Valence state of iron and molybdenum cations under conditions of anionic deficiency in Sr2FeMoO6–δ

The activation energy of oxygen diffusion in strontium ferromolybdate Sr2FeMoO6–δ was determined by the Merzhanov technique based on the temperature dependences of the oxygen desorption dynamics. It was found that the activation energy has a minimal value of 76.7 kJ/mol at δ = 0.005 and maximum value of 156.3 kJ/mol at δ = 0.06. It was suggested that, with an increase in the oxygen vacancies concentration, an interaction occurs between them and the nearest cations with the subsequent formation of associates of various types that are less mobile than the single anion vacancies. According to the Mössbauer spectroscopy data, it was established that the appearance of oxygen vacancies and their ordering contribute to the isomer shift, and some of the iron ions occupy the tetrahedral (or close to it) positions in the lattice. This indicates the formation of associates of oxygen vacancies. The results of XPS studies have shown that the increase in the concentration of oxygen vacancies results in a decrease of the Mo6+ and Fe2+ concentration. At the same time, the number of Mo5+ and Fe3+ cations increases due to the redistribution of the electron density, and molybdenum cations in a different valence state (Mo4+) appear.publishe

Degree of phase transformations in the conditions of polythermal synthesis of SrBaFeMoO6–δ

The sequence of phase transformations during the crystallization of SrBaFeMoO6–δ by the solid-phase technique from a stoichiometric mixture of simple oxides SrCO3 + BaCO3 + 0.5Fe2O3 + MoO3 was studied. It has been established that the synthesis of barium – strontium ferromolybdate proceeds through a series of sequential - parallel stages. It was found that to minimize the effect of intermediate reaction products, it is necessary to use combined synthesis modes. As a result of using combined synthesis modes for annealing for 20 h and T = 1443 K in vacuum of 10−5 Torr at the pressure of residual oxygen gas 10−8 Pa, it was possible to obtain a single-phase barium – strontium ferromolybdate compound with superstructural ordering of iron and molybdenum cations.publishe

Modelling and Fabrication of Micro-SOFC Membrane Structure

Fabrication process of micro-SOFC membrane structure using the bulk micromachining of silicon technique with SiO2 and Si3N4 sacrificial layers is presented in this study. The process involves back side photolithography, magnetron sputtering of platinum thin films, thermal evaporation of YSZ electrolyte, deep reactive ion etching of silicon, and, finally, release of free-standing membrane using CF4/O2 plasma etching.X-ray analysis shows the cubic phase of YSZ electrolyte and platinum electrodes. Modelling of normal stress distribution in the micro-SOFC structure with the Si3N4 sacrificial layer shows that at high temperatures the substrate expands less than the coating, causing tensile stresses in the substrate area next to the coating and compressive stresses in the coating, as the substrate material has a lower coefficient of thermal expansion than the layered Pt/YSZ/Pt coating. DOI: http://dx.doi.org/10.5755/j01.ms.20.2.5585</p

Effect of Ag nanocube optomechanical modes on plasmonic surface lattice resonances

Noble metal nanoparticles patterned in ordered arrays can interact and generate hybrid plasmonic–photonic resonances called surface lattice resonances (SLRs). Dispersion curves help explain how the Bragg coupling conditions and radiation patterns create dipolar and quadrupolar SLRs, but they assume that the nanoparticles are static structures, which is inaccurate at ultrafast time scales. In this article, we examine how local surface plasmon resonances (LSPRs) supported by cubic Ag nanocrystals are modulated by ultrafast photophysical processes that generate optomechanical modes. We use transient absorbance spectroscopy measurements to demonstrate how the LSPRs of the nanoparticles modulate the SLR of the array over time. Two primary mechanical breathing modes of Ag nanocubes were identified in the data and input into electromagnetic models to examine how fluctuations in shape affect the dispersion diagram. Our observations demonstrate the impact of optomechanical processes on the photonic length scale, which should be considered in the design of SLR-based devices

Synthesis and Electron-Beam Evaporation of Gadolinium-Doped Ceria Thin Films

Gadolinium-doped ceria (GDC) nanopowders, prepared using the co-precipitation synthesis method, were applied as a starting material to form ceria-based thin films using the electron-beam technique. The scanning electron microscopy (SEM )analysis of the pressed ceramic pellets&rsquo; cross-sectional views showed a dense structure with no visible defects, pores, or cracks. The AC impedance spectroscopy showed an increase in the total ionic conductivity of the ceramic pellets with an increase in the concentration of Gd2O3 in GDC. The highest total ionic conductivity was obtained for Gd0.1Ce0.9O2-&delta; (&sigma;total is 11 &times; 10&minus;3 S&#8729;cm&minus;1 at 600 &deg;C), with activation energies of 0.85 and 0.67 eV in both the low- and high-temperature ranges, respectively. The results of the X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma optical emission spectrometer (ICP-OES) measurements revealed that the stoichiometry for the evaporated thin films differs, on average, by ~28% compared to the target material. The heat-treatment of the GDC thin films at 600 &deg;C, 700 &deg;C, 800 &deg;C, and 900 &deg;C for 1 h in the air had a minor effect on the surface roughness and the morphology. The results of Raman spectroscopy confirmed the improvement of the crystallinity for the corresponding thin films. The optimum heat-treating temperature for thin films does not exceed 800 &deg;C

Synthesis and electron-beam evaporation of gadolinium-doped ceria thin films

Gadolinium-doped ceria (GDC) nanopowders, prepared using the co-precipitation synthesis method, were applied as a starting material to form ceria-based thin films using the electron-beam technique. The scanning electron microscopy (SEM )analysis of the pressed ceramic pellets’ cross-sectional views showed a dense structure with no visible defects, pores, or cracks. The AC impedance spectroscopy showed an increase in the total ionic conductivity of the ceramic pellets with an increase in the concentration of Gd2O3 in GDC. The highest total ionic conductivity was obtained for Gd0.1Ce0.9O2-δ (σtotal is 11 × 10−3 S∙cm−1 at 600 °C), with activation energies of 0.85 and 0.67 eV in both the low- and high-temperature ranges, respectively. The results of the X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma optical emission spectrometer (ICP-OES) measurements revealed that the stoichiometry for the evaporated thin films differs, on average, by ~28% compared to the target material. The heat-treatment of the GDC thin films at 600 °C, 700 °C, 800 °C, and 900 °C for 1 h in the air had a minor effect on the surface roughness and the morphology. The results of Raman spectroscopy confirmed the improvement of the crystallinity for the corresponding thin films. The optimum heat-treating temperature for thin films does not exceed 800 °C

Microstructuring of electrospun mats employing femtosecond laser

Electrospun mats from nano/micro-fibers with control porosity and pore shape may be ideal candidate for tissue engineering scaffolds. In this study three type of poly(vinyl alcohol) (PVA) mats of 48-65 µm thickness with different nano/micro-fibers diameters mostly of 100-200 nm were deposited by electrospinning process. Controlled density porosity in the electrospun mats was introduced by Yb:KGW femtosecond laser micromachining system. The influence of electrospun mat micro structure, the distance between the adjacent laser ablation points, the number of femtosecond laser pulses on quality and structure of laser irradiated holes were investigated. It was demonstrated that the quality of irradiated holes depend on structure of electrospun mats (diameter of nano/micro-fibers, thickness of mats) and femtosecond laser processing parameters. Varying the distance between points and number of applied femtosecond laser pulses it is possible to fabricate electrospun mats with pores of 22-36 μm diameter.DOI: http://dx.doi.org/10.5755/j01.ms.21.1.10249</p

Wavelength-tailored enhancement of Raman scattering on a resonant plasmonic lattice

Routine single-molecule analysis using surface-enhanced Raman scattering (SERS) is still out of reach using conventional substrates based on corrugated metallic surfaces. Tailoring the substrate to a specific excitation wavelength is an effective way to improve the SERS enhancement factor. Here, we present a comprehensive theoretical and experimental study of wavelength-tailored SERS substrates with improved sensitivity, exploiting the surface lattice resonance (SLR) in a plasmonic lattice comprised of assembled Ag nanoparticles. We tuned the SLR close to 532 nm and evaluated its effect on SERS. We found that SLR-based substrates had 10 times overall higher sensitivity and 100 times higher sensitivity at the target wavelength compared to non-tuned counterparts. Furthermore, we compared monomer and tetramer unit cell cases and found that the combined effect of tuned SLR and hot spots further improves the enhancement factor more than 400 times over a substrate with a random layer of nanoparticles