Ordered Mesoporous Intermetallic Ga-Pt Nanoparticles: Phase-Controlled Synthesis and Performance in Oxygen Reduction Electrocatalysis.

The intermetallic phase control is a promising strategy to optimize the physicochemical properties of ordered intermetallic compounds and engineer their performance in various (electro)catalytic reactions. However, the intermetallic phase-dependent catalytic performance is still rarely reported because of the difficulty in synthesizing ordered intermetallics with precisely controlled phase structures at atomic level, especially having ordered mesoscopic structure/morphology. Here, we successfully reported a precise synthesis of two phase-pure mesoporous intermetallic gallium-platinum (meso-i-Ga-Pt) nanoparticles, including meso-i-Ga3 Pt5 with an orthorhombic space group and meso-i-Ga1 Pt1 with a non-symmorphic chiral cubic space group. The intermetallic phase control of ordered meso-i-Ga-Pt nanoparticles was realized by carefully tuning the induced Ga salts with different anions that optimized the free energies during the synthesis. The intermetallic phase-dependent catalytic performance of ordered meso-i-Ga-Pt was systematically evaluated for oxygen reduction reaction (ORR) electrocatalysis, with completely opposite catalytic performance in alkaline media. Interestingly, ordered meso-i-Ga1 Pt1 catalyst with chiral atomic arrangements disclosed unexpected high ORR activity and stability with 5.9 and 3.2 enhancement factors in mass activity compared to those of meso-i-Ga3 Pt5 and commercial Pt/C.

Crystal Structures of AlCr2 and MoSi2 : Same Structure Type vs. Different Bonding Pattern.

In a joint effort utilizing modified sample preparation, microscopy, X-ray diffraction and micro-fabrication, it became possible to prepare single crystals of the "hidden" phase AlCr2 . High-resolution X-ray diffraction analysis is described in detail for two crystals with the similar overall composition, but different degree of disorder, which seems to be the main cause for the differing unit cell parameters. Chemical bonding analysis of AlCr2 in comparison to prototypical MoSi2 shows pronounced differences reflecting the interchange of main group element vs. transition metal as majority component.

Intermetallic Phase Evolution of Cold-Sprayed Ni-Ti Composite Coatings: Influence of As-Sprayed Chemical Composition.

Owing to low-temperature deposition conditions and high deposition rate, cold spray offers unique advantages in manufacturing a wide variety of metallic and composite coatings including metal matrix composites produced from physically blended powders. One of the challenges of producing composite coatings using cold spray is the deviation of coatings composition from the blended feedstock powder composition. This is of utmost importance as it affects the composition and phase evolution of intermetallic forming coatings during post spray heat treatment. In this work, cold spray of composite Ni-Ti coatings and formation of intermetallics from post spray heat treatment were investigated as a first step to examine the potential of producing equiatomic bulk Ni-Ti by cold spray. Three different physically blended Ni and Ti powders mixtures were sprayed on titanium substrates to address the coating composition variation from the blended feedstock powder and study its influence on phase evolution during post spray heat treatment. High-density and well-dispersed composite coatings were achieved for each case. EDS analysis revealed as-sprayed coatings with 10.5, 35.9 and 56.9 at.% Ni (and with balanced Ti ratios) from the three powder mixtures. Annealing treatments were conducted at 400, 500 and 900 °C for 1 and 2 h and comparative studies of the intermetallic compound formations were carried out. Microstructural investigation showed that all three equilibrium intermetallics phases of binary Ni-Ti phase diagram (Ni3Ti, Ti2Ni and NiTi) formed in the two Ni-rich composite coatings with NiTi phase being maximum in the coating with the closest composition to equiatomic ratio while only Ti2Ni phase formed in the Ti-rich coating after annealing. Thermal etching analysis of coatings showed that NiTi phase forms with a gradient microstructure from Ti splats boundary toward the center of splats, which is attributed to the grain refinement of CS samples at splat boundary and intermetallic nucleation mechanism.

Influence of intermetallic phase (TiFe) on the microstructural evolution and mechanical properties of as-cast and quenched Ti-Mo-Fe alloys.

This study presents the phase analysis, microstructural characteristics, and mechanical property evaluation of the as-cast and quenched Ti-15Mo-xFe alloys with high iron content ranging from 4 to 12 weight percent. All the four alloys were produced in a vacuum-arc melting furnace. Heat treatment in the form of solution treatment was performed in a muffle furnace at a temperature of 1100 °C, with 1-h holding time and the samples were rapidly quenched in ice-brine. X-ray diffractometer (XRD) was used to analyses the phases present in each alloy whereas the optical microscope (OM) was employed to track the microstructural evolution and percentage porosity. The mechanical properties of the alloys were evaluated using a tensile test and compression test method while the micro-Vickers hardness measurements were conducted to evaluate hardness of the alloys. The XRD patterns of as-cast showed peaks belonging to the ß and α″ phases and intermetallic B2 TiFe phases. The as quenched XRD peaks illustrated ß phase only and Fe·Ti·O2 phases. The as-cast OM micrographs revealed equiaxed ß grains, substructures, dendritic structure, and pores forming around the grain boundaries. The quenched OM showed only ß equiaxed grains with pores throughout the grain boundaries. The tensile properties such as ultimate tensile strength (UTS) and elastic modulus (E) of as-cast TMF0 were 264 MPa and 79 GPa respectively and these properties changed upon quenching to 411 MPa and 66 GPa respectively. The elastic modulus of TMF1 in as-cast condition was 74 GPa. The UTS and E of TMF1, TMF2, and TMF3 in as-cast and quenched conditions were not recorded due to the fragility of the samples that failed prior to yielding any useful data. The compressive strength in as-cast and in quenched condition decreased with an increase in Fe content. The micro-Vickers hardness in as-cast and quenched conditions showed a similar trend with hardness increasing slightly upon quenching for TMF0, TMF1, and TMF3 alloys but slightly decreased in the case of TMF2. The fracture surfaces of all the as-cast and quenched alloys were comprised of ductile and brittle fracture.

Intrinsic Visible Plasmonic Properties of Colloidal PtIn2 Intermetallic Nanoparticles.

Materials that intrinsically exhibit localized surface plasmon resonance (LSPR) in the visible region have been predominantly researched on nanoparticles (NPs) composed of coinage metals, namely Au, Ag, and Cu. Here, as a coinage metal-free intermetallic NPs, colloidal PtIn2 NPs with a C1 (CaF2 -type) crystal structure are synthesized by the liquid phase method, which evidently exhibit LSPR at wavelengths similar to face-centered cubic (fcc)-Au NPs. Computational simulations pointed out differences in the electronic structure and photo-excited electron dynamics between C1-PtIn2 and fcc-Au NPs; reduces interband transition and stronger screening with smaller number of bound d-electrons compare with fcc-Au are unique origins of the visible plasmonic nature of C1-PtIn2 NPs. These results strongly indicate that the intermetallic NPs are expected to address the development of alternative plasmonic materials by tuning their crystal structure and composition.

Evaluation of Effect of Ti Addition to Zinc Bath on Kinetics of Growth of Alloy Layer Formed in Process of Hot-Dip Galvanisation on Steel Substrate.

Faced with the raw material crisis in Zn resources, researchers are facing the challenge of developing technology for producing zinc coatings that are thinner than those that have been produced to date. This would make it possible to reduce Zn consumption in the hot-dip galvanisation process. The study included an experiment that involved dip galvanising steel samples in baths of different Ti concentrations; this process was carried out at 450 °C and 550 °C. The use of this additive made it possible to reduce the growth of the alloy layer in the obtained zinc coatings. Using an optical microscope, observations were made of the microstructures of the resulting coatings, which made it possible to determine the thickness of the alloy layer in the coating. Thanks to the use of scanning electron microscopy with EDS analysis, however, it was possible to plot the chemical composition of the studied coatings and accurately observe the morphology of the formed phases. An intermetallic Zn-Fe-Ti phase was observed in the coatings formed in a Ti-added bath, which can affect the growth inhibition of the alloy layer in the zinc coating.

Microstructural Characteristics of High-Pressure Die Casting with High Strength-Ductility Synergy Properties: A Review.

In response to the increased emphasis on reducing carbon emissions, the demand for lightweight, high-performance structural materials is quickly increasing, and Mg alloys, because of their having the lowest density among the common engineering metals, have demonstrated considerable advantages and prospective applications in contemporary industry. High-pressure die casting (HPDC), owning to its high efficiency and low production cost, is the most extensively utilized technique in commercial Mg alloy applications. The high room-temperature strength-ductility of HPDC Mg alloys plays an important role in their safe use, particularly in the automotive and aerospace industries. With respect to HPDC Mg alloys, their mechanical properties highly rely on their microstructural characteristics, particularly the intermetallic phases, which are further dependent on the alloys' chemical compositions. Therefore, the further alloying of traditional HPDC Mg alloys, such as Mg-Al, Mg-RE, and Mg-Zn-Al systems, is the most adopted method to further improve their mechanical properties. Different alloying elements lead to different intermetallic phases, morphologies, and crystal structures, which can have helpful or harmful effects on an alloy's strength or ductility. The methods aimed at regulating and controlling the strength-ductility synergy of HPDC Mg alloys have to arise from an in-depth understanding of the relationship between the strength-ductility and the components of the intermetallic phases of various HPDC Mg alloys. This paper focuses on the microstructural characteristics, mainly the intermetallic phases (i.e., components and morphologies), of various HPDC Mg alloys with good strength-ductility synergy, aimed at providing insight into the design of high-performance HPDC Mg alloys.

Microstructure and Phase Composition of Ti-Al-C Materials Obtained by High Voltage Electrical Discharge/Spark Plasma Sintering.

Titanium-based composite materials arouse interest in fields like aerospace, transportation, medicine, and other applications. This research project presents the analysis of phase composition of sintered Ti-Al-C composite materials under high voltage electrical discharge. The new technology, described in the previous work of the authors, allows to synthesise the composites containing various intermetallics, carbides, and nanostructures. The samples of Ti-Al-C powder composites were tested by SEM, Raman spectroscopy, and XRD. It was determined that the treatment of the powder by high voltage electrical discharge (HVED) and further sintering at high temperatures using the spark plasma sintering (SPS) method encouraged the formation of the intermetallic reinforcing phases, carbides, and different nanocarbon structures like graphene and fullerenes, as well as pure graphite. Intermetallic phases and nanocarbon structures improved the mechanical and physical properties of the composites. By using the experimental methods mentioned above, the phase composition of Ti-Al-C powder composites obtained at different sintering temperatures was determined. It was revealed that new composite materials produced by HVED and further SPS were rich with carbides, intermetallics, and MAX phases. Therefore, the carbon nanostructures (graphene and graphite) were detected existing in the structure of the produced new Ti-Al-C composite material. All these reinforcing particles improved the microstructure and the mechanical properties of the composites, as was proved in the previous research by the authors and by the different scientific resources. This project is a pilot experimental work, therefore not all peaks of Raman and XRD were detected; they will be analysed in future works.

Kinetics of Intermetallic Phase Precipitation in Manual Metal Arc Welded Duplex Stainless Steels.

The article presents the influence of heat treatment on the kinetics of transformations in lean duplex LDX2101 steel and a weld made of standard duplex 2209 material, which was welded by manual metal arc welding. Changes in the microstructure, hardness, and magnetic phase content were analyzed after heat treatment was conducted at a temperature of 800 °C for a period ranging from 15 to 1440 min. Light and scanning microscopy, Vickers hardness measurements, and magnetic phase content measurements using a ferritoscope were used for the research. In the LDX2101 steel, the presence of δ-ferrite and γ austenite was identified and additional Cr2N nitrides were observed in the heat-affected zone. After heat treatment, the decomposition of δ ferrite into γ2 austenite and Cr2N nitrides was observed in both areas. In the case of weld made by the coated electrode in 2209 grade, a ferritic-austenitic microstructure with allotriomorphic austenite (γA), Widmanstätten austenite (γW), and idiomorphic austenite (γI) and δ-ferrite area with "bee swarms" of fine precipitations of chromium nitrides Cr2N and non-metallic inclusions (NMIs) of slag, formed during the welding process, are observed in the as-welded state. After heat treatment, the presence of the χ phase (after 15 min of annealing) and the σ phase (after 120 min of annealing) was additionally identified. The kinetics of intermetallic phase evolution in welds made from 2209 material were presented. The obtained results of hardness measurements and metallographic tests were correlated, which allowed for a quick check of the precipitation processes on the used element.

Characterization of the Interface between Aluminum and Iron in Co-Extruded Semi-Finished Products.

Within the framework of the Collaborative Research Center 1153, we investigated novel process chains for the production of bulk components with different metals as joining partners. In the present study, the co-extrusion of coaxially reinforced hollow profiles was employed to manufacture semi-finished products for a subsequent die-forging process, which was then used for the manufacture of hybrid bearing bushings. The hybrid hollow profiles, made of the aluminum alloy EN AW-6082 paired with either the case-hardening steel 20MnCr5, the stainless steel X5CrNi18-10, or the rolling bearing steel 100Cr6, were produced by Lateral Angular Co-Extrusion. Push-out tests on hybrid hollow sections over the entire sample cross-section showed shear strengths of 44 MPa ± 8 MPa (100Cr6) up to 63 MPa ± 5 MPa (X5CrNi18-10). In particular, the influence of force and form closure on the joint zone could be determined using specimen segments tested in shear compression. Locally, shear strengths of up to 131 MPa (X5CrNi18-10) were demonstrated in the shear compression test. From these samples, lamellae for microstructural analysis were prepared with a Focused Ion Beam. Detailed analyses showed that for all material combinations, a material bond in the form of an ultra-thin intermetallic phase seam with a thickness of up to 50 nm could be established.

A biodegradable in situ Zn-Mg2Ge composite for bone-implant applications.

Zinc (Zn)-based composites have received extensive attention as promising biodegradable materials due to their unique combination of moderate biodegradability, biocompatibility, and functionality. Nevertheless, the low mechanical strength of as-cast Zn-based composites impedes their practical clinical application. Here we reported the mechanical properties, corrosion behavior, wear properties, and cytotoxicity of in situ synthesized biodegradable Zn-xMg2Ge (x = 1, 3, and 5 wt.%) composites for bone-implant applications. The mechanical properties of Zn-xMg2Ge composites were effectively improved by alloying and hot-rolling due to particle reinforcement of the Mg2Ge intermetallic phase and dynamic recrystallization. The hot-rolled (HR) Zn-3Mg2Ge composite exhibited the best mechanical properties, including a yield strength of 162.3 MPa, an ultimate tensile strength of 264.3 MPa, an elongation of 10.9%, and a Brinell hardness of 83.9 HB. With an increase in Mg2Ge content, the corrosion and degradation rates of the HR Zn-xMg2Ge composites gradually increased, while their wear rate decreased and then increased in Hanks' solution. The diluted extract (12.5% concentration) of the HR Zn-3Mg2Ge composite showed the highest cell viability compared to the other HR composites and their as-cast pure Zn counterparts. Overall, the HR Zn-3Mg2Ge composite can be considered a promising biodegradable Zn-based composite for bone-implant applications. STATEMENT OF SIGNIFICANCE: This paper reports the mechanical properties, corrosion behavior, wear properties, and cytotoxicity of in situ synthesized biodegradable Zn-xMg2Ge (x = 1, 3, and 5 wt.%) composites for bone-implant applications. Our findings demonstrated that the mechanical properties of Zn-xMg2Ge composites were effectively improved by alloying and hot-rolling due to Mg2Ge particle reinforcement and dynamic recrystallization. The hot-rolled Zn-3Mg2Ge composite showed superior cytocompatibility, satisfying corrosion and degradation rates, and the best mechanical properties including a yield strength of 162.3 MPa, an ultimate tensile strength of 264.3 MPa, and an elongation of 10.9%.

On the Disintegration of A1050/Ni201 Explosively Welded Clads Induced by Long-Term Annealing.

The paper presents the microstructure and phase composition of the interface zone formed in the explosive welding process between technically pure aluminum and nickel. Low and high detonation velocities of 2000 and 2800 m/s were applied to expose the differences of the welded zone directly after the joining as well as subsequent long-term annealing. The large amount of the melted areas was observed composed of a variety of Al-Ni type intermetallics; however, the morphology varied from nearly flat to wavy with increasing detonation velocity. The applied heat treatment at 500 °C has resulted in the formation of Al3Ni and Al3Ni2 layers, which in the first stages of growth preserved the initial interface morphology. Due to the large differences in Al and Ni diffusivities, the porosity formation occurred for both types of clads. Faster consumption of Al3Ni phase at the expense of the growing Al3Ni2 phase, characterized by strong crystallographic texture, has been observed only for the weld obtained at low detonation velocity. As a result of the extended annealing time, the disintegration of the bond occurred due to crack propagation located at the A1050/Al3Ni2 interface.

Up-Scaling of Thermomechanically Induced Laves Phase Precipitation in High Performance Ferritic (HiperFer) Stainless Steels.

Fully ferritic stainless steels, strengthened by Laves phase precipitates, were developed for high-temperature application in the next generation of ultra-super-critical thermal power plants. Based on the rapid occurrence of thermomechanically induced precipitation in strengthening Laves phase particles, a novel thermomechanical process route for this class of steels was developed. A controlled precipitation of particles, in a desired morphology and quantity, and an optimization of the corresponding forging parameters was achieved on a laboratory scale. This article outlines the very first up-scaling experiment with these optimized forging parameters from the laboratory scale to the industrial scale. The precipitation behavior was analyzed, utilizing digital particle analysis of scanning electron microscopy (SEM) images, to estimate and compare the phase fraction of the precipitated Laves phase, as well as the particle size and distribution. Due to the up-scaling in the forging process, the behavior of the precipitation changed and the precipitation strengthening effect was decreased, in comparison with the laboratory scale.

Evaluation of Structure and Corrosion Behavior of FeAl Alloy after Crystallization, Hot Extrusion and Hot Rolling.

The paper presents the results of tests on the corrosion resistance of Fe40Al5Cr0.2TiB alloy after casting, plastic working using extrusion and rolling methods. Examination of the microstructure of the Fe40Al5Cr0.2TiB alloy after casting and after plastic working was performed on an Olympus GX51 light microscope. The stereological relationships of the alloy microstructure in the state after crystallization and after plastic working were determined. The quantitative analysis of the structure was conducted after testing with the EBSD INCA HKL detector and the Nordlys II analysis system (Channel 5), which was equipped with the Hitachi S-3400N microscope. Structure tests and corrosion tests were performed on tests cut perpendicular to the ingot axis, extrusion direction, and rolling direction. As a result of the tests, it was found that the crystallized alloy has better corrosion resistance than plastically processed material. Plastic working increases the intensity of the electrochemical corrosion of the examined alloy. It was found that as-cast alloy is the most resistant to corrosion in a 5% NaCl compared with the alloys after hot extrusion and after hot rolling. The parameters in this study show the smallest value of the corrosion current density and corrosion rate as well as the more positive value of corrosion potential.

Microstructural Evolution and Phase Formation in 2nd-Generation Refractory-Based High Entropy Alloys.

Refractory-based high entropy alloys (HEAs) of the 2nd-generation type are new intensively-studied materials with a high potential for structural high-temperature applications. This paper presents investigation results on microstructural evolution and phase formation in as-cast and subsequently heat-treated HEAs at various temperature-time regimes. Microstructural examination was performed by means of scanning electron microscopy (SEM) combined with the energy dispersive spectroscopy (EDS) mode of electron probe microanalysis (EPMA) and qualitative X-ray diffraction (XRD). The primary evolutionary trend observed was the tendency of Zr to gradually segregate as the temperature rises, while all the other elements eventually dissolve in the BCC solid solution phase once the onset of Laves phase complex decomposition is reached. The performed thermodynamic modelling was based on the Calculation of Phase Diagrams method (CALPHAD). The BCC A2 solid solution phase is predicted by the model to contain increasing amounts of Cr as the temperature rises, which is in perfect agreement with the actual results obtained by SEM. However, the model was not able to predict the existence of the Zr-rich phase or the tendency of Zr to segregate and form its own solid solution-most likely as a result of the Zr segregation trend not being an equilibrium phenomenon.

Evolution of Nanoporous Surface Layers on Gas-Atomized Ti60Cu39Au1 Powders during Dealloying.

Nanoporous golf ball-shaped powders with a surface porous layer consisting of fcc Cu and Cu3Au phases have been fabricated by selectively dissolving gas-atomized Ti60Cu39Au1 powders in 0.13 M HF solution. The distribution profiles of the Ti2Cu and TiCu intermetallic phases and powder size play an important role of the propagation of the selective corrosion frontiers. The final nanoporous structure has a bimodal characteristic with a finer nanoporous structure at the ridges, and rougher structure at the shallow pits. The powders with a size of 18⁻75 m dealloy faster due to their high crystallinity and larger powder size, and these with a powder size of smaller than 18 m tend to deepen uniformly. The formation of the Cu3Au intermetallic phases and the finer nanoporous structure at the ridges proves that minor Au addition inhibits the fast diffusion of Cu adatoms and decreases surface diffusion by more than two orders. The evolution of the surface nanoporous structure with negative tree-like structures is considered to be controlled by a percolation dissolution mechanism.

Multiscale Morphology of Nanoporous Copper Made from Intermetallic Phases.

Many application-relevant properties of nanoporous metals critically depend on their multiscale architecture. For example, the intrinsically high step-edge density of curved surfaces at the nanoscale provides highly reactive sites for catalysis, whereas the macroscale pore and grain morphology determines the macroscopic properties, such as mass transport, electrical conductivity, or mechanical properties. In this work, we systematically study the effects of alloy composition and dealloying conditions on the multiscale morphology of nanoporous copper (np-Cu) made from various commercial Zn-Cu precursor alloys. Using a combination of X-ray diffraction, electron backscatter diffraction, and focused ion beam cross-sectional analysis, our results reveal that the macroscopic grain structure of the starting alloy surprisingly survives the dealloying process, despite a change in crystal structure from body-centered cubic (Zn-Cu starting alloy) to face-centered cubic (Cu). The nanoscale structure can be controlled by the acid used for dealloying with HCl leading to a larger and more faceted ligament morphology compared to that of H3PO4. Anhydrous ethanol dehydrogenation was used as a probe reaction to test the effect of the nanoscale ligament morphology on the apparent activation energy of the reaction.

Synthesis and structure determination of Ce6Cd23Te: a new chalcogen-containing member of the RE6Cd23T family (RE is a rare-earth metal and T is a late group 14, 15 and 16 element).

The ternary phase hexacerium tricosacadmium telluride, Ce6Cd23Te, was synthesized by a high-temperature reaction of the elements in sealed Nb ampoules and was structurally characterized by powder and single-crystal X-ray diffraction. The structure, established from single-crystal X-ray diffraction methods, is isopointal with the Zr6Zn23Si structure type (Pearson symbol cF120, cubic space group Fm-3m), a filled version of the Th6Mn23 structure with the same space group and Pearson symbol cF116. Though no Cd-containing rare-earth metal binaries are known to form with this structure, it appears that the addition of small amounts of a p-block element allows the formation of such interstitially stabilized ternary compounds. Temperature-dependent direct current (dc) magnetization measurements suggest local-moment magnetism arising from the Ce3+ ground state, with possible valence fluctuations at low temperature, inferred from the deviations from the Curie-Weiss law.

Structural chemistry and number theory amalgamized: crystal structure of Na11Hg52.

The recently elucidated crystal structure of the technologically important amalgam Na11Hg52 is described by means of a method employing some fundamental concept of number theory, namely modular arithmetical (congruence) relations observed between a slightly idealized set of atomic coordinates. In combination with well known ideas from group theory, regarding lattice-sublattice transformations, these allow for a deeper mutual understanding of both and provide the structural chemist with a slightly different kind of spectacles, thus enabling a distinct viw on complex crystal structures in general.