Effects of friction stir processing and nano-hydroxyapatite on the microstructure,hardness,degradation rate and in-vitro bioactivity of WE43 alloy for biomedical applications

Nowadays,magnesium alloys are emerging in biomedical implants for their similar properties to natural bones.However,the rapid degradation of magnesium alloys in biological media hinders successful implantation.Refinement of microstructure,as well as reinforcement particles can significantly improve the degradation rate.In this work,multi-pass friction stir processing(FSP)was proposed to synthesize WE43/nano-hydroxyapatite(n HA)surface composite,the microstructure,reinforced particle distribution,micro-hardness,corrosion behavior and in-vitro bioactivity were studied.The subsequent FSP passes of WE43 alloy and WE43/n HA composite refined the grain size which was reduced by 94.29%and 95.92%(2.63 and 1.88μm,respectively)compared to base metal after three passes.This resulted in increasing the microhardness by 120%(90.86 HV0.1)and 135%(105.59 HV0.1)for the WE43 and WE43-n HA,respectively.It is found that increasing FSP passes improved the uniform distribution of n HA particles within the composite matrix which led to improved corrosion resistance and less degradation rate.The corrosion rate of the FSPed WE43/n HA composite after three passes was reduced by 38.2%(4.13 mm/year)and the degradation rate was reduced by 69.7%(2.87 mm/y).This is attributed to secondary phase(Mg24Y5and Mg41Nd5)particle fragmentation and redistribution,as well as a homogeneous distribution of n HA.Additionally,the growing Ca-P and Mg(OH)2layer formed on the surface represented a protective layer that reduced the degradation rate.The wettability test revealed a relatively hydrophilic surface with water contact angle of 49.1±2.2°compared to 71.2±2.1°for base metal.Also,biomineralization test showed that apatite layer grew after immersion 7d in simulated body fluid with atomic ratio of Ca/P 1.60 approaching the stoichiometric ratio(1.67)indicating superior bioactivity of FSPed WE43/n HA composite after three passes.These results raise that the grain refinement by FSP and introduction of n HA particles significantly improved the degradation rate and in-vitro bioactivity of WE43 alloy for biomedical applications.

A review of linear friction welding of Ni -based superalloys

Ni-based superalloys are one of the most important materials employed in high-temperature applications within the aerospace and nuclear energy industries and in gas turbines due to their excellent corrosion,radiation,fatigue resistance,and high-temperature strength.Linear friction welding(LFW)is a new joining technology with near-net-forming characteristics that can be used for the manu-facture and repair of a wide range of aerospace components.This paper reviews published works on LFW of Ni-based superalloys with the aim of understanding the characteristics of frictional heat generation and extrusion deformation,microstructures,mechanical proper-ties,flash morphology,residual stresses,creep,and fatigue of Ni-based superalloy weldments produced with LFW to enable future optim-um utilization of the LFW process.

Effects of laser processing parameters on solidification microstructures of ternary Al_2O_3/YAG/ZrO_2 eutectic in situ composite and its thermal property

Rapid surface resolidification with a high powered CO2-laser was performed in preparing directionally solidified Al2O3/YAG/ZrO2 ternary eutectic ceramic in situ composite.The effects of laser processing parameters on the solidification microstructure characteristics and thermal properties were studied by scanning electron microscopy(SEM),energy dispersive spectroscopy(EDS),X-ray diffractometry(XRD)and synthetically thermal analysis(STA).Detailed investigations of the influence of laser power and scanning rate on the preparation and microstructural parameters of the ternary eutectic were presented.Moreover, the eutectic phase separation rule at high temperature was discussed.The results indicate that solidification microstructure of the ternary eutectic composite is greatly influenced by the laser processing parameters.The synthetically thermal analysis shows that the eutectic temperature of ternary Al2O3/YAG/ZrO2 composite is 1 738℃,well matching the phase diagram of Al2O3-Y2O3-ZrO2.

Effect of hot isostatic pressure on the microstructure and tensile properties of γ'-strengthened superalloy fabricated through induction-assisted directed energy deposition

The microstructure characteristics and strengthening mechanism of Inconel738LC(IN-738LC) alloy prepared by using induction-assisted directed energy deposition(IDED) were elucidated through the investigation of samples subjected to IDED under 1050℃ preheating with and without hot isostatic pressing(HIP,1190℃,105 MPa,and 3 h).Results show that the as-deposited sample mainly consisted of epitaxial columnar crystals and inhomogeneously distributed γ’ phases in interdendritic and dendritic core regions.After HIP,grain morphology changed negligibly,whereas the size of the γ’ phase became increasingly even.After further heat treatment(HT,1070℃,2 h + 845℃,24 h),the γ’ phase in the as-deposited and HIPed samples presented a bimodal size distribution,whereas that in the as-deposited sample showed a size that remained uneven.The comparison of tensile properties revealed that the tensile strength and uniform elongation of the HIP + HTed sample increased by 5% and 46%,respectively,due to the synergistic deformation of bimodal γ’phases,especially large cubic γ’ phases.Finally,the relationship between phase transformations and plastic deformations in the IDEDed sample was discussed on the basis of generalized stability theory in terms of the trade-off between thermodynamics and kinetics.

Tuning the surface electronic structure of noble metal aerogels to promote the electrocatalytic oxygen reduction

The sluggish kinetics of the oxygen reduction reaction(ORR)is the bottleneck for various electrochemical energy conversion devices.Regulating the electronic structure of electrocatalysts by ligands has received particular attention in deriving valid ORR electrocatalysts.Here,the surface electronic structure of Ptbased noble metal aerogels(NMAs)was modulated by various organic ligands,among which the electron-withdrawing ligand of 4-methylphenylene effectively boosted the ORR electrocatalysis.Theoretical calculations suggested the smaller energy barrier for the transformation of O^(*) to OH^(*) and downshift the d-band center of Pt due to the interaction between 4-methylphenylene and the surface metals,thus enhancing the ORR intrinsic activity.Both Pt3Ni and Pt Pd aerogels with 4-methylphenylene decoration performed significant enhancement in ORR activity and durability in different media.Remarkably,the 4-methylphenylene modified Pt Pd aerogel exhibited the higher halfwave potential of 0.952 V and the mass activity of 10.2 times of commercial Pt/C.This work explained the effect of electronic structure on ORR electrocatalytic properties and would promote functionalized NMAs as efficient ORR electrocatalysts.

Comparative review of corrosion-resistant coatings on metal bipolar plates of proton exchange membrane fuel cells

In the realm of proton exchange membrane fuel cells(PEMFCs),the bipolar plates(BPs)are indispensable and serve pivotal roles in distributing reactant gases,collecting current,facilitating product water removal,and cooling the stack.Metal BPs,characterized by outstanding manufacturability,cost-effectiveness,higher power density,and mechanical strength,are emerging as viable alternatives to traditional graphite BPs.The foremost challenge for metal BPs lies in enhancing their corrosion resistance and conductivity under acidic conditions,necessitating the application of various coatings on their surfaces to ensure superior performance.This review summarizes and compares recent advancements in the research of eight distinct types of coatings for BPs in PEMFCs,including noble metal,carbide,ni-tride,and amorphous carbon(a-C)/metal compound composite coatings.The various challenges encountered in the manufacturing and fu-ture application of these coatings are also delineated.

Effects of the extrusion parameters on microstructure,texture and room temperature mechanical properties of extruded Mg-2.49Nd-1.82Gd-0.2Zn-0.2Zr alloy

Microstructure,texture,and mechanical properties of the extruded Mg-2.49Nd-1.82Gd-0.2Zn-0.2Zr alloy were investigated at different extrusion temperatures(260 and 320℃),extrusion ratios(10:1,15:1,and 30:1),and extrusion speeds(3 and 6 mm/s).The experimental results exhibited that the grain sizes after extrusion were much finer than that of the homogenized alloy,and the second phase showed streamline distribution along the extrusion direction(ED).With extrusion temperature increased from 260 to 320℃,the microstructure,texture,and mechanical properties of alloys changed slightly.The dynamic recrystallization(DRX)degree and grain sizes enhanced as the extrusion ratio increased from 10:1 to 30:1,and the strength gradually decreased but elongation(EL)increased.With the extrusion speed increased from 3 to 6 mm/s,the grain sizes and DRX degree increased significantly,and the samples presented the typical<2111>-<1123>rare-earth(RE)textures.The alloy extruded at 260℃ with extrusion ratio of 10:1 and extrusion speed of 3 mm/s showed the tensile yield strength(TYS)of 213 MPa and EL of 30.6%.After quantitatively analyzing the contribution of strengthening mechanisms,it was found that the grain boundary strengthening and dislocation strengthening played major roles among strengthening contributions.These results provide some guidelines for enlarging the industrial application of extruded Mg-RE alloy.

Shock Raman spectra and structural transformation of powdered TKX-50 by the plate impact experiments combined with real-time Raman detection

As an energetic material of great interest,the work capacity of dihydroxylammonium 5,5’-bistetrazole-1,1’-diolate(TKX-50)has been questioned recently.Although some research groups have explored the reasons for the low working ability of TKX-50,the plane impact experiment on powdered TKX-50 is obviously closer to the practical application,and the conclusions based on this are more guiding.Hence,we performed shock Hugoniot measurements of powdered TKX-50 between 5.65 and 16.29 GPa.The plane impact experiments of powdered TKX-50 were carried out and the shocked Raman spectra were collected.By Raman spectroscopy analysis,a new peak of powdered TKX-50 was found between19.47 GPa and 24.96 GPa,which may be caused by decomposition/phase transition and was related with the low work capacity.

Evolution of molecular structure of TATB under shock loading from transient Raman spectroscopic technique

By combination of the transient Raman spectroscopic measurement and the density functional theoretical calculations,the structural evolution and stability of TATB under shock compression was investigated.Due to the improvement in synchronization control between two-stage light gas gun and the transient Raman spectra acquisition,as well as the sample preparation,the Raman peak of the N-O mode of TATB was firstly observed under shock pressure up to 13.6 GPa,noticeably higher than the upper limit of 8.5 GPa reported in available literatures.By taking into account of the continuous shift of the main peak and other observed Raman peaks,we did not distinguish any structural transition or any new species.Moreover,both the present Raman spectra and the time-resolved radiation of TATB during shock loading showed that TATB exhibits higher chemical stability than previous declaration.To reveal the detailed structural response and evolution of TATB under compression,the density functional theoretical calculations were conducted,and it was found that the pressure make N-O bond lengths shorter,nitro bond angles larger,and intermolecular and intra-molecular hydrogen bond interactions enhanced.The observed red shift of Raman peak was ascribed to the abnormal enhancement of H-bound effect on the scissor vibration mode of the nitro group.

Pyrolysis of Copper Phthalocyanine as Non-noble Metal Electrocatalysts for Oxygen Reduction Reaction

We investigated the relationship between oxygen reduction reaction(ORR)activity and the pyrolysis temperature(650-850℃)of CuPc in alkaline solution.The highly active sites were formed through the decomposition of CuPc or Cu-N_(4) structure after releasing 4-nitrophthalonitrile.Cu-Nx incorporated with carbon were the main active sites.The XPS measurement results show that,at lower temperature,the contents of pyridinic-N and pyrrolic-N account for the most of the total N.As the temperature is higher than 750℃,the content of graphitic N(26.11%)increases and pyridinic-N(58.81%)becomes the dominant specie.When the temperature is higher than 850℃,the content of graphitic N increases remarkably and becomes the dominant species.Moreover,the specific surface areas decrease with increased pyrolysis temperature.Benefiting from the synergistic effect,the pyrolysis temperature at 750℃of CuPc displays superior electrocatalytic properties.The obtained results reveal that the fabricated non-noble metal catalysts can be used as low-cost,efficient catalyst for water splitting ORR in metal-air batteries and fuel cells.

Surface deterioration dependent on the crystal facets of spinel LiNi_(0.5)Mn_(1.5)O_(4) cathode active material

The spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)cathode active materials(CAMs)are considered a promising alternative to commercially available cathodes such as layered and polyanion oxide cathodes,primarily due to their notable safety and high energy density,particularly in their single-crystal type.Nevertheless,the industrial application of the LNMO CAMs is severely inhibited due to the interfacial deterioration and corrosion under proton-rich and high-voltage conditions.This study successfully designed and synthesized two typical types of crystal facets-exposed single-crystal LNMO CAMs.By tracking the electrochemical deterioration and chemical corrosion evolution,this study elucidates the surface degradation mechanisms and intrinsic instability of the LNMO,contingent upon their crystal facets.The(111)facet,due to its elevated surface energy,is found to be more susceptible to external attack compared to the(100)and(110)facets.Our study highlights the electrochemical corrosion stability of crystal plane engineering for spinel LNMO CAMs.

Evading strength−ductility trade-off of GH605 alloy using magnetic field-assisted undercooling treatment

Undercooling solidification under a magnetic field(UMF)is an effective way to tailor the microstructure and properties of Co-based alloys.In this study,by attributing to the UMF treatment,the strength−ductility trade-off dilemma in GH605 superalloy is successfully overcome.The UMF treatment can effectively refine the grains and increase the solid solubility,leading to the high yield strength.The main deformation mechanism in the as-forged alloy is dislocation slipping.By contrast,multiple deformation mechanisms,including stacking faults,twining,dislocation slipping,and their strong interactions are activated in the UMF-treated sample during compression deformation,which enhances the strength and ductility simultaneously.In addition,the precipitation of hard Laves phases along the grain boundaries can be obtained after UMF treatment,hindering crack propagation during compression deformation.

Significance-based optimization of processing parameters for thin-walled aluminum alloy tube NC bending with small bending radius

Thin-walled aluminum alloy tube numerical control （NC） bending with small bending radius is a complex process with multi-factor coupling effects and multi-die constraints. A significance-based optimization method of the parameters was proposed based on the finite element （FE） simulation, and the significance analysis of the processing parameters on the forming quality in terms of the maximum wall thinning ratio and the maximum cross section distortion degree was implemented using the fractional factorial design. The optimum value of the significant parameter, the clearance between the tube and the wiper die, was obtained, and the values of the other parameters, including the friction coefficients and the clearances between the tube and the dies, the mandrel extension length and the boost velocity were estimated. The results are applied to aluminum alloy tube NC bending d50 mm×1 mm×75 mm and d70 mm×1.5 mm×105 mm （initial tube outside diameter D0 × initial tube wall thickness t0 × bending radius R）, and qualified tubes are produced.

Numerical simulation of temperature distribution and heat transfer during solidification of titanium alloy ingots in vacuum arc remelting process

In order to get a better understanding of the vacuum consumable arc remelting(VAR) processes and thus to optimize them,a 3D finite element model was developed for the temperature fields and heat transfer of titanium alloy ingots during VAR process.The results show that the temperature fields obtained by the simulation are well validated through the experiment results.The temperature distribution is different during the whole VAR process and the steady-state molten pool forms at 329 s for d100 mm × 180 mm ingots.At the initial stage of remelting,the heat dissipation of crucible bottom plays an important role in the whole heat dissipation system.At the middle of remelting,the crucible wall becomes a major heat dissipation way.The effect of cooling velocity on the solidification structure of ingots was investigated based on the temperature fields and the results can well explain the macrostructure of titanium alloy ingots.

Growth restriction effects during solidification of aluminium alloys

The effects of solute elements during solidification on the grain size are very important and can be quantified by the growth-restriction parameter Q,and Q possesses the better correlation with the grain size. Based on the constitutional undercooling generated by the growth of an adjacent grain during the initial solidification,the growth-restriction parameter Q is deduced and a comprehensive physical basis of Q is obtained by using an initial solute distributing equation. For the alloys with more potent nucleants,Q is a suitable predictor of the grain size. For less potent nucleants,the relative grain size(RGS) is a more accurate prediction of the grain size. This prediction coincides with the experimental behaviors for Al-Ti and Al-Cu alloys with lower solute content.

Prediction of tri-modal microstructure under complex thermomechanical processing history in isothermal local loading forming of titanium alloy

To control the tri-modal microstructure and performance,a prediction model of tri-modal microstructure in the isothermal local loading forming of titanium alloy was developed.The staged isothermal local loading experiment on TA15alloy indicates that there exist four important microstructure evolution phenomena in the development of tri-modal microstructure,i.e.,the generation of lamellarα,content variation of equiaxedα,spatial orientation change of lamellarαand globularization of lamellarα.Considering the laws of these microstructure phenomena,the microstructure model was established to correlate the parameters of tri-modal microstructure and processing conditions.Then,the developed microstructure model was integrated with finite element(FE)model to predict the tri-modal microstructure in the isothermal local loading forming.Its reliability and accuracy were verified by the microstructure observation at different locations of sample.Good agreements between the predicted and experimental results suggest that the developed microstructure model and its combination with FE model are effective in the prediction of tri-modal microstructure in the isothermal local loading forming of TA15alloy.

Effect of solidification parameters on the microstructures of a single crystal Ni-based superalloy AM3

A single crystal Ni-based superalloy AM3 was processed at withdraw rates of 3.5, 10, 50, 100, 200, and 500 μm·s-1, respectively.The as-cast microstructures and solidification segregation ratio were characterized with various withdraw rates.The shape and size of carbide microstructures were determined.As expected, the primary and secondary dendrite arm spacings (PDAS and SDAS) decrease with the increase of withdraw rate.The highest volume fraction of eutectic γ/γ' is observed at the 100 μm·s-1 withdraw rate.The volume fraction of eutectic γ/γ' does not appear to be a strong function of the withdraw rate.With increasing withdraw rate, interface morphologies change in the sequence of planar, cellular, and dendrite.There is a general refinement of the microstructure as the withdraw rate increases.EPMA analysis showed that withdraw rate does not have obvious influence on the segregation of elements.

Effect of solidification rate on MC-type carbide morphology in single crystal Ni-base superalloy AM3

In order to study the effect of the withdrawing rate on carbide morphology,MC-type carbide in single crystal superalloy AM3 was systematically investigated with sample growth rates from 3.5 μm/s to 500 μm/s.The carbide morphologies were investigated by scanning electron microscopy(SEM),and the electron probe microanalysis(EPMA) was used to characterize the carbide composition.The results indicate that the solidification rate is the important factor governing MC carbide growth morphology,size and distribution,composition and growth mechanism.With the increase of withdrawing rate,nodular,rod-like,Chinese script types of carbide morphology are observed.For the low withdrawing rate,with the increase of withdrawing rate,the carbide size becomes larger.For the case of dendritic interface,the carbide size becomes smaller with refinement of dendrites as withdrawing rate increases.The volume fraction of carbides increases with the withdrawing rate increasing.

Influences of processing parameters on microstructure during investment casting of nickel-base single crystal superalloy DD3

The effects of solidification variables on the as-cast microstructures of nickel-base single crystal superalloy DD3 have been investigated by using the modified Bridgman apparatus. The experiments were performed under a thermal gradient of approximately 45 K.cm-1 and at withdrawal rates ranging from 30 to 200 m.s-1. The experimental results show that the primary and secondary dendritic arm spacings （PDAS and SDAS） decrease when the withdrawal rate is increased. Compared with the theoretical models of PDAS, the results are in good agreement with Trivedi＇s model. The relationships of PDAS and SDAS with withdrawal rates can be described as ;λ1 = 649.7V-0.24±0.02 and λ2 = 281 V-0.32±0.03, respectively. In addition, the size of the λ2 phase significantly decreases with increasing withdrawal rate.

Phase field investigation on the initial planar instability with surface tension anisotropy during directional solidification of binary alloys

Phase field investigation reveals that the stability of the planar interface is related to the anisotropic intensity of surface tension and the misorientation of preferred crystallographic orientation with respect to the heat flow direction. The large anisotropic intensity may compete to determine the stability of the planar interface. The destabilizing effect or the stabilizing effect depends on the misorientation. Moreover, the interface morphology of initial instability is also affected by the surface tension anisotropy.