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.

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.

Synthesis and Photocatalytic Activity of TiO_2/V_2O_5 Composite Catalyst Doped with Rare Earth Ions

TiO2/V2O5 catalyst doped with rare earth ions was prepared by sol-gel method. Titanium tetrapropoxide and vanadium pentoxide were used as precursor of the composite catalyst and rare earth ions were used as dopant. The crystal phases, crystalline sizes, microstructure, absorption spectra of doped composite catalyst were studied by XRD, EDS, FT-IR and UV-Vis. Photoactivity of the prepared catalyst under ultraviolet irradiation were evaluated by degradation of methyl orange （MO） in aqueous solution. It is shown that the prepared catalyst is composed of anatase and futile. The rare earth ions are highly dispersed in composite catalyst. All the doped catalysts appear higher photocatalytic activity than TiO2/V2O5 catalyst and catalyst doped with Ce^4＋ present the best activity to MO.

A novel fused iron catalyst for ammonia synthesis promoted with rare earth gangue

Rare earth gangue, which mainly consists of mixtures of light rare earths such as lanthana, ceria, neodymium oxide and praseodymium oxide, was used as the promoter of fused iron catalysts for ammonia synthesis. The result showed that the activity of the catalyst promoted with rare earth gangue was comparable with those of commercial iron catalysts with high amount of cobalt. The role of rare earths was owed to their advantages for favoring the deep reduction of the main composite in catalyst, i.e., iron oxide. This fmding indicated that the use of rare earth gangue could decrease the content of cobalt or even completely replace cobalt, which was used to be regarded as unsub- stitutable promoters for high performance ammonia catalyst; therefore, the cost of fused iron catalysts would decrease significantly.

Physicochemical and isomerization property of Pt/SAPO-11 catalysts promoted by rare earths

Monometallic catalyst Pt/SAPO-11 was prepared by impregnation method.Bimetallic catalysts LaPt/SAPO-11 or CePt/SAPO-11 was prepared by sequential impregnation method.The catalysts were characterized by X-ray diffraction(XRD),nitrogen adsorption,temperature-programmed desorption of ammonia(NH3-TPD),and Fourier transform infrared spectroscopy(FT-IR) techniques.The results showed that with the addition of rare earths the BET surface areas,pore volume,the amount of Bronsted acid and the total acidity of catalys...

Copolymerization of Styrene with N-phenylmaleimide by Rare Earth Coordination Catalysts

Copolymerization of styrene (St) with N-phenylmaleimide (NPMI) was studied with rare earth coordination catalyst Nd(naph)3-AlEt3 in toluene. Characterization of the copolymers showed that the copolymers possess an alternating structure.

Low-temperature activation of methane over rare earth metals promoted Zn/HZSM-5 zeolite catalysts in the presence of ethylene

At low temperature of 723 K, methane can be easily activated in the presence of ethylene in the feed, and converted to higher hydrocarbons （C2-C4） and aromatics （C6-C10）, through its reaction over rare metals modified Zn/HZSM-5 zeolite catalysts without undesirable carbon oxides formation. Methane can get 37.3% conversion over the above catalysts under low temperature, and the catalysts show a longer lifetime than usual metal supported HZSM-5 zeolite catalysts without adding any rare earth metals. The effects of methane activation over various rare earth metal promoted Zn/HZSM-5 catalysts on the products and influences of several reaction conditions such as temperature, catalyst lifetime and molar ratio of CH4/C2H4 have been discussed.

Hydrogen production through diesel steam reforming over rare-earth promoted Ni/γ-Al_2O_3 catalysts

Rare-earth （La, Ce, Yb） promoted Ni/γ-Al2O3 catalysts were prepared by impregnation method. Activity and carbon formation resistance of the prepared catalysts were evaluated under various reaction conditions. Catalyst characterizations with TG, TPR and H2 chemisorption were carried out to investigate the promoting mechanism. Experimental results show that rare-earth promoters, especially Yb promoter, obviously improve the activity and carbon formation resistance of Ni/γ-Al2O3 catalyst, and Yb-Ni catalyst shows even higher performance than several commercial catalysts. According to the characterization results, Yb promoter enhances the interaction between the active metal and support, thus increasing the active metal＇s dispersion and improving its performance. Furthermore, the obvious difference in diesel conversion between Yb-Ni catalyst and others was shown in the temperature range of 450-550 °C, which would be the reason for its excellent carbon resistance.

Hydrogen production from coke oven gas over LiNi/γ-Al_2O_3 catalyst modified by rare earth metal oxide in a membrane reactor

The performance of LiNi/γ-Al2O3 catalysts modified by rare earth metal oxide （La2O3 or CeO2） packed on BCFNO membrane reactor was discussed for the partial oxidation of methane （POM） in coke oven gas （COG） at 875 ℃. The NiO/γ-Al2O3 catalysts with different amounts of La2O3 and CeO2 were prepared with the same preparation method and under the same condition in order to compare the reaction performance （oxygen permeation, CH4 conversion, H2 and CO selectivity） on the membrane reactor. The results show that the oxygen permeation flux increased significantly with LiNiREOx/γ-Al2O3 （RE = La or Ce） catalysts by adding the element of rare earth especially the Ce during the POM in COG. Such as, the Li15wt%CeO29wt%NiO/γ-Al2O3 catalyst with an oxygen permeation flux of 24.71 ml·cm^-2·min^-1 and a high CH4 conversion was obtained in 875 ℃. The resulted high oxygen permeation flux may be due to the added Ce that inhibited the strong interaction between Ni and Al2O3 to form the NiAl2O4 phase. In addition, the introduction of Ce leads up to an important property of storing and releasing oxygen.