Synthesis and Magnetic Properties of Hematite Particles in a ‘‘Nanomedusa’’ Morphology

We present the synthesis, characterization, and magnetic properties of hematite particles in a peculiar “nanomedusa” morphology. The particles were prepared from an iron-silica complex by a hydrothermal process in a solution consisting of ethyl acetate and ethanol. The particles’ morphology, structure, and chemical composition were investigated by transmission electron microscopy, powder X-ray diffraction, and scanning electron microscope equipped with an energy-dispersive X-ray spectrometer. The “hairy” particles consist of a spherical-like core of about 100 nm diameter and fibrous exterior composed of thin “legs” of 5 nm diameter grown along one preferential direction. The particles’ cores are crystalline and undergo a magnetic phase transition to a weakly ferromagnetic state at a temperature of 930K thatmatches reasonably the N´eel temperature of bulk hematite. However, unlike bulk hematite that undergoesMorin transition to an antiferromagnetic state around room temperature and small hematite nanoparticles that are superparamagnetic, the “nanomedusa” particles remain weakly ferromagnetic down to the lowest investigated temperature of 2K. Each particle thus represents a nanodimensional “hairy” ferromagnet in a very broad temperature interval, extending much above the room temperature. Such high-temperature ferromagnetic nanoparticles are not frequently found among the nanomaterials

The effect of surface oxidation on the catalytic properties of Ga3Ni2 intermetallic compound for carbon dioxide reduction

Background: In a routine handling of a catalyst material, exposure to air can usually not be avoided. For noble metal catalysts that are resistant to oxidation, this is not an issue, but becomes important for intermetallic catalysts composed of two or more non-noble chemical elements that possess much different standard enthalpies of the oxide formation. The element with higher affinity to oxygen concentrates on the surface in the oxide form, whereas the element with lower affinity sinks into the subsurface region. This changes the number of active sites and the catalytic performance of the catalyst. We have investigated the instability of the surface composition to oxidation of the Ga3Ni2 noble metal-free intermetallic compound, a new catalyst for the CO2 reduction to CO, CH4 and methanol. Methods: The instability of the oxidized Ga3Ni2 surface composition to different heating-annealing conditions was studied by X-ray photoelectron spectroscopy (XPS), used to determine the elemental composition and the chemical bonding in the near-surface region. The dispersion of active sites available for the chemisorption of H-2 and CO on the Ga3Ni2 catalyst surface was determined by H-2 and CO temperature-programmed desorption. CO2 conversion experiments were performed by using the catalyst material reduced in hydrogen at temperatures of 300 and 600 degrees C. Results: XPS study of the Ga3Ni2 surface subjected to different heating-annealing conditions has revealed that the concentration of Ga at the oxidized surface is strongly enhanced and the concentration of Ni is strongly depleted with respect to the values in the bulk. By annealing the surface at 600 degrees C in ultra-high vacuum, the oxides have evaporated and thermal diffusion of atoms near the surface has partially reconstructed the surface composition towards the energetically more favorable bulk value, whereas annealing at a lower temperature of 300 degrees C was ineffective to change the surface composition. Catalytic tests were in agreement with the XPS results, where an increased CO2 conversion for the catalyst reduced with hydrogen at a higher temperature followed an increased Ni/Ga surface concentration ratio. Conclusions: The instability of the active surface chemical composition to oxidation in air must be taken into account when considering noble metal-free intermetallic catalysts as alternatives to the conventional catalysts based on noble metals. Ga3Ni2 and other Ga-Ni intermetallic compounds are good examples of binary intermetallic catalysts, whose catalytic performance is strongly affected by exposure to the air

Sterilization of polypropylene membranes of facepiece respirators by ionizing radiation

Ionizing radiation has been identified as an option for sterilization of disposable filtering facepiece respirators in situations where the production of the respirators cannot keep up with demand. Gamma radiation and high energy electrons penetrate deeply into the material and can be used to sterilize large batches of masks within a short time period. In relation to reports that sterilization by ionizing radiation reduces filtration efficiency of polypropylene membrane filters on account of static charge loss, we have demonstrated that both gamma and electron beam irradiation can be used for sterilization, provided that the respirators are recharged afterwards

Complex magnetism of single-crystalline AlCoCrFeNi nanostructured high-entropy alloy

Summary: We have investigated magnetism of the Al28Co20Cr11Fe15Ni26 single-crystalline high-entropy alloy. The material is nanostructured, composed of a B2 matrix with dispersed spherical-like A2 nanoparticles of average diameter 64 nm. The magnetism was studied from 2 to 400 K via direct-current magnetization, hysteresis curves, alternating-current magnetic susceptibility, and thermoremanent magnetization time decay, to determine the magnetic state that develops in this highly structurally and chemically inhomogeneous material. The results reveal that the Cr-free B2 matrix of composition Al28Co25Fe15Ni32 forms a disordered ferromagnetic (FM) state that undergoes an FM transition at TC≈ 390 K. The Al- and Ni-free A2 nanoparticles of average composition Co19Cr56Fe25 adopt a core-shell structure, where the shells of about 2 nm thickness are CoFe enriched. While the shells are FM, the nanoparticle cores are asperomagnetic, classifying into the broad class of spin glasses. Asperomagnetism develops below 15 K and exhibits broken-ergodicity phenomena, typical of magnetically frustrated systems

Nanostructure and local polymorphism in “ideal-like” rare-earths-based high-entropy alloys

Rare-earths-based hexagonal high-entropy alloys (HEAs) composed of the elements from the heavy half of the lanthanide series (from Gd to Lu, with the exception of Yb) and yttrium are much closer to an ideal solid solution than HEAs composed of other elements from the entire periodic system. Using the method of high-frequency levitation melting, three candidates for a physical realization of an ideal HEA were synthesized, an Y-Gd-Tb-Dy-Ho, a Gd-Tb-Dy-Ho-Lu and a Tb-Dy-Ho-Er-Tm, and a study of their structure and composition was performed to see how close to ideal HEA samples can be prepared. We found that all three HEAs exhibit a nanostructure of a hexagonal close-packed (hcp) matrix and rod-like cubic close-packed (ccp) precipitates of the lengths 200–600 nm and widths 50–100 nm. EDS analysis has revealed a general trend that the precipitates are slightly enriched in the elements with larger atomic radii relative to the matrix. The origin of the nanostructure that represents a local hcp ↔ ccp polymorphism at zero external pressure appear to be lattice distortions (equivalent to a chemical pressure), occurring due to the minute differences of the elements' atomic radii. The volume per atom is slightly larger in the ccp precipitates that are enriched in larger atoms, so that the lattice distortions can be better accommodated and minimized, which reduces the lattice strain energy that contributes to the mixing enthalpy ΔHmix ≠ 0. The employed synthesis route, which is standard for the preparation of alloys of high structural quality, did not lead to a physical realization of an ideal HEA in the most promising theoretical candidates

The effect of scandium on the structure, microstructure and superconductivity of equimolar Sc-Hf-Nb-Ta-Ti-Zr refractory high-entropy alloys

In this study, we investigate the scandium-containing Sc-Hf-Nb-Ta-Ti-Zr system of refractory high-entropy alloys (HEAs). Using the arc-melting method, we synthesized nine equimolar alloys (five 4-, three 5- and one 6-component), with all of them containing Sc. The alloys were characterized by XRD, electron microscopy and EDS, while superconductivity was investigated via electrical resistivity, specific heat and the Meissner effect. The results were compared to the parent Hf-Nb-Ta-Ti-Zr refractory HEAs, forming a single-phase body-centered cubic (bcc) structure and quite homogeneous microstructure. The addition of Sc produces a two-phase structure in the Sc-Hf-Nb-Ta-Ti-Zr alloys, with one phase being bcc and the other hexagonal close-packed (hcp). The hcp phase absorbs practically all Sc, whereas the Sc-poor bcc phase is identical to the bcc phase in the Hf-Nb-Ta-Ti-Zr parent system. Upon the Sc addition, the microstructure becomes very inhomogeneous. Large bcc dendrites (10–100 µm) are homogeneous in the central parts, but become a fine dispersion of sub-micron precipitates of the bcc and hcp phases close to the edges. The interdendritic regions are also a fine dispersion of the two phases. Superconductivity of the Sc-Hf-Nb-Ta-Ti-Zr alloys originates from the bcc phase fraction, which demonstrates identical superconducting parameters as the bcc Hf-Nb-Ta-Ti-Zr parent alloys, while the Sc-containing hcp phase fraction is non-superconducting