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.

Effect and Mechanism of Rare Earth Hydrotalcite Inhibiting Coal Spontaneous Combustion

A hydrotalcite(layered double hydroxide, LDH) inhibitor which is suitable for the whole process of coal spontaneous combustion and a LDH inhibitor containing rare earth lanthanum elements were prepared. The inhibition effect and mechanism were analyzed by scanning electron microscopy(SEM),X-ray diffraction(XRD), thermal performance analysis, in-situ diffuse reflectance infrared spectroscopy and temperature-programmed experiment. The results have shown that the inhibitor containing lanthanum can play a good inhibitory role in every stage of coal oxidation. During the slow oxidation of coal samples, the inhibitor containing lanthanum ions can slow down the oxidation process of coal and increase the initial temperature of coal spontaneous combustion. At the same time, because the hydroxyl groups in LDHs are connected with-COO-groups on the coal surface through hydrogen bonds, the stability of coal is improved. With the increase of temperature, LDHs can remove interlayer water molecules and reduce the surface temperature of coal. CO release rate of coal samples decreases significantly after adding inhibitor containing lanthanum element, and the maximum inhibition rate of the inhibitor is 58.1%.

Association between Exposure of Rare Earth Elements and Outcomes of In Vitro Fertilization-Embryo Transfer in Beijing

Objective The study aimed to investigate the impact of rare earth elements(REEs)exposure on pregnancy outcomes of in vitro fertilization-embryo transfer(IVF-ET)by analyzing samples from spouses.Methods A total of 141 couples were included.Blood and follicular fluid from the wives and semen plasma from the husbands,were analyzed for REEs using inductively coupled plasma mass spectrometry(ICP-MS).Spearman's correlation coefficients and the Mann–Whitney U test were used to assess correlations and compare REE concentrations among three types of samples,respectively.Logistic models were utilized to estimate the individual REE effect on IVF-ET outcomes,while BKMR and WQS models explored the mixture of REE interaction effects on IVF-ET outcomes.Results Higher La concentration in semen(median 0.089 ng/mL,P=0.03)was associated with a lower fertilization rate.However,this effect was not observed after artificial selection intervention through intracytoplasmic sperm injection(ICSI)(P=0.27).In semen,the REEs mixture did not exhibit any significant association with clinical pregnancy.Conclusion Our study revealed a potential association between high La exposure in semen and a decline in fertilization rate,but not clinical pregnancy rate.This is the first to report REEs concentrations in follicular fluid with La,Ce,Pr,and Nd found at significantly lower concentrations than in serum,suggesting that these four REEs may not accumulate in the female reproductive system.However,at the current exposure levels,mixed REEs exposure did not exhibit reproductive toxicity.

Improvement strategy on thermophysical properties of A_(2)B_(2)O_(7)-type rare earth zirconates for thermal barrier coatings applications:A review

The A_(2)B_(2)O_(7)-type rare earth zirconate compounds have been considered as promising candidates for thermal barrier coating(TBC) materials because of their low sintering rate,improved phase stability,and reduced thermal conductivity in contrast with the currently used yttria-partially stabilized zirconia (YSZ) in high operating temperature environments.This review summarizes the recent progress on rare earth zirconates for TBCs that insulate high-temperature gas from hot-section components in gas turbines.Based on the first principles,molecular dynamics,and new data-driven calculation approaches,doping and high-entropy strategies have now been adopted in advanced TBC materials design.In this paper,the solid-state heat transfer mechanism of TBCs is explained from two aspects,including heat conduction over the full operating temperature range and thermal radiation at medium and high temperature.This paper also provides new insights into design considerations of adaptive TBC materials,and the challenges and potential breakthroughs are further highlighted for extreme environmental applications.Strategies for improving thermophysical performance are proposed in two approaches:defect engineering and material compositing.

Wetting front migration model of ion-adsorption rare earth during the multi-hole unsaturated liquid injection

In the process of ion-adsorption rare earth ore leaching,the migration characteristics of the wetting front in multi-hole injection holes and the influence of wetting front intersection effect on the migration distance of wetting fronts are still unclear.Besides,wetting front migration distance and leaching time are usually required to optimize the leaching process.In this study,wetting front migration tests of ionadsorption rare earth ores during the multi-hole fluid injection(the spacing between injection holes was 10 cm,12 cm and 14 cm)and single-hole fluid injection were completed under the constant water head height.At the pre-intersection stage,the wetting front migration laws of ion-adsorption rare earth ores during the multi-hole fluid injection and single-hole fluid injection were identical.At the postintersection stage,the intersection accelerated the wetting front migration.By using the Darcy’s law,the intersection effect of wetting fronts during the multi-hole liquid injection was transformed into the water head height directly above the intersection.Finally,based on the Green-Ampt model,a wetting front migration model of ion-adsorption rare earth ores during the multi-hole unsaturated liquid injection was established.Error analysis results showed that the proposed model can accurately simulate the infiltration process under experimental conditions.The research results enrich the infiltration law and theory of ion-adsorption rare earth ores during the multi-hole liquid injection,and this study provides a scientific basis for optimizing the liquid injection well pattern parameters of ion-adsorption rare earth in situ leaching in the future.

Differential Expression Analysis of Proteins Regulated by Rare Earth Cerium in Soybean Leaves at Seedling Stage

This study was to explore the functional mechanism of rare earth regulating soybean leaves and the characteristics and functions of differentially expressed proteins under the regulation of rare earth. In this study, Dongnong 42 was used as material, and 30 mg·L^(-1) CeCl_(3) solution was sprayed on soybean leaves at the seedling stage. Tandem mass tag(TMT) quantitative proteomics technique and bioinformatics analysis were used to identify soybean leaf proteins. A total of 8 510 proteins were identified, and 127 differentially expressed proteins(DEPs) in response to rare earth cerium regulation were identified, among which 64 were upregulated and 63 were down-regulated. The gene ontology(GO) annotation indicated that DEPs were mainly involved in metabolic process, cellular process, response to stimulus, biological regulation, and response to a stimulus;DEPs in cell module categories were mainly involved in cells, cell part, organelle, membrane, membrane part, organelle par, and protein-containing complex;DEPs in molecular functional categories were mainly involved in catalytic activity, binding and antioxidant activity. Kyoto encyclopedia of genes and genomes(KEGG) pathway significantly enriched starch and sucrose metabolism, glycolysis/gluconeogenesis, galactose metabolism, pentose phosphate pathway, and MAPK signaling pathway-plant. These DEPs were mainly involved in photosynthesis, glucose metabolism and stress response. Forty-six differential protein interaction networks were identified by protein interaction network analysis. This experiment provided a reference for studies of the mechanism of rare earth cerium regulating soybean leaf function from the proteomic perspective.

Disorganizing rare earth ions may improve quantum infor mation storage

A new paper in Nature Physics shows that by cramming lots of rare earth ions into a crystal,some will form pairs that act as highly coherent qubits,thus debunking the idea that solid-state qubits need to be super dilute in an ultra-clean material to achieve long lifetimes.According to the study's authors,one of the major barriers to practical quantum computing has been how to make qubits that retain their quantum information long enough to be useful.

Leaching characteristics of ion-adsorption type rare earths ore with magnesium sulfate

Magnesium sulfate was proposed to be leaching agent to deal with the ion-adsorption type rare earths ore to reduce or even eliminate ammonia?nitrogen emissions. The effects of temperature, particle size and stirring speed on rare earth leaching process and the leaching behaviors of the single rare earth element were investigated in order to reveal the rare earth leaching characteristics. Besides, the comparison of leaching effects between magnesium sulfate and ammonium sulfate was also studied. The results showed that the rare earth leaching process could be well described with inner diffusion control model and the apparent activation energy was 9.48 kJ/mol. The leaching behaviors of the single rare earth element were brought into correspondence with rare earths. Moreover, when the concentration of leaching agent was 0.20 mol/L, the rare earth leaching efficiency could all reach above 95% and the leaching efficiency of aluminum impurities could be restrained by 10% using magnesium sulfate compared with ammonium sulfate.

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.

Influence of rare earth Ce on hot deformation behavior of as-cast Mn18Cr18N high nitrogen austenitic stainless steel

The hot deformation behavior of Mn18Cr18N and Mn18Cr18N+Ce high nitrogen austenitic stainless steels at 1173-1473 K and 0.01-1 s^(-1) were investigated by thermal compression tests.The influence mechanism of Ce on the hot deformation behavior was analyzed by Ce-containing inclusions and segregation of Ce.The results show that after the addition of Ce,large,angular,hard,and brittle inclusions(TiN-Al_(2)O_(3),TiN,and Al_(2)O_(3)) can be modified to fine and dispersed Ce-containing inclusions(Ce-Al-O-S and TiN-Ce-Al-O-S).During the solidification,Ce-containing inclusions can be used as heterogeneous nucleation particles to refine as-cast grains.During the hot deformation,Ce-containing inclusions can pin dislocation movement and grain boundary migration,induce dynamic recrystallization(DRX)nucleation,and avoid the formation and propagation of micro cracks and gaps.In addition,during the solidification,Ce atoms enrich at the front of solid-li-quid interface,resulting in composition supercooling and refining the secondary dendrites.Similarly,during the hot deformation,Ce atoms tend to segregate at the boundaries of DRX grains,inhibiting the growth of grains.Under the synergistic effect of Ce-containing inclusions and Ce segregation,although the hot deformation resistance and hot deformation activation energy are improved,DRX is more likely to occur and the size of DRX grains is significantly refined,and the problem of hot deformation cracking can be alleviated.Finally,the microhardness of the samples was measured.The results show that compared with as-cast samples,the microhardness of hot-deformed samples increases signific-antly,and with the increase of DRX degree,the microhardness decreases continuously.In addition,Ce can affect the microhardness of Mn18Cr18N steel by affecting as-cast and hot deformation microstructures.

Effect of rare earth on morphology and dispersion of TiB2 phase in Al-Ti-B alloy refiner

To investigate the effect of rare earth on size and distribution of TiB2 phase in aluminum alloy refiner,Al-5Ti-1B-RE master alloy was fabricated,and its microstructure and phase constitutions were investigated by the combination of first principles calculations and experimental investigation.The calculated results reveal that Ce has the most effective modification ability due to the most positive adsorption energy and the largest charge transfer value compared with other rare earth elements.Results of experimental investigation indicate that the addition of rare earth in the Al-5Ti-1B alloys can greatly refine the particle size of TiB2,improve the distribution of particles and lead to better refinement effect than that of the Al-5Ti-1B alloys without rare earth.Moreover,Ce has the best optimization effect,which agrees well with the calculated results.

Effect of surfactant addition on leaching process of weathered crust elution-deposited rare earth ores with magnesium sulfate

Surfactants were proposed to be added into magnesium sulfate solution to improve the leaching process of weathered crust elution-deposited rare earth ores(WREOs).Effects of surfactants and their concentration on the seepage of leaching solutions and the leaching efficiency of rare earth(RE)and aluminum(Al)were investigated,and the leaching kinetics,the mass transfer process,the adhesion work and the adhesion work reduction factor were analyzed to reveal its strengthening leaching mechanism.The results show that cetyltrimethylammonium bromide(CTAB)has a better strengthening effect on the leaching process than dodecyl trimethyl ammonium bromide(DTAB),sodium dodecyl sulfate(SDS),sodium oleate and oleic acid.In the presence of 0.04%CTAB in 0.2 mol/L solution,the permeability coefficient of WREOs increases from 0.945×10^(-5)to 1.640×10^(-5)cm·s^(-1),and the leaching efficiency of RE increases from 80%to 90%,confirming the promotion of surfactants on the leaching process of WREOs.Kinetic analysis shows that the leaching process conforms to the inner diffusion control model,and the leaching kinetics equations of RE and Al related to CTAB content are obtained.Mass transfer discussion shows a smaller height equivalent to theoretical plate(HETP)of RE and Al at CTAB content of 0.04%,suggesting the higher mass transfer efficiency here.According to the interfacial properties of leaching solutions,the calculated adhesion work and the adhesion work reduction factor further demonstrate the strengthening leaching effect of CTAB on the leaching process of WREOs.

Rare earth elemental and Sr isotopic evidence for seawater intrusion event of the Songliao Basin 91 million years ago

Petrogenesis of lacustrine dolostone is closely related with paleo-lake water conditions.Here we report the high spatial-resolution petrographic and geochemical results of a lacustrine dolomite nodule from the Qingshankou Formation,the Songliao Basin.Sedimentary and elemental signatures confirm the protogenetic origin of this nodule and its effectiveness in recording geochemical characteristics of paleo-lake water during dolomitization.The low Y/Ho ratios,middle rare earth element(MREE)enrichment and subtle positive Eu anomalies within the nodule indicate a fresh water source.However,the Sr isotope values in the core of the nodule(0.7076-0.7080)are close to contemporaneous seawater(0.7074),yet different from the modern river(0.7120)and the host black shale(0.7100).On the premise of excluding the influence of hydrothermal fluids,the significantly low strontium isotope values of the lacustrine dolomite might be caused by seawater interference during dolomitization.Our findings demonstrate that lacustrine dolomite within black shales is not only a faithful tracer of diagenetic water environment,but also a novel and easily identified mineralogical evidence for episodic seawater intrusion event(91 Ma)in the Songliao Basin,which supplements other paleontological and geochemical evidence.

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.

Effect of Rare Earths on Diffusion Coefficient and Transfer Coefficient of Carbon during Carburizing

The diffusion coefficient of carbon in surface layer of steel-20 rare earth carburixed at 880 degreesC and 900 degreesC for 8 h was calculated by substituting the measured layer depths into the diffusion equation. The mathematical model of the transfer coefficient of carbon was deduced based on the kinetics of weight gain during gas carburizing. The calculated results show that the main reason why the gas carburizing process is accelerated is due to the obvious increase in the diffusion coefficient and transfer coefficient of carbon resulted from the addition of RE.

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 Earths on Tribological Properties of Carbon Fibers Reinforced PTFE Composites

Carbon fibers （CF） were surface treated with air-oxidation and rare earths （RE）, respectively. The effect of RE surface treatment on tensile strength and tribological properties of CF reinforced polytetrafluoroethylene （PTFE） composites was invest/gated. Experimental results revealed that RE was superior to air ox/dation in improving the tensile strength, elongation, and the tensile modulus of CF reinforced PTFE （CF/PTFE） composite. Compared to the untreated and air-oxidated CF/PTFE composite, the RE treated composite had the lowest friction coefficient and specific wear rate under a given applied load and reciprocating sliding frequency. The RE treatment effectively improved the interfacial adhesion between CF and PTFE. With strong interfacial coupling, the carbon fibers carried most of the load, and direct contact and adhesion between PTFE and the counterpart were reduced, accordingly the friction and wear properties of the composite were improved.

Effect of Rare Earths on Plant under Supplementary Ultraviolet-B Radiation: Ⅰ Effect of Cerium on Growth and Photosynthesis in Rape Seedlings Exposed to Supplementary Ultraviolet-B Radiation

Effect of cerium （Ce^3＋） on growth and photosynthesis in rape seedlings exposed to two levels of ultraviolet-B radiation （UV-B, 280 - 320 nm） was studied with hydroponics under laboratory conditions. The growth of rape seedlings exposed to two levels of UV-B irradiation （0.15 and 0.35 W· m^-2/T2） was both heavily restrained. The aboveground growth indices including stem （plant） height, leaf number, leaf area, leaf fresh/dry weight and stem fresh/dry weight were obviously decreased by 13.2% - 44.1% （T1） and 21 .4% - 49.3% （T2）. Compared to CK, and except active absorption area of roots, the belowground indices main root length, root volume and fresh/dry weight by 14.1% -35.6% （T1） and 20.3% - 42.6% （T2）, respectively. For Ce ＋ UV-B treatments, the aboveground and belowground growth indices were decreased by 4.1% - 23.6%, 5.2% -23.3% （Ce＋T1） and 10.8% -28.4%, 7.0% -27.8% （Ce ＋T2）, lower than those of UV-B treatments mentioned above. These results show that Ce has protective effect on plant against injury of UV-B radiation. Furthermore, the protective effect of Ce on seedlings exposed to T1 level of UV-B radiation is superior to T2 level. Chlorophyll content, net photosynthesis rate, transpiration rate, stomatal conductance and water use efficiency in UV-B treatments decrease dramatically, whereas intercellular CO2 concentration increases. Although these indices in Ce ＋ UV-B treatments decrease compared with those of CK, the decrease in Ce ＋ UV-B treatments are lower than those in UV-B treatment. This phenomenon indicates that the ecophysiological protective effect of Ce is based on improving photosynthesis in plants. The dynamic curves of photosynthesis indices show that the course of light-repair is shortened and the injury to rape seedlings by UV-B radiation stress is alleviated by Ce.

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.

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.