Project description:Additive manufacturing of high-entropy alloys combines the mechanical properties of this novel family of alloys with the geometrical freedom and complexity required by modern designs. Here, a non-beam approach to additive manufacturing of high-entropy alloys is developed based on 3D extrusion of inks containing a blend of oxide nanopowders (Co3O4 + Cr2O3 + Fe2O3 + NiO), followed by co-reduction to metals, inter-diffusion and sintering to near-full density CoCrFeNi in H2. A complex phase evolution path is observed by in-situ X-ray diffraction in extruded filaments when the oxide phases undergo reduction and the resulting metals inter-diffuse, ultimately forming face-centered-cubic equiatomic CoCrFeNi alloy. Linked to the phase evolution is a complex structural evolution, from loosely packed oxide particles in the green body to fully-annealed, metallic CoCrFeNi with 99.6 ± 0.1% relative density. CoCrFeNi micro-lattices are created with strut diameters as low as 100 μm and excellent mechanical properties at ambient and cryogenic temperatures.
Project description:High-entropy alloys (HEAs) have intriguing material properties, but their potential as catalysts has not been widely explored. Based on a concise theoretical model, we predict that the surface of a quaternary HEA of base metals, CoCrFeNi, should go from being nearly fully oxidized except for pure Ni sites when exposed to O2 to being partially oxidized in an acidic solution under cathodic bias, and that such a partially oxidized surface should be more active for the electrochemical hydrogen evolution reaction (HER) in acidic solutions than all the component metals. These predictions are confirmed by electrochemical and surface science experiments: the Ni in the HEA is found to be most resistant to oxidation, and when deployed in 0.5 M H2SO4, the HEA exhibits an overpotential of only 60 mV relative to Pt for the HER at a current density of 1 mA/cm2.
Project description:Soft magnetic high-entropy alloy thin films (HEATFs) exhibit remarkable freedom of material-structure design and physical-property tailoring, as well as, high cut-off frequencies and outstanding electrical resistivities, making them potential candidates for high-frequency magnetic devices. In this study, a CoCrFeNi film with excellent soft magnetic properties is developed by forming a novel core-shell structure via native oxidation, with ferromagnetic elements Fe, Co, and Ni as the core and the Cr oxide as the shell layer. The core-shell structure enables a high saturation magnetization, enhances the electrical resistivity, and thus reduces the eddy-current loss. For further optimizing the soft magnetic properties, O is deliberately introduced into the HEATFs, and the O-incorporated HEATFs exhibit an electrical resistivity of 237 µΩ·cm, a saturation magnetization of 535 emu cm-3 , and a coercivity of 23 A m-1 . The factors that determine the ferromagnetism and coercivity of the CoCrFeNi-based HEATFs are examined in detail by evaluating the microstructures, magnetic domains, chemical valency, and 3D microscopic compositional distributions of the prepared films. These results are anticipated to provide insights into the magnetic behaviors of soft magnetic HEATFs, as well as aid in the construction of a promising material-design strategy for these unique materials.
Project description:Possibilities of enhancing mechanical properties of brittle intermetallic containing high entropy alloys (HEAs) using novel processing and microstructural design strategies were investigated in the present work. For this purpose, homogenized CoCrFeNi2.1Nb0.2 HEA consisting of FCC matrix and complex Laves phase particles was successfully processed by severe cold- or cryo-rolling to 90% reduction in thickness followed by annealing (800 °C/1 hour(h)). As compared to cold-rolling, cryo-rolling resulted in a finer lamellar nanostructure and decidedly greater fragmentation of the Laves phase. Upon annealing, the cold-rolled HEA showed a recrystallized FCC matrix dispersed with D019 structured ε nano-precipitates. In contrast, the finer nanostructure and greater driving force for accelerated precipitation of profuse nano-precipitates at the early stages of annealing inhibited recrystallization in the cryo-rolled HEA and resulted in the formation of heterogeneous microstructure consisting of retained deformed and recrystallized regions. The novel heterogeneous microstructure of the cryo-rolled and annealed HEA resulted in a remarkable enhancement in strength-ductility synergy. The present results indicated that cryo-rolling could be used as an innovative processing strategy for tailoring heterogeneous microstructure and achieving novel mechanical properties.
Project description:The corrosion characteristics and passive behavior of as-cast Ni40Fe30Co20Al10 medium-entropy alloy (MEA) fabricated by the vacuum arc melting technique were investigated in 3.5 wt.% NaCl, 0.5 M HCl, and 0.5 M H2SO4 solutions. Although the impact of different solutions on the corrosion current density was not pronounced, the corrosion potential values of MEAs in H2SO4, HCl and NaCl solutions were -0.37, -0.58 and -1.16 V, respectively, indicating that the resistance to general corrosion in acidic solutions becomes strengthened. Through electrochemical passive region tests, surface morphology analysis and ICP testing, it was found that, due to the high-entropy effect and uniform single-phase structure, an optimized and stable passive film formed specifically in the Cl--containing solution. The ion concentrations in the passive region of MEA in NaCl solution were an order of magnitude lower than those of other two samples, suggesting that its passive film formed exhibits a more prominent capacity to inhibit metal dissolution. Compared with electrochemical reactions in H2SO4 and HCl solutions, MEA shows enhanced pitting resistance in NaCl solution, which could be attributed to the presence of abundant unoxidized metal atoms (51.9 at.%). Al is identified as the primary component in the formation of the passive film, which plays a protective role for the Co-rich interior of the MEA. Although MEA has a relatively high passivation current in the H2SO4 solution, it has the widest passivation zone (1.87 V), indicating the optimized stability of the formed passive film. Moreover, it displays a high level of resistance to pitting corrosion in the solution containing only H+- and free of Cl-. Both the MEAs show significant grain-boundary corrosion in H2SO4 and HCl solutions. Among them, the MEA in HCl experiences more severe intragranular corrosion. Notably, MEA withstands the erosion of a single Cl-- or H+-containing solution, but it is unable to resist the synergistic effect of a solution containing both H+ and Cl-.
Project description:Recently, a number of ternary half-Heusler compounds have been predicted independently by several research groups as candidates for 3D topological insulators. In this work, we report the observation of a two-dimensional (2D) weak antilocalization (WAL) effect, one of the hall-marks of topological surface states, and Shubnikov-de Hass (SdH) quantum oscillations in <110> oriented DyPdBi (DPB) thin films grown on MgO (100) substrates. The films prepared by pulsed laser deposition technique under the optimized conditions, showed a textured structure with (110) planes parallel to the (100) plane of MgO. The measured WAL effect follows the Hikami-Larkin-Nagaoka (HLN) model and the extracted values of phase coherence length (lϕ) and α are ~420 nm and ~-0.52 respectively. The power law variation of lϕ (~T-0.46) indicates the presence of the 2D surface states in DPB film. The Dirac nature of the surface states is further confirmed by Landau-level fan diagram analysis of SdH oscillations of the magneto-transport data. This analysis shows a finite Berry phase of 0.90π ± 0.16, reasonably close to the expected π value. Sheet Carrier density, ns ~ 2.56 × 1012 cm-2, calculated from the SdH oscillations (fSdH ~ 106 T) and Hall measurements agree well with each other. These findings demonstrate that the half Heusler DPB thin films (~15-20 nm) can be used as a suitable material for investigating the novel intrinsic quantum transport properties of surface Dirac fermions.
Project description:A new way for synthesizing porous composite with cobalt species and N-doped carbon nanotubes (NDCNTs) was reported here by using cobalt salts and melamine mixtures as precursor. The Co(O)x/NDCNTs exhibited good activity of electrocatalytic O2 production. Furthermore, after reduced by H2, the Co-NDCNTs showed strong absorption of visible light and high catalytic activity of H2 production, which is 598.5 μmol g-1 h-1 under the visible light (λ > 420 nm). The results suggested that supramolecular preorganization of melamine monomers may be a promising method of synthesizing two-dimensional N-doped carbon nanotube with Co particles in it. The morphologies should be beneficial for the charge transport and separation. This work can encourage further synthesize new efficient noble-metal-free photocatalysts or electrocatalysts.
Project description:Among the existing materials for heat conversion, high-entropy alloys are of great interest due to the tunability of their functional properties. Here, we aim to produce single-phase high-entropy oxides composed of Co-Cr-Fe-Mn-Ni-O through spark plasma sintering (SPS), testing their thermoelectric (TE) properties. This material was successfully obtained before via a different technique, which requires a very long processing time. Hence, the main target of this work is to apply spark plasma sintering, a much faster and scalable process. The samples were sintered in the temperature range of 1200-1300 °C. Two main phases were formed: rock salt-structured Fm3̅m and spinel-structured Fd3̅m. Comparable transport properties were achieved via the new approach: the highest value of the Seebeck coefficient reached -112.6 μV/K at room temperature, compared to -150 μV/K reported before; electrical properties at high temperatures are close to the properties of the single-phase material (σ = 0.2148 S/cm, σ ≈ 0.2009 S/cm reported before). These results indicate that SPS can be successfully applied to produce highly efficient TE high-entropy alloys in a fast and scalable way. Further optimization is needed for the production of single-phase materials, which are expected to exhibit an even better TE functionality.
Project description:The interaction of water molecules and hydroxyl groups with titanium dioxide (TiO2) surfaces is ubiquitous and very important in anatase nanoparticle photocatalytic processes. Infrared spectroscopy, assisted by ab initio calculations of vibrational frequencies, can be a powerful tool to elucidate the mechanisms behind water adsorption. However, a straightforward comparison between measurements and calculations remains a challenging task because of the complexity of the physical phenomena occurring on nanoparticle surfaces. Consequently, severe computational approximations, such as harmonic vibrational ones, are usually employed. In the present work we partially address this complexity issue by overcoming some of the standard approximations used in theoretical simulations and employ the Divide and Conquer Semiclassical Initial Value Representation (DC-SCIVR) molecular dynamics. This method allows to perform simulations of vibrational spectra of large dimensional systems accounting not only for anharmonicities, but also for nuclear quantum effects. We apply this computational method to water and deuterated water adsorbed on the ideal TiO2 anatase(101) surface, contemplating both the molecular and the dissociated adsorption processes. The results highlight not only the presence of an anharmonic shift of the frequencies in agreement with the experiments, but also complex quantum mechanical spectral signatures induced by the coupling of molecular vibrational modes with the surface ones, which are different in the hydrogenated case from the deuterated one. These couplings are further analyzed by exploiting the mode subdivision performed during the divide and conquer procedure.
Project description:The cations of an ordered omphacite from the Tauern window were gradually disordered in piston cylinder experiments at temperatures between 850 and 1150 °C. The samples were examined by X-ray powder diffraction and then investigated using low-temperature calorimetry and IR spectroscopy. The low-temperature heat capacity data were used to obtain the vibrational entropies, and the line broadening of the IR spectra served as a tool to investigate the disordering enthalpy. These data were then used to calculate the configurational entropy as a function of temperature. The vibrational entropy does not change during the cation ordering phase transition from space group C2/c to P2/n at 865 °C but increases with a further temperature increase due to the reduction of short-range order.Supplementary informationThe online version contains supplementary material available at 10.1007/s00269-023-01260-7.