National Institute Of Materials Physics - Romania

Ferromagnetism in 3d metals is re-examined in a simple band model. It is shown that the molecular field model cannot account for the low values of coercive field in ferromagnetic pure metals, and that the standard Stoner theory of band ferromagnetism incorrectly evaluates the total electronic energy and cannot predict reasonable Curie temperatures. A simple band model for magnetism is formulated, yielding a criterion for ferromagnetism even in absence of a Hubbard term, involving only the density of states (DOS) at the Fermi level, its derivative and the filling of the 3d band. By introducing a double-peaked DOS, one may explain the occurrence of ferromagnetism in bcc Fe, hcp-fcc Co and fcc Ni, the stabilization of fcc-hcp or bcc structures across all 3d elements, the occurrence of antiferromagnetism in chromium, and derive reasonable Curie temperatures. 'Re-entrant' ferromagnetism is predicted at ultrahigh temperatures, suggesting an alternate origin for the geomagnetic field.

The effect of temperature on the features of the crystal and magnetic structures, as well as the magnetic properties of the solid solution of SrFe10.8In1.2O19 hexaferrite was investigated. The appearance of ferroelectric properties was detected at room temperature, which contradicts the generally accepted opinion on the description of the crystal structure of hexaferrites within the framework of the centrosymmetric P6(3)/mmc (No. 194) space group. The reasons of spontaneous polarization in solid solutions of hexaferrites remain controversial. No deviation from the collinear magnetic structure was found in the investigated temperature range from 1.5 to 350 K, while the thermal expansion of the unit cell was practically absent in the range from 1.5 to 50 K. The crystal structure of hexaferrites was considered in the framework of both centrosymmetric P6(3)/mmc and non-centrosymmetric P6(3)mc space groups, which allowed us to associate the emerging spontaneous polarization with unequal distortions of neighboring oxygen polyhedra.

Tuning the intrinsic structural and stoichiometric properties by different means is used for increasing the green energy production efficiency of complex oxide materials. Here, we report on the formation of self-assembled nanodomains and their effects on the photoelectrochemical (PEC) properties of LaFeO3 (LFO) epitaxial thin films as a function of layer's thickness. The variation with the film's thickness of the structural parameters such as in-plane and out-of-plane crystalline coherence length and the coexistence of different epitaxial orientation-SrTiO3// LFO, SrTiO3// LFO and [110] LFO//[10] STO, as well as the appearance of self-assembled nanodomains for film's thicknesses higher than 14 nm, is presented. LFO thin films exhibit different epitaxial orientations depending on their thickness, and the appearance of self-assembled nanopyramids-like domains after a thickness threshold value has proven to have a detrimental effect on the PEC functional properties. Using Nb:SrTiO3 as conductive substrate and 0.5 M NaOH aqueous solution for PEC measurements, the dependence of the photocurrent density and the onset potential vs. RHE on the structural and stoichiometric features exhibited by the LFO photoelectrodes are unveiled by the X-ray diffraction, high-resolution transmission electron microscopy, ellipsometry, and Rutherford backscattering spectroscopy results. The potentiodynamic PEC analysis has revealed the highest photocurrent density J(photocurrent) values (up to 1.2 mA/cm(2)) with excellent stability over time, for the thinnest LFO/Nb:SrTiO3 sample, both cathodic and anodic behavior being noticed. Noticeably, the LFO thin film shows unbiased hydrogen evolution from water, as determined by gas chromatography in aqueous 0.5 M NaOH solution under constant illumination.

NiO-loaded SnO2 powders were prepared involving two chemical procedures. The mesoporous SnO2 support was synthesized by a hydrothermal route using Brij 35 non-ionic surfactant as a template. The nickel loadings of 1 and 10 wt.%. NiO were deposited by the wet impregnation method. The H2S sensing properties of xNiO-(1-x)SnO2 (x = 0, 1, 10%) thick layers deposited onto commercial substrates have been investigated with respect to different potential interfering gases (NO2, CO, CO2, CH4, NH3 and SO2) over a wide range of operating temperatures and relative humidity specific for in-field conditions. Following the correlation of the sensing results with the morphological ones, 1wt.% NiO/SnO2 was selected for simultaneous electrical resistance and work function investigations. The purpose was to depict the sensing mechanism by splitting between specific changes over the electron affinity induced by the surface coverage with hydroxyl dipoles and over the band bending induced by the variable surface charge under H2S exposure. Thus, it was found that different gas-interaction partners are dependent upon the amount of H2S, mirrored through the threshold value of 5 ppm H2S, which from an applicative point of view, represents the lower limit of health effects, an eight-hour TWA.

Fibres of poly(methyl methacrylate) were obtained by electrospinning, subjected to coating with a gold layer and then attached on a thin polyethylene terephthalate substrate in order to obtain flexible electrodes for biosensing applications. The morphology of these electrodes, investigated by scanning electron microscopy showed multilayers of random oriented fibres of approx. 400 nm diameter. The electrochemical characterization of these flexible electrodes was performed by cyclic voltammetry and electrochemical impedance spectroscopy in acid and neutral media, in the absence and in the presence of redox probes, proving their superior performance (e.g. 5fold current density value) when compared to planar gold electrodes obtained on silicon wafers. The electrodes obtained from conductive electrospun polymeric fibres nets were tested by cyclic voltammetry and amperometry for the detection of hydrogen peroxide with a sensitivity of 0.84 mA cm-2 mM-1 and a detection limit of 20.40 ?M. The immobilization of the model enzyme glucose oxidase at the surface of the gold-coated electrospun polymeric fibres electrode was investigated and the obtained biosensor was applied for glucose determination in aqueous solutions by fixed potential amperometry with a sensitivity of 3.10 ?A cm-2 mM-1, a detection limit of 0.33 mM, and reduced interferences. Also, the practical applicability of the biosensor was tested for the detection of glucose in artificial sweat and serum samples.

Peppers are consumed all over the world, have several benefits to human health, such as antioxidant properties that can prevent diseases related to free radicals such as cardiovascular, inflammatory diseases, cancer, among others. This work aimed to evaluate the antioxidant capacity (AOC) of 36 varieties of peppers through ABTS and DPPH radical scavenging, electroanalytical assays, and to verify the vasorelaxant properties of selected samples. The greater the amount of capsaicin found in the extracts, the higher the AOC the greater the vasorelaxation. Naga had the highest scoring for antioxidant capacity, pout showed the lowest antioxidant capacity, vase pyramid intermediate level, whereas the capsaicin content followed the same trend. Extracts from all pepper varieties studied presented vasorelaxant properties in independent and dependent endothelial pathways.

This Special Issue was devoted to developments made in Physical Vapour Deposited (PVD) biomedical coatings for various healthcare applications. The scrutinized PVD methods were Radio-Frequency Magnetron Sputtering (RF-MS), Cathodic Arc Evaporation, Pulsed Electron Deposition and its variants, Pulsed Laser Deposition, and Matrix Assisted Pulsed Laser Evaporation (MAPLE), due to their great promise especially in the dentistry and orthopaedics. These methods have yet to gain traction for industrialization and large-scale application in biomedicine. A new generation of implant coatings can be made available by the (1) incorporation of organic moieties (e.g., proteins, peptides, enzymes) into thin films by innovative methods such as combinatorial MAPLE, (2) direct coupling of therapeutic agents with bioactive glasses or ceramics within substituted or composite layers via RF-MS, or (3) by innovation in high energy deposition methods such as arc evaporation or pulsed electron beam methods.

The magnetic properties of thin-film multilayers [Fe/Py]/FeMn/Py are investigated as a function of temperature and thickness of the antiferromagnetic FeMn spacer using SQUID magnetometry. The observed behavior differs substantially for the structures with 6 nm and 15 nm FeMn spacers. While the 15 nm FeMn structure exhibits exchange pinning of both ferromagnetic layers in the entire measurement temperature interval from 5 to 300 K, the 6 nm FeMn structure becomes exchange de-pinned in the vicinity of room temperature. The depinned state is characterized by a single hysteresis loop centered at zero field and having enhanced magnetic coercivity. The observed properties are explained in terms of finite-size effects and possible ferromagnetic interlayer coupling through the thin antiferromagnetic spacer.

Magnetite (Fe3O4) and ferrite (MFe2O4, M = Mn, Zn) hydrophobic magnetic nanoparticles with various shapes and sizes were synthesized by high-temperature reaction of organic precursor solutions. Spherical, cubic, hexagonal, and octahedral shapes and sizes ranging from 10 to 100 nm were obtained. It has been proven that the reported high capability of tailoring the shape and the size of the surface-coated nanoparticles allows controlling a variety of properties that are relevant to many potential applications. Structurally well-formed hydrophobic magnetic nanoparticles with high saturation magnetization values are reported. The hydrophobic oleic acid shell was successfully transformed by a simple and environmentally friendly oxidative scission method into azelaic acid. The morphostructural characteristics, size distributions, chemical composition, and magnetic properties of the resulting hydrophilic nanoparticles were investigated by electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, Mossbauer spectroscopy, superconducting quantum interference device, and vibrating sample magnetometry. Magnetic hyperthermia measurements have been performed in a specially designed sample holder placed in an inductor with copper windings assuring alternating magnetic fields of safely biological amplitude-frequency products. The optimal shape with a specific size range for nanoparticles dispersed in various carriers providing the best heating efficiency is reported.

Highly dispersed supported NbOx species were prepared via a deposition precipitation-carbonization (DPC)-like method. As precursors for niobium species and carrier ammonium niobate(V) oxalate hydrate and humins were used. Characterization of the resulted catalysts indicated bi-functional acid-base niobium species anchored onto a highly hydrophobic graphite-like carbon structure. These catalysts were investigated in the one-pot conversion of glucose to 5-hydroxymethylfurfural (HMF) in a biphasic system consisting of a mixture of a 20 wt% NaCl aqueous solution phase and an organic extracting phase (methyl-isobutyl-ketone (MIBK), 2-tert-butylphenol (TBP) or 2sec-butylphenol (SBP)). The optimization conditions afforded the highest yield to HMF (96 %) for the GHNb1.2 catalyst (with 2.5 wt%Nb), the base/acid sites ratio of 1.76, in biphasic TBP/water system, at 180 ?C after 8 h.