Exceptional reversed yield strength asymmetry in a rare-earth free Mg alloy containing quasicrystal precipitates

This work reports an exceptional reversed yield strength asymmetry at room temperature for a rare-earth free magnesium alloy containing a mass of fine dispersed quasicrystal(I-phase)precipitates.Although exhibiting traditional basal texture,it owns an exceptional CYS/TYS as high as~1.17.Electron back-scattered diffraction(EBSD)and transmission electron microscopy(TEM)examinations indicate pyramidal and prismatic dislocations plus tensile twinning being activated after immediate yielding in compression while basal and non-basal dislocations in tension.I-phase particles transferred the concentrated stress by self-twinning to provide the driving force for tensile twin initiating in neighboring grains,thereby significantly increasing the critical resolved shear stress of tensile twinning to possibly the level of pyramidal slip,finally leading to the dominance of pyramidal slip plus tensile twinning in texture grains.This results in a higher contribution on yield strength by~55 MPa in compression than in tension,which reasonably agrees with the experimental yield strength difference(~38 MPa).It can be concluded that I-phase particles influence deformation modes in tension and in compression,finally result in reversed yield strength asymmetry.

Fundamental Research and Application Exploration of Optoelectronic Materials and Nanocomposite Materials of Rare Earth

This project is set in one of the international frontier research fields in inorganic solid chemistry.At present, the research in organic/inorganic hybrid materials and nanocomposite optoelectronic functional materials is under the spotlight in the realm of materials science; there remain quite a few difficulties hiding in the traditional synthesis methods.For instance, the reaction cycle is generally too long, rare earth luminescence components are covalently grafted onto the matrix network, and the stability and luminescence properties are quite poor.Hence, Prof.Zhang and his colleagues proposed a series of new methods and technologies through systematic studies to prepare organic/inorganic hybrid materials and nanocomposite optoelectronic functional materials, striving to solve those kinds of problems.Through many years' efforts, a scientific basis was established by the scientists for the design and performance of the materials, which is recognized of great practical significance.

Solvent impregnated resin prepared using task-specific ionic liquids for rare earth separation

A novel bifunctional task-specific ionic liquid(TSIL),i.e.[trialkylmethylammonium][sec-nonylphenoxy acetate]([A336] [CA-100]) was impregnated on intermediate polarized XAD-7 resin,and the prepared solvent impreganated resin(SIR) was studied for rare earth(RE) separation.Adsorption ability of the SIR was indicated to be obviously higher than that prepared by [A336][NO3] because of the functional anion of [A336][CA-100].Adsorption kinetics,adsorption isotherm,separation and desorption of the SIR were also stu...

Boosting Chemodynamic Therapy by the Synergistic Effect of Co‑Catalyze and Photothermal Effect Triggered by the Second Near‑Infrared Light

In spite of the tumor microenvironments responsive cancer therapy based on Fenton reaction(i.e.,chemodynamic therapy,CDT)has been attracted more attentions in recent years,the limited Fenton reaction efficiency is the important obstacle to further application in clinic.Herein,we synthesized novel FeO/MoS2 nanocomposites modified by bovine serum albumin(FeO/MoS2-BSA)with boosted Fenton reaction efficiency by the synergistic effect of co-catalyze and photothermal effect of MoS2 nanosheets triggered by the second near-infrared(NIR II)light.In the tumor microenvironments,the MoS2 nanosheets not only can accelerate the conversion of Fe3+ions to Fe2+ions by Mo4+ions on their surface to improve Fenton reaction efficiency,but also endow FeO/MoS2-BSA with good photothermal performances for photothermal-enhanced CDT and photothermal therapy(PTT).Consequently,benefiting from the synergetic-enhanced CDT/PTT,the tumors are eradicated completely in vivo.This work provides innovative synergistic strategy for constructing nanocomposites for highly efficient CDT.

Optimizing the electronic spin state and delocalized electron of NiCo_(2)(OH)_(x)/MXene composite by interface engineering and plasma boosting oxygen evolution reaction

The electrocatalytic activity of transition-metal-based compounds is closely related to the electronic configuration.However,optimizing the surface electron spin state of catalysts remains a challenge.Here,we developed a spin-state and delocalized electron regulation method to optimize oxygen evolution reaction(OER)performance by in-situ growth of NiCo_(2)(OH)_(x) using Oswald ripening and coordinating etching process on MXene and plasma treatment.X-ray absorption spectroscopy,magnetic tests and electron paramagnetic resonance reveal that the coupling of NiCo_(2)(OH)_(x) and MXene can induce remarkable spin-state transition of Co^(3+)and transition metal ions electron delocalization,plasma treatment further optimizes the 3 d orbital structure and delocalized electron density.The unique Jahn-Teller phenomenon can be brought by the intermediate spin state(t2 _(g)^(5) e_(g)^(1))of Co^(3+),which benefits from the partial electron occupied egorbitals.This distinct electron configuration(t2_(g)^(5) e_(g)^(1))with unpaired electrons leads to orbital degeneracy,that the adsorption free energy of intermediate species and conductivity were further optimized.The optimized electrocatalyst exhibits excellent OER activity with an overpotential of 268 m V at 10 m A cm^(-2).DFT calculations show that plasma treatment can effectively regulate the d-band center of TMs to optimize the adsorption and improve the OER activity.This approach could guide the rational design and discovery of electrocatalysts with ideal electron configurations in the future.

Unlocking the potential of ultra-thin two-dimensional antimony materials:Selective growth and carbon coating for efficient potassium-ion storage

Antimony-based anodes have attracted wide attention in potassium-ion batteries due to their high theoretical specific capacities(∼660 mA h g^(-1))and suitable voltage platforms.However,severe capacity fading caused by huge volume change and limited ion transportation hinders their practical applications.Recently,strategies for controlling the morphologies of Sb-based materials to improve the electrochemical performances have been proposed.Among these,the two-dimensional Sb(2D-Sb)materials present excellent properties due to shorted ion immigration paths and enhanced ion diffusion.Nevertheless,the synthetic methods are usually tedious,and even the mechanism of these strategies remains elusive,especially how to obtain large-scale 2D-Sb materials.Herein,a novel strategy to synthesize 2D-Sb material using a straightforward solvothermal method without the requirement of a complex nanostructure design is provided.This method leverages the selective adsorption of aldehyde groups in furfural to induce crystal growth,while concurrently reducing and coating a nitrogen-doped carbon layer.Compared to the reported methods,it is simpler,more efficient,and conducive to the production of composite nanosheets with uniform thickness(3–4 nm).The 2D-Sb@NC nanosheet anode delivers an extremely high capacity of 504.5 mA h g^(-1) at current densities of 100 mA g^(-1) and remains stable for more than 200 cycles.Through characterizations and molecular dynamic simulations,how potassium storage kinetics between 2D Sb-based materials and bulk Sb-based materials are explored,and detailed explanations are provided.These findings offer novel insights into the development of durable 2D alloy-based anodes for next-generation potassium-ion batteries.

Interface defect induced upgrade of K-storage properties in KFeSO4Fcathode: From lowered Fe-3d orbital energy level to advancedpotassium-ion batteries

KFeSO_(4)F(KFSF)is considered a potential cathode due to the large capacity and low cost.However,the inferior electronic conductivity leads to poor electrochemical performance.Defect engineering can facilitate the electron/ion transfer by tuning electronic structure,thus providing favorable electrochemical performance.Herein,through the regulation of surface defect engineering in reduced graphene oxide(rGO),the Fe–C bonds were formed between KFSF and rGO.The Fe–C bonds formed work in regulating the Fe-3d orbital as well as promoting the migration ability of K ions and increasing the electronic conductivity of KFSF.Thus,the KFSF@rGO delivers a high capacity of 119.6 mAh g^(-1).When matched with a graphite@pitch-derived S-doped carbon anode,the full cell delivers an energy density of 250.5 Wh kg^(-1) and a capacity retention of 81.5%after 400 cycles.This work offers a simple and valid method to develop high-performance cathodes by tuning defect sites.

The corrosion characteristic and mechanism of Mg-5Y-1.5Nd-xZn-0.5Zr(x=0,2,4,6 wt.%)alloys in marine atmospheric environment

The microstructure and precipitated phases of as-cast Mg-5Y-1.5Nd-x Zn-0.5Zr(x=0,2,4,6 wt.%)alloys were investigated by optical microscopy,scanning electron microscopy,energy-dispersive spectrometry and X-ray Diffraction.The exposure corrosion experiment of these magnesium alloys was tested in South China Sea and KEXUE vessel atmospheric environment.The corrosion characteristic and mechanism of magnesium alloys of Mg-5Y-1.5Nd-x Zn-0.5Zr(x=0,2,4,6 wt.%)alloys were analyzed by weight loss rate,corrosion depth,corrosion products and corrosion morphologies.The electrochemical corrosion tests were also measured in the natural seawater.The comprehensive results showed that Mg-5Y-1.5Nd-4Zn-0.5Zr magnesium alloy existed the best corrosion resistance whether in the marine atmospheric environment and natural seawater environment.That depended on the microstructure,type and distribution of precipitated phases in Mg-5Y-1.5Nd-4Zn-0.5Zr magnesium alloy.Sufficient quantity anodic precipitated phases in the microstructure of Mg-5Y-1.5Nd-4Zn-0.5Zr alloy played the key role in the corrosion resistance.

Efficient enrichment and selective recovery of rare earths from sulfate leachate of ion-adsorption type rare earth ore by extraction with HPOAc

The efficient enrichment and separation of rare earth elements(REEs) from sulfate leachates of ionadsorption type rare earth ore(IATREO) is still a challenge.This work presents a novel extractant 2-(bis((2-ethylhexyl)oxy)phosphoryl)-2-hydroxyacetic acid(HPOAc) for the selective extraction and efficie nt enrichment of REEs from sulfate leachates of IATREO.HPOAc exhibits higher extraction ability for all fifteen REEs(Ⅲ) than naphthenic acid(NA) at pH_(ini)=1,56.Furthermore,it has no drawbacks of di-(2-ethylhexyl) phosphoric acid(P204) and 2-ethylhexyl phosphoric acid mono-2-ethylhexylester(P507)such as weak extraction ability towards light REEs(Ⅲ) and high stripping acidity for heavy REEs(Ⅲ).It has better separation performance for metal ion impurities than P204 and P507,especially for the typical impurity Al(Ⅲ).Furthermore,the HPOAc system has better phase separation behavior and extraction pheno mena.A simulated operation with two-stage counte r-current extraction and single-stage stripping of REEs was carried out using unsaponified HPOAc.The recovery of REEs reaches 98.7%.The concentration of REEs increases from 0.44 to 130.35 g/L,indicating a nearly 300-fold increase.Furthermore,the content of REEs increases from 77.8 wt% to 97.6 wt%.So HPOAc has the potential to selectively recover REEs from sulfate leachates of IATREO.

Synergistic extraction and separation of thorium from rare earths in chloride media using mixture of Cextrant 230 and Cyanex 923

In order to lower the usage of expensive Cyanex 923 and increase the extraction capacity of the system of Cextrant 230,the synergistic extraction of thorium from chloride media by a mixture of Cextrant 230 and Cyanex 923 was investigated.The maximum synergistic enhancement coefficient(R)of 1.53 is obtained at 1:1 molar ratio of Cextrant 230/Cyanex 923.The syne rgistic extracted species of Th^(4+)is determined as ThCl_(4)·2Cextrant 230·Cyanex 923.The synergistic extraction of Th^(4+)is an entropy-driven exothermic process.The loading capacity of 0.60 mol/L mixed extractant for thorium is about 17.10 g/L(calculated as ThO_(2)),and the loaded thorium in the organic phase can be effectively stripped by distilled water.For comparison,rare earth cations are barely extracted under the similar conditions,suggesting that the mixtures can be applied to separate thorium from rare earths.A cascade extraction process was developed based on the synergistic extraction system to separate thorium from the hydrochloric acid leaching of bastnaesite.The content of thorium in the leaching solution decreases obviously from 19.90 mg/L to1.4μg/L by 3 stages of extraction,which is superior to sole Cextrant 230 or Cyanex 923.The introduction of Cextrant 230 into the extraction system not only lowers the usage of Cyanex 923 but also enhances the selective extraction of thorium at low acidity,implying that the synergistic extraction system can selectively extract thorium more efficiently and economically than the sole systems.

Application of Choline Chloride·xZnCl2 Ionic Liquids for Preparation of Biodiesel

The inexpensive and moisture-stable Lewis-acidic ionic liquids were prepared and applied for transesterification of soybean oil to biodiesel.The influences of molar ratio of methanol to soybean oil,reaction temperature and amount of ionic liquids were investigated.The transesterification of soybean oil to biodiesel catalyzed by choline chloride·xZnCl2 ionic liquids showed many advantages such as mild conditions and lower cost.On the other hand,the non-ideal yield and complicated separation between biodiesel and soybean oil were also investigated and analyzed.The improvement on the systems of choline chloride·xZnCl2 was proposed for further investigation.

Reducing the tension-compression yield asymmetry of extruded Mg-Zn-Ca alloy via equal channel angular pressing

The influence of equal channel angular pressing on the tension-compression yield asymmetry of extruded Mg-5.3 Zn-0.6 Ca(weight percent)alloy has been investigated.The microstructure was obviously refined by the large strain during the equal channel angular pressing,accompanied with very fine Ca_(2)Mg_(6)Zn_(3) phases with average diameter of 70 nm.The weak tension-compression yield asymmetry after equal channel angular pressing is mainly attributed to the reduced volume fraction of extension twinning during the compression,because the slope(k)of twinning in Hall-Petch relationship is higher than that of dislocation slip,and the twinning deformation is difficult to take place with decreasing grain size.The basal slip is more active in the alloy after equal channel angular pressing,due to the non-basal texture components,which hinders the twinning activation and reduces the yield asymmetry.Furthermore,the presence of fine precipitate restricts the twinning activation,which also contributes to the reduction of yield asymmetry.

Modifying microstructures and tensile properties of Mg-Sm based alloy via extrusion ratio

Microstructure and tensile properties of a Mg-Sm-Zn-Zr alloy with various extrusion ratios(ERs)of 6.9,10.4 and 17.6 were systematically investigated.It was identified that,greater ER increased dynamic recrystallization(DRX)fraction and coarsened DRX grains,which further suggests weakened basal fiber texture for the studied alloy.This is mainly due to the rising temperature from massive deformation heat when hot-extrusion.As a result,greater ER corresponds to a decreased strength but improved ductility.Finally,transmission electron microscopy(TEM)observations reveal that the dominant intermetallic phase,Mg_(3)Sm,is metastable,and it will transform into Mg_(41)Sm_(5)during extrusion with high-ER.This transformation leads to the accumulation of surplus Sm and Zn atoms,which induces the precipitation of Sm Zn_(3)phase at the surface of Mg_(41)Sm_(5)matrix.

A comparison study of Ce/La and Ca microalloying on the bio-corrosion behaviors of extruded Mg-Zn alloys

The influences of Ca and Ce/La microalloying on the microstructure evolution and bio-corrosion resistances of extruded Mg-Zn alloys have been systematically investigated in the current study.Compared with single Ca or Ce/La addition,the Ca-Ce/La cooperative microalloying results in an outstanding grain refinement,because the fine secondary phase particles effectively hinder the recrystallized grain growth.The coarse Ca2Mg6Zn3 phases promote the formation of Ca3(PO4)2 or hydroxyapatite particles during the immersion process and accelerate the dissolution of the corrosion product film,which destroys its integrity and results in the deterioration of anti-corrosive performance.The Ce/La elements can be dispersed within the conventional Mg7Zn3 phases,which reduce the internal galvanic corrosion between Mg matrix and the secondary phases,leading to an obvious improvement of corrosion resistance.Therefore,the Ca-Ce/La cooperative microalloying achieves a homogenous fine-grained microstructure and improves the protective ability of surface film,which will pave a new avenue for the design of biomedical Mg alloys in the coming future.

Extraction Kinetics of Lanthanum in Chloride Medium by Bifunctional Ionic Liquid [A336][CA-12] Using a Constant Interfacial Cell with Laminar Flow

The extraction kinetics of La(III) from aqueous chloride solutions into n-heptane solutions of bifunctional ionic liquid extractant [A336][CA-12](tricaprylmethylammonium sec-octylphenoxy acetic acid) was investigated using a constant interfacial cell with laminar flow. The effects of stirring speed, temperature and specific interfacial area on the extraction rate were examined. The results indicate that mass transfer kinetics of La(III) is a mixed-controlled process influenced by interfacial reaction. On the basis of mass transfer kinetic results in the extraction of La(III) by [A336][CA-12], the extraction rate equation of La(III) is proposed in terms of pseudo-firstorder constants, which is supported by the measured thermodynamic equations. The mass-transfer kinetic model deduced from the rate controlling step is adequate to interpret the experimental data qualitatively.

Mechanically Strong Proteinaceous Fibers:Engineered Fabrication by Microfluidics

Lightweight and mechanically strong natural silk fibers have been extensively investigated over the past decades.Inspired by this research,many artificial spinning techniques(wet spinning,dry spinning,electrospinning,etc.)have been developed to fabricate robust protein fibers.As the traditional spinning methods provide poor control over the as-spun fibers,microfluidics has been integrated with these techniques to allow the fabrication of biological fibers in a well-designed manner,with simplicity and cost efficiency.The mechanical behavior of the developed fibers can be precisely modulated by controlling the type iop and size of microfluidic channel,flow rate,and shear force.This technique has been successfully used to manufacture a broad range of protein fibers,and can accelerate the production and application of protein fibers in various fields.This review outlines recent progress in the design and fabrication of protein-based fibers based on microfluidics.We first briefly discuss the natural spider silk-spinning process and the microfluidics spinning process.Next,the fabrication and mechanical properties of regenerated protein fibers via microfluidics are discussed,followed by a discussion of recombinant protein fibers.Other sourced protein fibers are also reviewed in detail.Finally,a brief outlook on the development of microfluidic technology for producing protein fibers is presented.

Microstructure and mechanical properties of die-cast AZ91D magnesium alloy by Pr additions

Mg-9Al-xPr(x=0.4,0.8 and 1.2,mass fraction,%)magnesium alloys were prepared by high-pressure die-casting technique.The effects of Pr on the microstructures of die-cast Mg-9Al based alloy were investigated by XRD and SEM.Needle-like Al11Pr3 phase and polygon Al6Mn6Pr phase are found in the microstructure.With 0.4%Pr addition,fine needle-like Al11Pr3 phase and a small amount of polygon Al6Mn6Pr phase near the grain boundary are found in the microstructure.Increasing Pr addition to 0.8%, lots of coarse needle-like Al11Pr3 phase within grain and polygon Al6Mn6Pr phase on grain boundary are observed.Further increasing Pr addition,the size of needle-like Al11Pr3 phase decreases,while the size of polygon Al6Mn6Pr relatively increases.The mass fraction of Pr at around 0.8%is considered to be suitable to obtain the optimal mechanical properties.The optimal mechanical properties are mainly resulted from grain boundary strengthening obtained by precipitates and solid solution.

Surface density of synthetically tuned spinel oxides of Co^(3+) and Ni^(3+) with enhanced catalytic activity for methane oxidation

Spinel oxides containing Co and Ni are a promising substitute as a noble metal catalyst for methane combustion.Achieving a complete oxidation of methane under 400°C remains challenging,andhydrothermal 60 h NiClittle impact on activity,especially at high space velocities due to the long hydrothermal time with less absorbed oxygen species and crystal defects.Overall,these results help clarify methane activa-tion mechanisms and aid the development of more efficient low-cost catalysts.

Solvent Extraction of Yttrium by Task-specific Ionic Liquids Bearing Carboxylic Group

A new kind of hydrophobic ionic liquids [1-alkyl-3-（1-carboxylpropyl）im][PF6] has been synthesized, and their extraction.properties for Y（III） in the nitric acid medium was also investigated. The effects of extractant concentration, equilibrium pH of aqueous phase, salt concentration, temperature etc. were discussed. The results show that this kind of Task-Specific Ionic Liquid （TSIL） needs to be saponified before being used for the Y（III） extraction, and the extraction is-acid dependent,-and the extraction efficiency increases with the aqueous phase acldity decreasing. Furthermore, the loaded organic phase is easy to be stripped; more than 95% Y（III） could be stripped from the loaded organic phase when the stripping acidity is higher than 0.07 mol-L-1. The slope analysis technique is used to investigate the extraction mechanism, and a possible cation-exchange extraction mechanism is proposed in the oresent extraction system.

Hardening effect and precipitation evolution of an isothermal aged Mg-Sm based alloy

The age-hardening behavior and precipitation evolution of an isothermal aged Mg-5Sm-0.6Zn-0.5Zr(wt.%) alloy have been systematically investigated by means of transmission electron microscopy(TEM) and atomic-resolution high-angle annular dark field scanning transmission electron microscopy(HAADF-STEM). The Vickers hardness of the present alloy increases first and then decreases with ageing time. The sample aged at 200 ℃ for 10 h exhibits a peak-hardness of 90.5 HV. In addition to the dominant β_(0)’ precipitate(orthorhombic,a = 0.642 nm, b = 3.336 nm and c = 0.521 nm) formed on {11-20}α planes, a certain number of γ’’ precipitate(hexagonal, a = 0.556 nm and c = 0.431 nm) formed on basal planes are also observed in the peak-aged alloy. Significantly, the basal γ’’ precipitate is more thermostable than prismatic β_(0)’ precipitate in the present alloy. β_(0)’ precipitates gradually coarsened and were even likely to transform into β_(1) phase(face centered cubic, a = 0.73 nm) with the increase of ageing time, which accordingly led to a gradual decrease in number density of precipitates and finally resulted in the decreased hardness and mechanical property in the over-aged alloys.