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.

Accelerated intermetallic phase amorphization in a Mg-based high-entropy alloy powder

We describe a novel mechanism for the synthesis of a stable high-entropy alloy powder from an otherwise immiscible Mg-Ti rich metallic mixture by employing high-energy mechanical milling.The presented methodology expedites the synthesis of amorphous alloy powder by strategically injecting entropic disorder through the inclusion of multi-principal elements in the alloy composition.Predictions from first principles and materials theory corroborate the results from microscopic characterizations that reveal a transition of the amorphous phase from a precursor intermetallic structure.This transformation,characterized by the emergence of antisite disorder,lattice expansion,and the presence of nanograin boundaries,signifies a departure from the precursor intermetallic structure.Additionally,this phase transformation is accelerated by the presence of multiple principal elements that induce severe lattice distortion and a higher configurational entropy.The atomic size mismatch of the dissimilar elements present in the alloy produces a stable amorphous phase that resists reverting to an ordered lattice even on annealing.

Tin-mediated carbon-confined Pt_(3)Co ordered intermetallic nanoparticles as highly efficient and durable oxygen reduction electrocatalysts for rechargeable zinc-air batteries

The development of electrocatalysts for the oxygen reduction reaction(ORR) that bears high selectivity,exceptional activity,and long-term stability is crucial for advancing various green energy technologies.Intermetallics composed of platinum and transition metals are considered to be promising candidates for this purpose.However,they typically face challenges such as unfavorable intrinsic activity and a propensity for particle aggregation,diminishing their ORR performance.Against this backdrop,we present our findings on a N-doped carbon confined Pt_(3)Co intermetallic doped with p-block metal tin(Pt_(3)Co_(x)Sn_(1-x)/NC).The introduction of Sn induces lattice strain due to its larger atomic size,which leads to the distortion of the Pt_(3)Co lattice structure,while the coupling of carbon polyhedra inhibits the particle aggregation.The optimized Pt_(3)Co_(0.8)Sn_(0.2)/NC catalyst demonstrates an impressive half-wave potential of 0.86 V versus RHE,surpassing both Pt_(3)Co/NC and Pt_(3)Sn/NC catalysts.Moreover,the Pt_(3)Co_(0.8)Sn_(0.2)/NC exhibits a mass-specific activity as high as 1.4 A mg_(Pt)^(-1),ranking it in the top level among the intermetallicsbased ORR electrocatalysts.When further employed as a cathode material in a self-assembled zinc-air battery,it shows stable operation for over 80 h.These results underscore the significant impact of lattice strain engineering through the strategic doping of p-block metal in the carbon-confined Pt_(3)Co intermetallic,thereby enhancing the catalytic efficiency for the ORR.

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.

Transforming Cu into Cu_(2)O/RuAl intermetallic heterojunction for lowering the thermodynamic energy barrier of the CO_(2) reduction and evolution reactions in Li-CO_(2) battery

The Li-CO_(2) battery has been under the spotlight of future battery technologies since it can achieve CO_(2)utilization and energy conversion simultaneously.However,its advancement is hampered by poor energy efficiency and limited reversibility due to the sluggish kinetics of the CO_(2) reduction and evolution reactions.Herein,a multiscale nanoporous interpenetrating phase nanohybrid of RuAl intermetallic and Cu_(2)O(MP-Cu_(2)O/RuAl) was carved by driving synchronous phase and microstructure evolutions through dealloying of one RuCuAl master alloy.The built-in RuAl intermetallic and Cu_(2)O closely stack to form abundant nano-interfaces with revolutionized electronic structure,The theoretical simulations reveal that the Cu_(2)O/RuAl interface can distinctly reduce the energy barrier of the Li_(2)CO_(3) decomposition reaction,The interconnected pore channels with large surface area can enhance catalytic site accessibility,mass transfer,and uniform deposition of the discharge products.In situ differential electrochemical mass spectrometry discloses that the CO_(2)-to-electron ratio during charging coincides with the theoretical value of 3/4,demonstrating the high efficacy of MP-Cu_(2)O/RuAl in achieving the recycling of CO_(2).The dealloying protocol provides an affordable platform to empower transition metal oxides into high-efficiency electrocatalysts by hybridizing with metallic nano-sponge for advancing the application of Li-CO_(2)batteries.

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.

Effect of Fe and Mo additions on microstructure and mechanical properties of TiAl intermetallics

The ductility of TiAl intermetallics can be improved through stabilizing the ductile β phase.New β-stabilized Ti-45Al-xFe-yMo（x,y=1,2,3,4） alloys were designed through adding the β stabilizing elements Fe and Mo.The microstructural evolution and deformation behavior of the Ti-45Al-xFe-yMo alloys were investigated.The results show that the amount of β（B2） phase is increased with the increase of alloying elements.Mo shows a higher capability for stabilizing the β phase than Fe.In the optimized Ti-45Al-3Fe-2Mo alloy,the grains are significantly refined to about 12 μm,and this alloy shows a very good hot ductility at the elevated temperature.

Effect of pore structures on corrosion resistance of porous Ni_3Al intermetallics

Porous Ni3Al intermetallics were fabricated by elemental powder reactive synthesis method, using carbamide powders as space holders. Corrosion behavior of porous Ni3Al intermetallics was investigated in a 6 mol/L KOH solution using electrochemical methods and immersion test. Effect of porous structures on the corrosion behavior of the porous Ni3Al intermetallics was studied. The results indicate that the porous Ni3Al intermetallics with higher porosities suffer more serious corrosion than the ones with lower porosities because the complicated interconnected porous structures and the large true surface areas exist in the samples with a higher porosity. But the corrosion rates of the porous Ni3Al intermetallics are not proportional to the true surface areas. The reason is that the pore size, pore size distribution and pore shape of the porous Ni3Al intermetallics change with the increasing porosity. All the porous Ni3Al intermetallics with different porosities exhibit excellent corrosion resistance in a strong alkali solution.

Tortuosity factor for porous FeAl intermetallics fabricated by reactive synthesis

The tortuosity factor is the most critical parameter for the pore characteristic of porous materials. The tortuosity factor for porous FeAl intermetallics was studied based on the Darcy law and Hagen-Poiseuille equation. Porous stainless steel with the same pore structure parameter as porous FeAl was fabricated by powder metallurgy method for comparison. The results show that the tortuosity factor of porous FeAl intermetallics is smaller than that of porous stainless steel when their pore structure parameters are the same. The average tortuosity factor is 2.26 for the porous FeAl material and 2.92 for the porous stainless steel, calculated by Hagen-Poiseuille equation. The reason of the different tortuosity factors for porous FeAl and porous stainless steel was also explored through studying the pore formation mechanisms of the two types of porous materials.

Intermetallics and phase relations of Mg-Zn-Ce alloys at 400 ℃

The crystal structures,compositions and phase relations of the intermetallics of Mg-Zn-Ce system in the Mg-rich corner at 400 ℃ were identified through equilibrium alloy method.For Mg-Zn-Ce system,there is a linear ternary compound（T phase）,whose chemical formula is（Mg1-xZnx）11Ce.The range of Zn content in T phase is from 9.6% to 43.6%（molar fraction）.The crystal structure of T phase is C-centered orthorhombic lattice with lattice parameters of a=0.96-1.029 nm,b=1.115-1.204 nm,c=0.940-1.015 nm.And the lattice parameters of T phase are decreasing a little with increasing Zn content.According to the results of composition and crystal structure,the maximal solubility of Zn in Mg12Ce is about 7.8%（molar fraction）,and the chemical formula of the solid solution can be identified as（Mg1-xZnx）12Ce.The isothermal section of Mg-Zn-Ce system in Mg-rich corner at 400 ℃ was constructed.

Tuning mechanical properties for β(B2)-containing TiAl intermetallics

Based on the analyses of the microstructures and phase diagrams of the TiAl-based alloy, the relationship among the composition, structure and mechanical properties of the B2-containing y-TiAI alloys was reviewed. The refinement of microstructures and improvement of mechanical properties of TiA1 alloy through stabilization of the β/B2 phase were reviewed. The mechanism of the superplastic behavior of the B2-containing y-TiAI alloys was discussed. With a reasonable addition of β-stabilizer, metastable B2 phase can be maintained, which is favorable for fine-grained structure and better high-temperature deformation behaviors. The mechanical properties of the B2-containing TiAI alloy, including the deformability and elevated temperature properties, can also be improved with doping elements and subsequent hot-working processes. The above mentioned researches discuss a new way for developing TiAI alloys with comprehensive properties, including good deformability and creep resistance.

Microstructure and mechanical properties of TiAl-based alloy prepared by double mechanical milling and spark plasma sintering

A fine-grained TiAl alloy with a composition of Ti-45Al-2Cr-2Nb-1B-0.5Ta-0.225Y （mole fraction, %） was prepared by double mechanical milling（DMM） and spark plasma sintering（SPS）. The relationship among sintering temperature, microstructure and mechanical properties was studied. The results show that the morphology of double mechanical milled powder is regular with size in the range of 20-40 μm and mainly composed of TiAl and Ti3Al phases. The main phase TiAl and few phases Ti3Al, Ti2Al and TiB2 were observed in the SPSed alloys. For samples sintered at 900 ℃ the equiaxed crystal grain microstructure is achieved with size in the range of 100-200 nm. With increasing the SPS temperature from 900 ℃to 1000 ℃ the size of equiaxed crystal grain obviously increases, the microhardness decreases from HV658 to HV616, and the bending strength decreases from 781 MPa to 652 MPa. In the meantime, the compression fracture strength also decreases from 2769 MPa to 2669 MPa, and the strain to fracture in compression increases from 11.69% to 17.76%. On the base of analysis of fractographies, it shows that the compression fracture transform of the SPSed alloys is intergranular rupture.

Dynamic behavior and fracture mode of TiAl intermetallics with different microstructures at elevated temperatures

Experimental studies were conducted on the tensile behaviors and fracture modes of TiAl（Ti-46.5Al-2Nb-2Cr） alloys with near gamma（NG） equiaxed and near lamellar（NL） microstructures over a temperature range from room temperature to 840 ℃ and a strain rate range of 0.001-1 350 s-1.The results indicate that the alloys are both temperature and strain rate dependent and they have a similar dependence.The dynamic strength is higher than the quasi-static strength but almost insensitive to high strain rate range of 320-1 350 s-1.The brittle-to-ductile transition temperature（BDTT） increases with increasing strain rates.NG TiAl yields obviously,while NL TiAl does not.Below BDTT,as the temperature increases,the fracture modes of the two alloys change from planar cleavage fracture to a mixture of transgranular and intergranular fractures,and finally to totally intergranular fracture.

Formation and sedimentation of Fe-rich intermetallics in Al-Si-Cu-Fe alloy

Formation and sedimentation of Fe-rich intermetallics were studied in a commercial Al-Si-Cu-Fe alloy with extra additions of Mn. It is found that the introduction of extra Mn is an effective approach to lower the Fe level in the equilibrium liquid phase after sedimentation of solid Fe-rich phase at a temperature between its liquidus and solidus. The higher Mn/Fe mass ratio results in the lower Fe content in the retained alloy, during which Mn is also consumed and settled at the bottom of the melt as solid Fe-rich intermetallics. Therefore, the final Fe content in the alloy can be controlled by the Mn content and the holding temperature of the melt. The results confirmed a good agreement of the theoretical calculation and the experimental test with a specially designed 50 mm cylindrical casting. The sedimentation of Fe-rich intermetallics in the Al-Si-Cu-Fe alloy is completed at 600 °C after 10 min. The reduction of Fe content in the retained alloy is 31.4% when m（Mn）/m（Fe）=0.5 and 53.3% when m（Mn）/m（Fe）=1.0 in comparison with that in the original alloy. The settled Fe-rich intermetallics were identified as α-Al15（Fe,Mn）3Si2, which provided the lower balanced Fe concentration in the melt in comparison with other Fe-rich intermetallics.

Environmental Embrittlement of Fe-based, Co-based, Ni-based and Ti-based Intermetallics in Gaseous Hydrogen

The environmental embrittlement of intermetallics Co3Ti, Ni3Al, Fe3Al and TiAl has been investigated by measuring the tensile properties in oxygen and hydrogen at 2×l0-4/s strain rate. The results show that the hydrogen embrittlement factor in gaseous hydrogen (IH2 ) defined as[(δO2 -δH2 ) / δH2, ] ×l00% of above mentioned four intermetallics is decreased in the sequence of Co3Ti> Ni3Al> Fe3Al> TiAl. This phenomena can be explained by the different catalytic reaction on the surface of matrix metals (such as Ni, Co, Fe, Ti) with decomposition of H2 into atommic hydrogen, leading to hydrogen embrittlement.

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.