MAO.However,the MAO was not successfully completed for the silicate electrolytes with the addition of rare earths.After the magnesium alloy being treated by rare earth nitrate,the obtained MAO coating has advantages such as uniform distribution of thickness,improved corrosion resistance,and nice-uniform surface,as compared with the untreated magnesium alloy.In addition,the time of non-ESP,the voltage and current density of the MAO process obviously decrease.Cerium oxide doped on the surface of the magnesium alloy can significantly improve the corrosion resistance of the MAO coating and decrease the current density of the MAO process,as compared with lanthanum oxide,whereas the doped rare earths have no significant effect on the components of the MAO coating.

Effect of rare earth elements addition on thermal fatigue behaviors of AZ91 magnesium alloy

Influences of rare earth （RE） elements addition on thermal fatigue behaviors of AZ91 alloy were studied. Repeated heating and cooling cycles were applied on the samples at 170 and 210℃ to develop thermal fatigue cracks. Crack growth mechanisms and microstructural influences were investigated by optical and scanning electron microscopy （SEM） as well as energy dispersive X-ray spectroscopy （EDS）. Thermal fatigue behaviors were observed to improve successively by addition of the RE up to 2wt.%. This improvement was attributed to the consummation of aluminum in melt by precipitation of the needle shaped AII1RE3 phases. This process was attributed to the reduction of MglTAl12 phase volume fraction and consequent decrease of the brittle Mg/MglTAl12 interface which was the main reason for weak thermal properties of the alloy at rather high temperatures. Further additions of RE, however, reduced the thermal shock resistance of the samples by increasing the mean length of the brittle needle shaped phases.

Effect of rare earth on the microstructure and mechanical properties of as-cast Cu-30Ni alloy

Cu-30Ni-xRE （x = 0-0.213） alloys were prepared by a metal mould casting method. The effect of RE on the microstructure and mechanical properties of the alloys was investigated using optical microscope, scanning electronic microscope with energy-dispersive spectrometer, X-ray diffraction, and mechanical test. The results show that RE has obvious effect on refining dendrite structure and grain size, as well as on purifying the melting of Cu-30Ni alloy. With the increase of RE content, the ultimate tensile strength, yield strength, and elongation increase at first and then decrease after adding RE more than 0.095 wt.%. Cu-30Ni-0.095RE alloy possesses preferable mechanical properties, i.e., the ultimate tensile strength, yield strength, and elongation are 308 MPa, 125 MPa, and 51.2%, respectively. The microstructure and mechanical properties are worsened with increasing RE content more than 0.095 wt.%. The improvement of mechanical properties of Cu-30Ni-0.095RE alloy is attributed to RE refining microstructure and purifying the matrix.

Corrosion Inhibition Mechanism of Rare Earth Metal on LC4 Al Alloy with Spilt Cell Technique

A new method of studying the corrosion inhibition mechanism of rare earth metal（REM） on LC4 Al alloy with the spilt cell technique was studied. The principle and experimental method of the spilt cell technique were analyzed. By measuring the change of net-electric current between the two electrodes caused by the change of the amount of oxygen in the solution and the addition of CeCl3, the influence of corrosive performance of CeCl3 on LC4 super-power aluminum ＂alloy in the 0.1 mol· L^-1 NaCl solution was investigated. Meanwhile, the conditional changes of pH values, CeCl3 solution, additire and time of performance were also studied. Finally, the features of electrode surface were revealed by using SEM and X-ray energy-dispersive spectrometry （EDS）. By combining these with other electric chemical techniques, such as potential-time curve, polarization curve et al.

Preparation and Corrosion Resistance of Rare Earth Conversion Coatings on AZ91 Magnesium Alloy

The feasibility of forming pollution-free and environmentally benign Ce-based rare earth conversion coatings （short for RECCs） on AZ91 magnesium alloy to enhance corrosion resistance was studied. The effect of optimum processing parameters on corrosion resistance of RECCs, such as density of treating solution, temperature and time of coating formation were discussed. Protective performance of conversion coatings on magnesium alloy was evaluated by moisture/heating test, anodic polarization, etc. The results show that Ce-based RECCs under moisture/heating condition can remain intact, with high coverage and no obvious corrosion phenomenon. Corrosion potential increases and passive phenomenon occurs while current density decreases, therefore Ce-based RECCs can improve corrosion resistance of AZ91 magnesium alloy. The morphology of Ce-based RECCs prepared under optimum process through SEM observation is found to be a few particles coherent to the base coating, and the coating has no cracks and exhibits apparent corrosion resistance during corrosion courses of AZ91 magnesium alloy.

Study on Nanocrystalline Rare Earth Mg-Based System Hydrogen Storage Alloys with AB_3-Type

A sort of rare earth Mg-based system hydrogen storage alloys with AB3-type was prepared by double-roller rapid quenching method. The alloys were nanocrystalline multi-phase structures composed of LaNi3 phase and LaNi5 phase by X-ray diffraction and scanning electron microscopy analyses, and the suitable absorption/desorption plateau was revealed by the measurement of P-C-I curve. Electrochemical studies indicate that the alloys exhibit good electrochemical properties such as high capacity and stable cycle life, and the discharge capacity is 369 mAh·g-1 at 0.2 C (72 mA·g-1), after 460 cycles, the capacity decay was only 19.4% at 2 C (720 mA·g-1).

Effect of Heat-Treatment Process on Properties of Rare Earth Mg-Based System Hydrogen Storage Alloys with AB_3-Type

The effect of heat-treatment process on the properties of Mm0.8Mg0.2(NiCoAlMn)3.5 hydrogen storage alloy was discussed. The electrochemical properties such as cycling stability, activation property, and the plateau voltage of the alloy which was heat-treated in various temperatures and times had different changes during the cycle process, the optimum heat-treatment conditions of this alloy were determined by this work.

Effect of Rare Earth on Microstructure of Vacuum Melting Ni-Based Self-Fluxing Alloy Coatings

The Ni-based self-fluxing alloy coating containing RE was acquired by the technique of vacuum melting on the hypoeutectoid steel (Fe-0.45%C) matrix. By X-ray diffraction, SEM and EDX, the microstructure and phase structure of section of coating and the microstructure near the interface between coating and matrix were investigated, and the effect of RE on microstructure of coating was also discussed. The results show that the microstructure of the NiCrBSi alloy coating is composed of Ni-based solid solution and a lot of massive, globular and needle secondary phases CrB, Ni_3B, Cr_7C_3, Cr_(23)C_6 among the solid solution. The metallurgical binding between steel matrix and coating is realized. RE makes needle phase of alloy coating vanish. New phases of NiB and Cr_(6.5)Ni_(2.5)Si are precipitated from alloy coating, and secondary phases of alloy coating are sphericized. Consequently, RE also hinders the diffusion of Ni, Cr and Si atoms from coating to matrix and Fe atoms from matrix to coating, holds back the dilution of Fe for NiCrBSi alloy coating, and assures the chemical composition of the alloy coating.

Effects of rare earth La on the microstructure and melting property of(Ag-Cu_(28))-30Sn alloys prepared by mechanical alloying

To obtain novel intermediate temperature alloy solders with a melting temperature of 400-600°C,nominal（Ag-Cu28）-30Sn alloys without or with a trace addition（0.5 or 1.0 wt.%） of rare earth（RE） element La were prepared by mechanical alloying.The aim of this research is to investigate the effects of the addition of La on the microstructures,alloying process and melting properties of（Ag-Cu28）-30Sn alloys.The results show that the addition of La produces no new phase.A trace amount of La addition can effectively refine the grain size,but the excessive addition of 1.0 wt.% La inhibits the alloying process.The influence of La on the melting temperatures of solder alloys is negligible.However,the trace addition of 0.5 wt.% La can distinctly reduce the fusion zone and improve the melting property of（Ag-Cu28）-30Sn alloys.

Friction and Wear Characteristics of Mg-Al Alloy Containing Rare Earths

The influence of rare earth on the friction and wear characteristics of magnesium alloy AZ91 and AM60 were studied. The results show that the wear resistance properties of rare earth magnesium alloys are better than those of matrix alloy under the testing conditions. The anti wear behaviour of AZ91 alloy is much better than that of AM60 alloy. In dry sliding process,magnesium alloys undergo a transition from mild wear to severe wear. The addition of rare earths refine the structure of alloys, improve the comprehensive behaviors of magnesium alloys, increase the stability of oxidation films on worn surfaces, enhance the loading ability of rare earth magnesium alloys, and delay the transition from mild wear to severe wear effectively.