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.

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.

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.

Three-dimensional characteristics of Fe-rich intermetal ics in gravity-cast Al-6Si alloys

Fe-rich intermetallics, especially β-Fe phase, usually forming in the microstructure of cast aluminum alloys, are very detrimental to mechanical properties. In the present work, the effects of Fe content on phase transformation and microstructures were analyzed using a 3D X-ray microscope. Based on the highresolution 3D X-ray computed tomography, the 3D characteristics of Fe-rich intermetallics and micropores in the gravity-cast Al-6 Si alloys with different Fe contents were investigated. In addition, the effect of intermetallics on the microporosity was discussed. The results show that with increasing the Fe content from 0.10 wt.% to 0.60 wt.%, the volume fraction of Fe-rich intermetallics and the volume of the largest size Fe-rich intermetallic increased, and the 3D morphology of intermetallics changed from fine flake to network aggregation. As the Fe contents increased, the shrinkage pores were characterized, which were rather complex due to the micropores promoted by the intermetallics interactions.

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.

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.

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.

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.