The influence of yttrium and manganese additions on the degradation and biocompatibility of magnesium-zinc-based alloys:In vitro and in vivo studies

The repair and regeneration of bone defects are highly challenging orthopedic problems.Recently,Mg-based implants have gained popularity due to their unique biodegradation and elastic modulus similar to that of human bone.The aim of our study is to develop a magnesium alloy with a controllable degradation that can closely match bone tissue to help injuries heal in vivo and avoid cytotoxicity caused by a sudden increase in ion concentration.In this study,we prepared and modified Mg-3Zn,Mg-3Zn-1Y,and Mg-2Zn-1Mn by hot extrusion,and used Mg-2.5Y-2.5Nd was as a control.We then investigated the effect of additions of Y and Mn on alloys'properties.Our results show that Mn and Y can improve not only compression strength but also corrosion resistance.The alloy Mg-2Zn-1Mn demonstrated good cytocompatibility in vitro,and for this reason we selected it for implantation in vivo.The degraded Mg-2Zn-1Mn implanted a bone defect area did not cause obvious rejection and inflammatory reaction,and the degradation products left no signs of damage to the heart,liver,kidney,or brain.Furthermore,we find that Mg-2Zn-1Mn can promote an osteoinductive response in vivo and the formation of bone regeneration.

Structural and magnetic properties of micropolycrystalline cobalt thin films fabricated by direct current magnetron sputtering

Pure cobalt(Co)thin films were fabricated by direct current magnetron sputtering,and the effects of sputtering power and pres-sure on the microstructure and electromagnetic properties of the films were investigated.As the sputtering power increases from 15 to 60 W,the Co thin films transition from an amorphous to a polycrystalline state,accompanied by an increase in the intercrystal pore width.Simultaneously,the resistivity decreases from 276 to 99μΩ·cm,coercivity increases from 162 to 293 Oe,and in-plane magnetic aniso-tropy disappears.As the sputtering pressure decreases from 1.6 to 0.2 Pa,grain size significantly increases,resistivity significantly de-creases,and the coercivity significantly increases(from 67 to 280 Oe),which can be attributed to the increase in defect width.Corres-pondingly,a quantitative model for the coercivity of Co thin films was formulated.The polycrystalline films sputtered under pressures of 0.2 and 0.4 Pa exhibit significant in-plane magnetic anisotropy,which is primarily attributable to increased microstress.

Engineering d-band states of(CuGa)_(x)Zn_(1-2x)Ga_(2)S_(4)material for photocatalytic syngas production

The d-band states of catalytic materials participate in adsorbing reactive intermediate species and determine the catalytic behaviors in CO_(2)reduction reactions.However,surface d-band states relating to the photocatalytic CO_(2)reduction reactions behaviors are rarely concerned.Herein,a slightly amount of Cd^(2+)is decorated on the surface of(CuGa)_(x)Zn_(1-2x)Ga_(2)S_(4)material(Cd^(2+)/(CuGa)_(x)Zn_(1-2x)Ga_(2)S_(4))to tune the surface d-band states for improved CO_(2)+2reduction reactions.The Cd/(CuGa)_(x)Zn_(1-2x)Ga_(2)S_(4)is fabricated via the facile ions-exchange method to make that slightly Zn2+is substituted by Cd^(2+).The Cd^(2+)/(CuGa)_(x)Zn_(1-2x)Ga_(2)S_(4)exhibits much enhanced photocatalytic activity in CO_(2)reduction reactions to produce CO and water splitting to produce H_(2).Physical characterizations show that the energy band structure is not changed obviously.Density functional theory reveals that Cd^(2+)/(CuGa)_(x)Zn_(1-2x)Ga_(2)S_(4)possesses a closer shift of d-band center to Fermi level than(CuGa)_(x)Zn_(1-2x)Ga_(2)S_(4),suggesting easier adsorption of CO_(2)reduction reactive intermediates after Cd^(2+)decoration.Further calculations confirm that a relatively reduced adsorption Gibbs energy of reactive intermediates in CO_(2)reduction reaction is required on Zn atoms in Cd^(2+)/(CuGa)_(x)Zn_(1-2x)Ga_(2)S_(4)material,benefiting the photocatalytic CO_(2)reduction reactions.This work engineers surface d-band states by surface Cd^(2+)decoration,which gives an effective strategy to design highly efficient photocatalysts for syngas production.

Engineering of carbon and other protective coating layers for stabilizing silicon anode materials

Silicon(Si)has been attracting extensive attention for rechargeable lithium(Li)‐ion batteries due to its high theoretical capacity and low potential vs Li/Li+.However,it remains challenging and problematic to stabilize the Si materials during electrochemical cycling because of the huge volume expansion,which results in losing electric contact and pulverization of Si particles.Consequently,the Si anode materials generally suffer from poor cycling,poor rate performance,and low coulomb efficiency,preventing them from practical applications.Up‐to‐date,there are numerous reports on the engineering of Si anode materials at microscale and nanoscale with significantly improved electrochemical performances.In this review,we will concentrate on various precisely designed protective layers for silicon‐based materials,including carbon layers,inorganic layers,and conductive polymer protective layer.First,we briefly introduced the alloying and failure mechanism of Si as anode materials upon electrochemical reactions.Following that,representative cases have been introduced and summarized to illustrate the purpose and advancement of protective coating layers,for instance,to alleviate pulverization and improve conductivity caused by volume expansion of Si particles during charge/discharge process,and maintain the surface stability of Si particles to form a stable solid‐electrolyte interphase layer.At last,possible strategies on the protective coating layer for stabilizing silicon anode materials that can be applied in the future have been indicated.

Perspectives in Electrochemical in situ Structural Reconstruction of Cathode Materials for Multivalent-ion Storage

Multivalent-ion(such as Zn^(2+),Mg^(2+),Al^(3+))batteries are considered as a prospective alternative for large-scale energy storage.However,the main problem of cathode materials for multivalent-ion batteries is the sluggish diffusion of multivalent ions.Many cathode materials will self-adjust under electrochemical conditions to achieve the optimal state for multivalent-ion storage.In this review,the significant role of electrochemical in situ structural reconstruction of cathode materials is suggested.The types,basic characteristics,and formation mechanisms of reconstructed phases have been systematically discussed and commented.The most important insight we pointed out is that the cathode materials with loose structures after in situ electrochemical activation are conducive to the reversible diffusion of multivalent ions.Moreover,several crucial issues of electrochemical activation and reconstruction were further analyzed and discussed.The challenges and future perspectives are presented in the final section.

Trimming the Degrees of Freedom via a K^(+) Flux Rectifier for Safe and Long‑Life Potassium‑Ion Batteries

High degrees of freedom(DOF)for K^(+)movement in the electrolytes is desirable,because the resulting high ionic conductivity helps improve potassium-ion batteries,yet requiring support from highly free and flammable organic solvent molecules,seriously affecting battery safety.Here,we develop a K^(+)flux rectifier to trim K ion’s DOF to 1 and improve electrochemical properties.Although the ionic conductivity is compromised in the K^(+)flux rectifier,the overall electrochemical performance of PIBs was improved.An oxidation stability improvement from 4.0 to 5.9 V was realized,and the formation of dendrites and the dissolution of organic cathodes were inhibited.Consequently,the K||K cells continuously cycled over 3,700 h;K||Cu cells operated stably over 800 cycles with the Coulombic efficiency exceeding 99%;and K||graphite cells exhibited high-capacity retention over 74.7%after 1,500 cycles.Moreover,the 3,4,9,10-perylenetetracarboxylic diimide organic cathodes operated for more than 2,100 cycles and reached year-scale-cycling time.We fabricated a 2.18 Ah pouch cell with no significant capacity fading observed after 100 cycles.

Effect of heat treatment on the microstructure and mechanical properties of a multidirectionally forged Mg-Gd-Y-Zn-Zr-Ag alloy

Multidirectional forging(MDF)was successfully applied to fabricate large-size Mg-Gd-Y-Zn-Zr-Ag alloy in this work and effects of T4,T5 and T6 treatments on the microstructure and mechanical properties of the as-forged alloy were analyzed.Results show that dynamic recrystallization(DRX)occurs and second phase particles precipitate along the grain boundary during the MDF process.After annealing treatment(T4),the volume fraction and size of dynamic precipitates slightly increase at a lower temperature(430℃)compared with those of MDFed sample,while they are dissolved into theα-Mg matrix at a higher temperature(450℃).At the meantime,short plate-shaped long-period stacking ordered(LPSO)phases are observed in the DRX grains of the MDFed sample and then dissolved into theα-Mg matrix during annealing at both temperatures.Typical basal texture is identified in the MDFed sample,but the basal pole tilts away from final forging direction and rare-earth texture component with<1121>orientation parallel to penultimate forging direction becomes visible after annealing.The T6 sample annealing at 430℃for 4 h and ageing at 200℃for 34 h exhibits the superior strength and ductility in this study.The ultimate tensile strength,tensile yield strength and elongation to failure,which is 455 MPa,308 MPa and 7.7%,respectively,are overall improved compared with the directly-aged(T5)sample.This paper provides a superior heat treatment schedule to manufacture high-performance large-scale Mg-Gd-Y-Zn-Zr-Ag components for industrial production.

Rational construction of Ag@MIL-88B(V)-derived hierarchical porous Ag-V_(2)O_(5) heterostructures with enhanced diffusion kinetics and cycling stability for aqueous zinc-ion batteries

With the advantages of the multiple oxidation states and highly open crystal structures,vanadium-based composites have been considered as the promising cathode materials for aqueous zinc-ion batteries(ZIBs).However,the inherent inferior electrical conductivity,low specific surface area,and sluggish Zn^(2+)diffusion kinetics of the traditional vanadium-based oxides have greatly impeded their development.Herein,a novel hierarchical porous spindle-shaped Ag-V_(2)O_(5) with unique heterostructures was rationally designed via a simple MOF-assisted synthetic method and applied as stable cathode for aqueous ZIBs.The high specific surface area and hierarchically porous superstructures endowed Ag-V_(2)O_(5) with sufficient electrochemical active sites and shortened the diffusion pathways of Zn^(2+),which was beneficial to accelerate the reversible transport of Zn^(2+)and deliver a high specific capacity(426 mA h g^(-1) at 0.1 A g^(-1) and 96.5%capacity retention after 100 cycles).Meanwhile,the self-built-in electric fields at the heterointerface of Ag-V_(2)O_(5) electrode could strengthen the synergistic coupling interaction between Ag and V_(2)O_(5),which can effectively enhance the electric conductivity and maintain the structural integrity,resulting in superb rate capability(326.1 mA h g^(-1) at 5.0 A g^(-1))and remarkable cycling stability(89.7%capacity retention after 2000 cycles at 5.0 A g^(-1)).Moreover,the reversible Zn^(2+)storage mechanism was further investigated and elucidated by kinetics analysis and DFT calculations.

Influence of Ga and Hg on microstructure and electrochemical corrosion behavior of Mg alloy anode materials

The effects of Hg and Ga on the electrochemical corrosion behavior of Mg-5%Hg (molar fraction) alloys were investigated by the measurement of polarization curves and galvanostatic test. The microstructure of the alloys and the corroded surface of the specimens were investigated by scanning electron microscopy, X-ray diffractometry and emission spectrum analysis. It can be concluded that the addition of 1%Ga (molar fraction) reduces corrosion current density from 26.98 mA/cm2 to 2.34 mA/cm2; while the addition of 1%Hg (molar fraction) increases corrosion current density. The addition of Ga and Hg both promotes the electrochemical activity of the alloys and the influence of Ga is more effective than Hg. Mg-5%Hg-1%Ga alloy has the best electrochemical activity, showing mean potential of -1.992 V. The activation mechanism of the magnesium alloy produced by Hg and Ga was put forward. Magnesium atoms are dissolved in liquid Hg and Ga to form amalgam and undergo severe oxidation at the amalgam/electrolyte interface.

Comprehensive analysis of the full-length transcripts and alternative splicing involved in clubroot resistance in Chinese cabbage

Chinese cabbage is an economically important Brassica vegetable worldwide, and clubroot, which is caused by the soilborne protist plant pathogen Plasmodiophora brassicae is regarded as a destructive disease to Brassica crops. Previous studies on the gene transcripts related to Chinese cabbage resistance to clubroot mainly employed RNA-seq technology,although it cannot provide accurate transcript assembly and structural information. In this study, PacBio RS II SMRT sequencing was used to generate full-length transcriptomes of mixed roots at 0, 2, 5, 8, 13, and 22 days after P. brassicae infection in the clubroot-resistant line DH40R. Overall, 39 376 high-quality isoforms and 26 270 open reading frames(ORFs) were identified from the SMRT sequencing data. Additionally, 426 annotated long noncoding RNAs(lncRNAs),56 transcription factor(TF) families, 1 883 genes with poly(A) sites and 1 691 alternative splicing(AS) events were identified. Furthermore, 1 201 of the genes had at least one AS event in DH40R. A comparison with RNA-seq data revealed six differentially expressed AS genes(one for disease resistance and five for defensive response) that are potentially involved in P. brassicae resistance. The results of this study provide valuable resources for basic research on clubroot resistance in Chinese cabbage.

Deformation mechanism,orientation evolution and mechanical properties of annealed cross-rolled Mg-Zn-Zr-Y-Gd sheet during tension

Mg-6.75Zn-0.57Zr-0.4Y-0.18Gd(wt.%)sheet with typical basal texture was produced by cross rolling and annealing.Room temperature tensile tests were subsequently conducted along rolling direction(RD),transverse direction(TD),and diagonal direction(RD45).Deformation mechanism and orientation evolution during the tension were investigated by quasi-in-situ electron backscatter diffraction observation and in-grain misorientation axis analysis.The results indicate that the activation of deformation mechanism mainly depends on the initial grain orientation.For RD sample,prismatic<a>slip plays an important role in the deformation of grains with<0001>axis nearly perpendicular to the RD.With the<0001>axis gradually tilted towards the RD,basal<a>slip becomes the dominant deformation mode.After the tensile fracture,the initial concentrically distributed{0001}pole is split into double peaks extending perpendicular to the RD,and the randomly distributed{1010}pole becomes parallel to the RD.The evolution in{0001}and{1010}poles during tension is related to the lattice rotation induced by basal<a>slip and prismatic<a>slip,respectively.TD and RD45 samples exhibit similar deformation mechanism and orientation evolution as the RD sample,which results in the nearly isotropic mechanical properties in the annealed cross-rolled sheet.

Segregation of Si and Mg at Fe(110)/Al(110) Interface

The interface structure and electronic properties of Fe(110)/Al(110) are investigated by the first-principles plane-wave pseudopotential method. The interface segregation position of Si and Mg is determined, and the effect of Mg and Si on the interface binding of Fe(110)/Al(110) is analyzed by combining the work of separation and charge density. The results show that the Fe(110)/Al(110) interface energy of FeHollow coordination is smaller and the interface structure is more stable. The Fe(110)/Al(110) interface separation surface in the form of Fe-Hollow coordination appears at the sub interface layer on the side of Al(110)near the interface. The interface structure of Mg and Si segregation is similar to that of undoped alloy elements.The calculations also suggest that Mg and Si segregate on the Al(110) side of the interface and occupy the Al lattice on the Al(110) side. The segregation of Mg and Si elements will reduce the interface binding, primarily because the Fe-Si bond and Fe-Mg bond are weaker than Fe-Al bond.

Experimental Investigation of Crystal Structure of Zr 0.98 NiGe 2.94 and Phase Equilibria in Zr-Ni-Ge System

Based on the results of electron probe microanalysis(EPMA)and X-ray diffraction(XRD),the isothermal sections of Zr-Ni-Ge ternary system at 973 K and 1173 K were constructed through alloy sampling approach.It is worth noting that the crystallographic information of the formerly reportedτ2(Zr_(0.98)NiGe_(2.94))was determined,which belongs to the space group Pbcm(No.57).Besides the formerly reported ternary compounds,τ1(Zr_(6)Ni_(16)Ge_(7)),τ_(2)(Zr_(0.98)NiGe_(2.94)),τ_(3)(Zr_(3)Ni_(4)Ge_(4)),τ_(4)(ZrNiGe)andτ_(5)(Zr_(2)Ni_(0.54)Ge_(0.46)),a new ternary phase namedτ_(6)with the composition of Zr_(39)Ni_(18)Ge_(43)was primarily detected in this work.In addition,an invariant reaction Ni_(5)Ge_(3)+τ_(4)τ_(1)+τ_(3)between 973 K and 1173 K was deduced.

Microstructure and mechanical properties of Fe/NbC composite layer prepared by in-situ reaction

NbC ceramic surface-reinforced steel matrix composites were prepared by an in-situ reaction method at different temperatures(1,050℃,1,100℃and 1,150℃)for different times(1 h,2 h and 3 h).The phase constitution,microstructure and fracture morphology of NbC ceramic surface-reinforced steel matrix composites were analyzed by XRD,SEM and EDS,and the effects of the in-situ reaction temperature and time on the mechanical properties were systematically studied.The results indicate that the NbC reinforcement layer is formed through the reaction between Nb atoms and carbon atoms diffused from the steel matrix to the Nb plate.The thickness of this reinforcement layer increases as the reaction time prolongs.Additionally,an increase in reaction temperature results in a thicker reinforcement layer,although the rate of increase gradually decreases.The relationship among the thickness of the Nb C reinforcement layer,the reaction time and temperature was established by data fitting.The optimal tensile performance is achieved at 1,100℃for 1 h,with a tensile strength of 228 MPa.It is also found that the defects between the reinforcement layer and the steel matrix are related to reaction temperature.At 1,100℃,these defects are minimal.Fracture mostly occurs in the NbC reinforced layer of the composites,and the fracture mode is characterized by typical intergranular brittle fracture.

Bio-inspired synthesis of nanomaterials and smart structures for electrochemical energy storage and conversion

Traditional synthetic methodologies are confronted with great challenges to fabricate complex nanomaterials with delicate design,high efficiency and excellent sustainability.During the past decade,bio-inspired synthesis has been extensively applied as an effective and efficient strategy for the fabrication of nanomaterials and nanostructures.Mimicking electrode materials at nanoscale in the aspect of either structure or functionality has been receiving surging interest because of their incomparable advantages and outperforming properties.In this review,we summarize the recent progresses on bio-inspired synthesis of nanomaterials and smart structures in the field of energy storage and conversion.Firstly,an overall introduction of bio-inspired synthetic strategies will be presented,with focus on the biotemplates and bio-resources.Following that,a library of complex mimicking structures featured by high-order,hierarchical porosity,or bionic function are introduced,with discussion on their chemical and physical properties associated with the structure.The enhanced electrochemical properties such as energy density,cycling stability,etc.in different electrochemical systems will be also discussed.At last,we will expand the perspectives regarding the advantages and limitations of bioinspired strategy and possible solutions in the future.

Preparation of FVS1212/FVS0812 materials and its mechanical properties

FVS1212/FVS0812 material was prepared by adding FVS1212 powder into FVS0812 powder. The structure and mechanical properties of materials were studied by means of X-Ray, tensile measurement, OM and SEM. The results show that adding proper content FVS1212 powders can improve the tensile strength of FVS0812 aluminum at room temperature and elevated temperature, and that the elongation of FVS1212/FVS0812 material is better than that of FVS1212 aluminum.

Covalent Organic Framework with 3D Ordered Channel and Multi-Functional Groups Endows Zn Anode with Superior Stability

Achieving a highly robust zinc(Zn)metal anode is extremely important for improving the performance of aqueous Zn-ion batteries(AZIBs)for advancing“carbon neutrality”society,which is hampered by the uncontrollable growth of Zn dendrite and severe side reactions including hydrogen evolution reaction,corrosion,and passivation,etc.Herein,an interlayer containing fluorinated zincophilic covalent organic framework with sulfonic acid groups(COF-S-F)is developed on Zn metal(Zn@COF-S-F)as the artificial solid electrolyte interface(SEI).Sulfonic acid group(-SO_(3)H)in COF-S-F can effectively ameliorate the desolvation process of hydrated Zn ions,and the three-dimensional channel with fluoride group(-F)can provide interconnected channels for the favorable transport of Zn ions with ion-confinement effects,endowing Zn@COF-S-F with dendrite-free morphology and suppressed side reactions.Consequently,Zn@COF-S-F symmetric cell can stably cycle for 1,000 h with low average hysteresis voltage(50.5 m V)at the current density of 1.5 m A cm^(-2).Zn@COF-S-F|Mn O_(2)cell delivers the discharge specific capacity of 206.8 m Ah g^(-1)at the current density of 1.2 A g^(-1)after 800 cycles with high-capacity retention(87.9%).Enlightening,building artificial SEI on metallic Zn surface with targeted design has been proved as the effective strategy to foster the practical application of high-performance AZIBs.

Effect of minor Sc and Zr addition on microstructures and mechanical properties of Al-Zn-Mg-Cu alloys

Three kinds of Al-Zn-Mg-Cu based alloys with 0.22%, 0.36%(Sc+Zr) (mass fraction, %), and without Sc, Zr addition were prepared by ingot metallurgy. By using optical microscopy, transmission electronic microscopy and scanning electron microscopy, the effects of microalloying elements of Sc, Zr on the microstructure of super-high-strength Al-Zn-Mg-Cu alloys related to mechanical properties were investigated. The tensile properties and microstructures of the studied alloys under different heat treatment conditions were studied. The addition of minor Sc, Zr results in the formation of Al3(Sc,Zr) particles. These particles are highly effective in refining the microstructures, retarding recrystallization, pinning dislocations and subboundaries. The strength of Al-Zn-Mg-Cu alloys was greatly improved by simultaneously adding minor Sc, Zr, meanwhile the ductility of the studied alloys remains at a higher level. The 0.36%(Sc+Zr) alloys gain the optimal properties after 465 ℃/h solution and 120 ℃/24 h aging. The increment of strength is mainly due to strengthening of fine grain and substructure and precipitation of Al3(Sc, Zr) particles.

Induction plasma spheroidization of tungsten and molybdenum powders

The melting, evaporation and oxidation behaviors as well as the solidification phenomena of tungsten and molybdenum in induction plasma were studied. Scanning electron microscopy was used to examine the morphology and the cross section of plasma-processed powders. X-ray diffraction was used to analyze the oxides formed on the particle surface of these two metals. The influence of spray chamber pressure on the spheroidization and oxidation phenomena was discussed. The results show that fewer Mo particles than W particles are spheroidized at the same powder feed rate under the same plasma spray condition although molybdenum has a lower melting point. A small fraction of tungsten is evaporized and condensed either on the surface of tungsten particles nearby or on the wall of spray chamber. Tungsten oxides were found in tungsten powder processed under soft vacuum condition. Extremely large grains form inside some spheroidized particles of tungsten powder.

Effect of minor Sc and Zr on microstructure and mechanical properties of Al-Zn-Mg-Cu alloy

A series of Al-8.2Zn-2.1Mg-2.3Cu based as-cast alloys and some plates with thickness of 4 mm containing minor Sc and Zr were prepared. The effect of joint addition of minor Sc and Zr on microstructure and mechanical properties of Al-Zn-Mg-Cu alloys were investigated by using OM, SEM with EDS and TEM. The results show that by adding 0.18% Zr (mass fraction) in the cast alloy, the grains can be refined to a certain degree, and by adding 0.18% Sc a little as well. Adding Sc and Zr can generate strong grain refinement effect and obtain a fine equiaxed grain structure, because primary Al3(ScxZr1- )precipitation forms in front of the x a-Al grains. The microstructure and tensile test results show that 0.18% addition of Zr does not bring higher tensile strength and elongation to the alloy of adding Sc, but a better inhibition to recrystallization. Recrystallization inhibiting effect is the strongest in the alloys with joint addition of Sc and Zr. When the content of Zr is unchanged, the strength and elongation of the alloys increase with increasing Sc addition. The increase of strength and elongation in the alloys is related to the refine grain strengthening, precipitation particles strengthening and substructure strengthening principles.