可降解Fe@Fe-Zn骨组织工程支架体外生物相容性研究

目的以多孔铁为基体,利用脉冲电沉积制备可降解多孔Fe@Fe-Zn复合材料骨组织工程支架,以期提高材料的降解速率和抗菌性能。方法通过调节脉冲频率,得到不同Zn含量的Fe-Zn合金层;使用电子探针、X射线衍射仪、扫描电镜来研究材料的元素含量、相组成和显微结构;通过压缩测试考察支架的力学性能;用体外浸泡来考察材料的降解性能;用浸提液培养分析材料对小鼠胚胎成骨细胞的黏附铺展和细胞活性的影响;用浸提液和直接培养来探究材料的抗大肠杆菌性能。结果随脉冲频率增加,合金中Zn含量减小;不同合金均为单一的α(Fe)相;电沉积组织致密,杂质含量低;Zn含量为7.5%(均以质量分数计)时,支架抗压屈服强度较多孔铁提升6%;复合材料的降解速率为0.44~0.48 mm/a,较多孔铁有显著改善;复合材料浸提液在稀释到25%(体积分数)时,表现出良好的细胞相容性,且随Zn含量增加,细胞活性增强;Zn含量为7.5%时,材料的抗菌性能最好。结论通过电沉积制备的Fe@Fe-Zn支架的腐蚀速率相较于多孔铁有明显提高。随合金层中Zn含量的增加,其细胞活性增强,抗菌性能提高。Fe@Fe-Zn有望发展为可广泛应用的可降解骨组织工程支架材料。

Characterizations on the instantaneously formed Ni-containing intermetallics in magnesium alloys

Instantaneous reactions of Al,Mn,Zn,Zr and Y with Ni by mixing the prepared Mg-8Al-0.4Mn,Mg-6Zn-2Y-0.5Zr and Mg-0.6Ni melts were investigated in this work to reveal the underlying mechanisms of their effects on the removal of Ni impurity.The results indicate three Ni-containing intermetallics,namely Al_(4)NiY,Al_(4)Ni(Y,Zr)and Al_(31)Ni_(2)Mn_(6).The former two phases present lath-like and have a relatively larger size(>20μm in length)than the latest one which is granular with the diameter of∼120 nm.This illustrates that Al and Y(/Zr)can efficiently remove Ni by forming Al_(4)NiY or Al_(4)Ni(Y,Zr)which would precipitate to the bottom of the melt.Furthermore,adding Y into Mg-Al based alloys can simultaneously remove Fe and Ni,which contributes their excellent corrosion resistance.Finally,this paper proposes two methods helped to efficiently remove Ni for both Mg-Al based alloys and Al-free Mg alloys,and both of them are also benefit to improve alloys’strength.

High-entropy L1_(2)-Pt(FeCoNiCuZn)_(3) intermetallics for ultrastable oxygen reduction reaction

Enhancing the stability of Pt-based electrocatalysts for the sluggish cathodic oxygen reduction reaction(ORR)is critical for proton exchange membrane fuel cells(PEMFCs).Herein,high-entropy intermetallic(HEI)L1_(2)-Pt(FeCoNiCuZn)3is designed for durable ORR catalysis.Benefiting from the unique HEI structure and the enhanced intermetallic phase stability,Pt(FeCoNiCuZn)3/C nanoparticles demonstrate significantly improved stability over Pt/C and PtCu_(3)/C catalysts.The Pt(FeCoNiCuZn)3/C exhibits a negligible decay of the half-wave potential during 30,000 potential cycles from 0.6 to 1.0 V,whereas Pt/C and PtCu_(3)/C are negatively shifted by 46 and 36 m V,respectively.Even after 10,000 cycles at potential up to 1.5 V,the mass activity of Pt(FeCoNiCuZn)3/C still shows~70%retention.As evidenced by the structural characterizations,the HEI structure of Pt(FeCoNiCuZn)3/C is well maintained,while PtCu_(3)/C nanoparticles undergo severe Cu leaching and particle growth.In addition,when assembled Pt(FeCoNiCuZn)3/C as the cathode in high-temperature PEMFC of 160℃,the H_(2)-O_(2)fuel cell delivers almost no degradation even after operating for 150 h,demonstrating the potential for fuel cell applications.This work provides a facile design strategy for the development of high-performance ultrastable electrocatalysts.

Sub-nanometer Pt_(2)In_(3) intermetallics as ultra-stable catalyst for propane dehydrogenation

Pt-based catalysts are the typical industrial catalysts for propane dehydrogenation(PDH),which still suffer from insufficient lo ng-term durability due to the structu ral instability and coke deposition.A commercial γ-Al_(2)O_(3) supported thermally robust sub-nanometer Pt2In3intermetallic catalyst with atomically ordered structure and rigorously separated Pt single atoms was fabricated,which showed outstanding robustness in 240 h long-term operation at 600℃ with the deactivation rate constant kdas low as0.00078 h^(-1), ranking among the lowest reported values.Based on various in situ characterizations and theoretical calculations,it was proved that the catalyst stability not only resulted from the separated Pt single-atom sites but also significantly affected by the distance of adjacent Pt atoms.An increasing distance to 3.25 A in the Pt_(2)In_(3)could induce a weak π-adsorption configuration of propylene on Pt sites,which facilitated the desorption of propylene and restrained the side reactions like coking.

Porous TiFe_(2) intermetallic compound fabricated via elemental powder reactive synthesis

Porous intermetallics show potential in the field of filtration and separation as well as in the field of catalysis.Herein,porous Ti Fe2intermetallics were fabricated by the reactive synthesis of elemental powders.The phase transformation and pore formation of porous TiFe2intermetallics were investigated,and its corrosion behavior and hydrogen evolution reaction(HER)performance in alkali solution were studied.Porous TiFe2intermetallics with porosity in the range of 34.4%-56.4%were synthesized by the diffusion reaction of Ti and Fe elements,and the pore formation of porous TiFe2intermetallic compound is the result of a combination of the bridging effect and the Kirkendall effect.The porous TiFe2samples exhibit better corrosion resistance compared with porous 316L stainless steel,which is related to the formation of uniform nanosheets on the surface that hinder further corrosion,and porous TiFe2electrode shows the overpotential of 220.6 and 295.6 mV at 10 and 100 mA·cm-2,suggesting a good catalytic performance.The synthesized porous Fe-based intermetallic has a controllable pore structure as well as excellent corrosion resistance,showing its potential in the field of filtration and separation.

Optimization of chemistry and process parameters for control of intermetallic formation in Mg sludges

Intermetallic formation in sludge during magnesium(Mg)melting,holding and high pressure die casting practices is a very important issue.But,very often it is overlooked by academia,original equipment manufacturers(OEM),metal ingot producers and even die casters.The aim of this study was to minimize the intermetallic formation in Mg sludge via the optimization of the chemistry and process parameters.The Al8Mn5 intermetallic particles were identified by the microstructure analysis based on the Al and Mn ratio.The design of experiment(DOE)technique,Taguchi method,was employed to minimize the intermetallic formation in the sludge of Mg alloys with various chemical compositions of Al,Mn,Fe,and different process parameters,holding temperature and holding time.The sludge yield(SY)and intermetallic size(IS)was selected as two responses.The optimum combination of the levels in terms of minimizing the intermetallic formation were 9 wt.%Al,0.15 wt.%Mn,0.001 wt.%(10 ppm)Fe,690℃ for the holding temperature and holding at 30 mins for the holding time,respectively.The best combination for smallest intermetallic size were 9 wt.%Al,0.15 wt.%Mn,0.001 wt.%(10 ppm)Fe,630℃ for the holding temperature and holding at 60 mins for the holding time,respectively.Three groups of sludge factors,Chemical Sludge(CSF),Physical Sludge(PSF)and Comprehensive Sludge Factors(and CPSF)were established for prediction of sludge yields and intermetallic sizes in Al-containing Mg alloys.The CPSF with five independent variables including both chemical elements and process parameters gave high accuracy in prediction,as the prediction of the PSF with only the two processing parameters of the melt holding temperature and time showed a relatively large deviation from the experimental data.The Chemical Sludge Factor was primarily designed for small ingot producers and die casters with a limited melting and holding capacity,of which process parameters could be fixed easily.The Physical Sludge Factor could be used for mass production with a single type of Mg alloy,in which the chemistry fluctuation might be negligible.In large Mg casting suppliers with multiple melting and holding furnaces and a number of Mg alloys in production,the Comprehensive Sludge Factor should be implemented to diminish the sludge formation.

Ultrafine ordered L1_(2)-Pt-Co-Mn ternary intermetallic nanoparticles as high-performance oxygen-reduction electrocatalysts for practical fuel cells

The long-range periodically ordered atomic structures in intermetallic nanoparticles(INPs)can significantly enhance both the electrocatalytic activity and electrochemical stability toward the oxygen reduction reaction(ORR)compared to the disordered atomic structures in ordinary solid-solution alloy NPs.Accordingly,through a facile and scalable synthetic method,a series of carbon-supported ultrafine Pt_3Co_(x)Mn_(1-x)ternary INPs are prepared in this work,which possess the"skin-like"ultrathin Pt shells,the ordered L1_(2) atomic structure,and the high-even dispersion on supports(L1_(2)-Pt_3Co_(x)Mn_(1-x)/~SPt INPs/C).Electrochemical results present that the composition-optimized L1_(2)-Pt_3Co_(0.7)Mn_(0.3)/~SPt INPs/C exhibits the highest electrocata lytic activity among the series,which are also much better than those of the pristine ultrafine Pt/C.Besides,it also has a greatly enhanced electrochemical stability.In addition,the effects of annealing temperature and time are further investigated.More importantly,such superior ORR electrocatalytic performance of L1_(2)-Pt_3Co_(0.7)Mn_(0.3)/~SPt INPs/C are also well demonstrated in practical fuel cells.Physicochemical characterization analyses further reveal the major origins of the greatly enhanced ORR electrocata lytic performance:the Pt-Co-Mn alloy-induced geometric and ligand effects as well as the extremely high L1_(2) atomic-ordering degree.This work not only successfully develops a highly active and stable ordered ternary intermetallic ORR electrocatalyst,but also elucidates the corresponding"structure-function"relationship,which can be further applied in designing other intermetallic(electro)catalysts.

SYNTHESIS OF INTERMETALLICS BY MECHANICAL ALLOYING

Mechanical alloying (MA), a solid-state powder processing method, is a 'far from equilibrium' synthesis technique which allows development of novel crystal structures and microstructures, leading to enhanced physical and mechanical properties. The ability to synthesize a variety of alloy phases including supersaturated solid solutions, nanocrystalline structures, amorphous phases and intermetallic compounds themselves is discussed. No extension of solubility using MA has been observed in the intermetallics studied. Nanostructured grains were observed in all compositions. Long time milling generally resulted in amorphous phase formation in large part because of the increase in grain boundary energy/mole with reduced grain size; good agreement with the Miedema model for amorphization was obtained in the Al-Fe system. Generally an anneal was required to form the intermetallic after MA; however,intermetallics with a large negative enthalpy of formation were detected in the MA condition. A study of the hot isostatic pressing of γ-TiAl powders produced by MA demonstrated that full density can be achieved at least 400℃ below the normal temperature required for conventional powder, that is 725℃ or below. Nanometered sized grains (≤100nm)were observed after HIP'ing up to 850℃.

EFFECT OF ALLOYING ELEMENTS ON SENSITIVITY TO ENVIRONMENTAL EMBRITTLEMENT OF L1_2 INTERMETALLICS

The effect of Zr doping in Ni 3Al and B doping in Co 3Ti intermetallics on the sensitivity to moisture induced environmental embrittlement and on the hydrogen diffusivity was investigated. The results show that both B in Co 3Ti and Zr in Ni 3Al do not reduce the hydrogen diffusivity along the grain boundaries, therefore can not suppress the moisture induced environmental embrittlement. The above mentioned behavior of Zr in Ni 3Al and B in Co 3Ti is attributed to the fact that Zr and B are not segregated on the grain boundaries.

INTERMETALLICS AS SUBSTITUTES FOR SUPERALLOYS

The application advances of TiAl, Ti3Al and Ni3Al base aUoys were denumstrated by Central Iron and Steel Research Institute, China. The recent research progresses on improving the reliability of cast TiAI were mainly presented and discussed. The characteristics of the self-oriented lamellar microstructure in cast TiAI were investigated in both as cast and as HlPed states. Based on the mechanical anisotropy of the cast lamellar microstructure, the component specific microstrueture design was proposed for a better performance and reliability of cast TiAl.

STUDY OF THE EFFECT OF BORON CONTENT ON THE ORDERED EXTENT OF THE Ni_3Al INTERMETALLICS COMPOUND BY AP-FIM

By using AP-FIM the varity of the ordered degree of Ni_3Al with L1_2 structure with B content was studied. The possibility of boron improving ductility was also discussed from bonding between Ni and Al atoms, and antisite defects in Ni_3Al. The extent of ordering is reduced with an increase in boron content and the autisite defects are most obvious for 0.52at.K B-doped sample that has the best ductility. Some results were verified by X-ray diffraction non. The addition of boron not only influences electron environment at grain boundary but also in the interior of Ni_3Al gm ins, the latter is favorable to improve the ductility of Ni_3Al grains.

Influence of mechanical alloying time on the properties of Fe_3Al intermetallics prepared by spark plasma sintering

The Fe3Al-based intermetallics were prepared by mechanical alloying and spark plasma sintering （SPS）, and the influence of milling time on the properties of materials was investigated. The phase identification was investigated by X-ray, and the surface morphology and fractography were observed by scanning electron microscope （SEM）. The mechanical properties such as bending strength, strain, and microhardness were tested. The results show that Fe reacts with Al completely to form Fe3Al during short SPS processing time. The relative densities of the sintered samples were nearly 100%. The mechanical properties of the sintered samples can be improved along with the milling time. The representative values are the bend strength of 1327 MPa and the microhardness of 434.

R&D STATUS ON INTERMETALLICS IN CHINA

This paper briefiy introduces the R&D of intermetallics in China. R&D on intermetallics in a national scale in China began near ten years ago. The investigation in past years focused on the fundamental research and materials development. A significant progress has been made. Various components that made of Ti3Al Ni3Al, TiAl and Fe3Al have been successfully manufactured Some of them have been evaluted. It is expected that some intermetallic alloys will be produced in an industrial scale in the near future.

A COMPONENT-SPECIFIC ALLOY DESIGN OF TiAl INTERMETALLICS

The metallographic observation and analyses of TiAl alloy cast ingots revealed that the preferably arranged γ/α_2 lamellar microstructure can be obtained in columnar dendritic cast ingot through controlling the Ti/Al atomic ratio. The experiments conf irmed that the preferably arranged γ/α_2 lamellar microstructure has excellent tensile strength and fracture toughness and tolerant tensile plasticity when the stress is applied parallel to the γ/α_2 interface.Based on these results and the working condition of the turbine blades,a component-specific alloy design has been suggested.

Phase stability,elastic properties and electronic structures of Mg-Y intermetallics from first-principles calculations

The phase stability,elastic properties and electronic structures of three typical Mg-Y intermetallics including Mg_(24)Y_(5),Mg_(2)Y and MgY are systematically investigated using first-principles calculations based on density functional theory.The optimized structural parameters including lattice constants and atomic coordinates are in good agreement with experimental values.The calculated cohesive energies and formation enthalpies show that either phase stability or alloying ability of the three intermetallics is gradually enhanced with increasing Y content.The single-crystal elastic constants C_(ij) of Mg-Y intermetallics are also calculated,and the bulk modulus B,shear modulus G,Young's modulus E,Poisson ratio v and anisotropy factor A of polycrystalline materials are derived.It is suggested that the resistances to volume and shear deformation as well as the stiffness of the three intermetallics are raised with increasing Y content.Besides,these intermetallics all exhibit ductile characteristics,and they are isotropic in compression but anisotropic to a certain degree in shear and stiffness.Comparatively,Mg_(24)Y_(5) presents a relatively higher ductility,while MgY has a relatively stronger anisotropy in shear and stiffness.Further analysis of electronic structures indicates that the phase stability of Mg-Y intermetallics is closely related with their bonding electrons numbers below Fermi level.Namely,the more bonding electrons number below Fermi level corresponds to the higher structural stability of Mg-Y intermetallics.

Preparation and properties of the Ni-Al/Fe-Al intermetallics composite coating produced by plasma cladding

A novel approach to produce an intermetallic composite coating was put forward.The microstructure,microhardness,and dry-sliding wear behavior of the composite coating were investigated using X-ray diffraction （XRD）,scanning electron microscopy （SEM）,energy dispersive spectrum （EDS） analysis,microhardness test,and ball-on-disc wear experiment.XRD results indicate that some new phases FeAl,Fe0.23Ni0.77Al,and Ni3Al exit in the composite coating with the Al2O3 addition.SEM results show that the coating is bonded with carbon steel metallurgically and exhibits typical rapid directional solidification structures.The Cr7C3 carbide and intermetallic compounds co-reinforced composite coating has a high average hardness and exhibits an excellent wear resistance under dry-sliding wear test compared with the Cr7C3 carbide-reinforced composite coating.The formation mechanism of the intermetallic compounds was also investigated.

First-principles calculations of structural,elastic and electronic properties of AB_(2)type intermetallics in Mg–Zn–Ca–Cu alloy

Electronic structure and elastic properties of MgCu_(2),Mg_(2)Ca and MgZn_(2)phases were investigated by means of first-principles calculations from CASTEP program based on density functional theory(DFT).The calculated lattice parameters were in good agreement with the experimental and literature values.The calculated heats of formation and cohesive energies shown that MgCu_(2)has the strongest alloying ability and structural stability.The elastic constants of MgCu_(2),Mg_(2)Ca and MgZn_(2)phases were calculated,the bulk moduli,shear moduli,Young's moduli and Poisson's ratio were derived.The calculated results shown that MgCu_(2),Mg_(2)Ca and MgZn_(2)are all ductile phases.Among the three phases,MgCu_(2)has the strongest stiffness and the plasticity of MgZn_(2)phase is the best.The density of states(DOS),Mulliken electron occupation number and charge density difference of MgCu_(2),Mg_(2)Ca and MgZn_(2)phases were discussed to analyze the mechanism of structural stability and mechanical properties.

ADVANCE IN Ti_3 Al AND TiAl INTERMETALLICS RESEARCH IN CISRI

Recent work on Ti_3Al base alloy,TAC-1, developed in CISRI, including investigations of effects of modification in alloying and TMP on microstructural characteristics and mechanical behaviour,indicates that alloy TAC -1 is very promising structural material for a number of elevated temperature applications. Stuody dealing with a reverse relation between RT ductility and toughness found on TiA base alloy, TAC-2, led to development of a special heat treatment technique for producing a fine filly lamellar microstructure (FFL), which gives a high and balancing ductility and toughness. This is also of significance for promoting engineering applications of this alloy.

STATUS UP DATE ON USE OF INTERMETALLICS FOR STRUCTURAL APPLICATIONS

Several key issues related to ductility and fracture toughness limiting the application of intermetallics were discussed. Progress made in resolving some of the issues was discussed. The paper addresses design methodology for low defect tolerant materials. Impact resistance of NiAl under engine simulative conditions has been studied. The impact test results demonstrated a need for materials possessing improved impact resistance for turbine blade and vane applications. Some of the production implementation issues were also discussed.

Intermetallics and phase transformations of the Zr-1.0Sn-0.3Nb-0.3Fe-0.1Cr alloy

Intermetallics and phase transformations of the zirconium-based alloy, Zr-1.0Sn-0.3Nb-0.3Fe-0.1Cr, were investigated by conventional X-ray diffraction （XRD）, differential scanning calorimetry （DSC）, and dilation measurement. Three types of precipitates, namely, （ZrNb）2Fe, Zr（CrFe）2, and Zr3Fe, were detected by XRD. The cubic Ti2Ni-type （ZrNb）2Fe was found to be the main precipitate in the alloy, and it was proposed to dissolve at 861℃, whereas Zr3Fe dissolved at 780℃ and Zr（CrFe）2 at 814℃. No precipitates were observed at a temperature higher than 900℃. The transformation-start temperature of α-Zr → β-Zr was reconfirmed to be 780℃, and the end temperature of α-Zr →βZr was determined to be 955℃. The dilation result also revealed that the martensitic transformation-start temperature, Ms, and the finish temperature, Mf, of this alloy were 741℃ and 645℃, respectively.