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

Enhanced UV Light-Emission of Zinc-Phosphate-Hydrate Hydrothermally-Grown on Cu Metal Substrates for Opto-Electronic Applications

In the present study, polycrystalline films of layered zinc phosphate hydrate are produced by a facile, low-temperature single-step hydrothermal fabrication method on top of Cu metal substrates. Despite containing structural water, the as-grown films remain crystalline, chemically stable, and electrically conductive. The photoluminescence spectrum obtained at room-temperature reveals the presence of a spectrally narrow, high-intensity ultraviolet band that consists of two Gaussian peaks at ≈377 and 383 nm and a UV-to-visible peak emission intensity ratio of ≈5.3. The electrical charge-transport properties remain Ohmic for electric fields of up to ≈2 kV m−1 and temperature (T) range of ≈223–368 K. The electrical conductivity is further found to vary exponentially with the inverse temperature, and the thermal activation energy, Ea is 285 ± 8 meV. A moderate UV-vis photoconduction effect is registered and assigned to light-assisted electronic transitions that involve near-band edge defect states. This study can potentially open a door to the engineering and deployment of water-based compounds with advanced, semiconducting-like attributes in short-wavelength opto-electronic devices

The role of the Fe/Mo cations ordering degree and oxygen non-stoichiometry on the formation of the crystalline and magnetic structure of Sr2FeMoO6‒δ

Single-phase Sr2FeMoO6-δ powders with various oxygen indices (δ) and degrees of the superstructural ordering (P) of the Fe/Mo cations were obtained from SrFeO2.52 and SrMoO4 reagents via solid-state synthesis. It has been established by means of the x-ray and neutron diffraction that, upon reducing the oxygen content and enhancing the superstructural ordering, the lengths of the Fe–O1 and Mo–O2 bonds in the crystal lattice increase, whereas the Fe–O2 and Mo–O1 bond lengths decrease. At the same time, the volume of the unit cell is reduced, which indicates an enhancement of the covalency degree of the bonds and stimulates a redistribution of the electron density, as well as an increase of the concentration of the spin-down charge carriers located in the conduction band on the Mo(t2g)↓ orbitals. This circumstance leads to an increase of the density of states at the Fermi level, accompanied by an amplification of the exchange interaction and elevation of the Curie temperature, which points to the leading role of the spin-polarized charge carriers at the Fermi level in the exchange interaction.publishe

Small-angle neutron scattering and magnetically heterogeneous state in Sr2FeMoO6–δ

Single-phase strontium ferromolybdate (Sr2FeMoO6–δ) samples with different degrees of the superstructural ordering of the Fe/Mo cations were obtained from partially reduced SrFeO3–х, SrMoO4 precursors by the solid-state technology. The study of the temperature dependences of the magnetization measured in the field-cooling and zero-field-cooling regimes indicated an inhomogeneous magnetic state of the samples. The presence of magnetic regions of different nature has also been revealed by the small-angle neutron scattering. For the Sr2FeMoO6–δ samples with different superstructural ordering of the Fe/Mo cations and for all values of the magnetic field induction in the range up to 1.5 T and of the scattering vector in the interval 0.1 >q >0.005 Å–1, the analytical dependence I ~ q–α obeys the Porod law (α ≈ 4), which corresponds to an object with a smooth and well-marked surface and polydisperse grain size. Deviations from the Porod law in the q > 0.1 Å–1 region and a weakening of the neutron scattering in applied magnetic fields may be ascribed to magnetic inhomogeneities with diameters D <6 nm, which are partially destroyed /oriented by magnetic fields В ≥1.5 T.publishe

Low-frequency magnetic sensing by magnetoelectric metglas/bidomain LiNbO3 long bars

We present an investigation into the magnetic sensing performance of magnetoelectric bilayered metglas / bidomain LiNbO3 long thin bars operating in a cantilever or free vibrating regime and under quasi-static and low-frequency resonant conditions. Bidomain single crystals of Y+128o-cut LiNbO3 were engineered by an improved diffusion annealing technique with a polarization macrodomain structure of the “head-to-head” and “tail-to-tail” type. Long composite bars with lengths of 30, 40 and 45 mm, as well as with and without attached small tip proof masses, were studied. ME coefficients as large as 550 V/cm∙Oe, corresponding to a conversion ratio of 27.5 V/Oe, were obtained under resonance conditions at frequencies of the order of 100 Hz in magnetic bias fields as low as 2 Oe. Equivalent magnetic noise spectral densities down to 120 pT/Hz1/2 at 10 Hz and to 68 pT/Hz1/2 at a resonance frequency as low as 81 Hz were obtained for the 45 mm long cantilever bar with a tip proof mass of 1.2 g. In the same composite without any added mass the magnetic noise was shown to be as low as 37 pT/Hz1/2 at a resonance frequency of 244 Hz and 1.2 pT/Hz1/2 at 1335 Hz in a fixed cantilever and free vibrating regimes, respectively. A simple unidimensional dynamic model predicted the possibility to drop the low-frequency magnetic noise by more than one order of magnitude in case all the extrinsic noise sources are suppressed, especially those related to external vibrations, and the thickness ratio of the magnetic-to-piezoelectric phases is optimized. Thus, we have shown that such systems might find use in simple and sensitive room-temperature low-frequency magnetic sensors, e.g., for biomedical applications.publishe

Magnetoelectric metglas/bidomain y + 140°-cut lithium niobate composite for sensing fT magnetic fields

We investigated the magnetoelectric properties of a new laminate composite material based on y+140°-cut congruent lithium niobate piezoelectric plates with an antiparallel polarized “head-to-head” bidomain structure and metglas used as a magnetostrictive layer. A series of bidomain lithium niobate crystals were prepared by annealing under conditions of Li2O outdiffusion from LiNbO3 with a resultant growth of an inversion domain. The measured quasi-static magnetoelectric coupling coefficient achieved |αE31| = 1.9 V·(cm·Oe)–1. At a bending resonance frequency of 6862 Hz, we found a giant |αE31| value up to 1704 V·(cm·Oe)–1. Furthermore, the equivalent magnetic noise spectral density of the investigated composite material was only 92 fT/Hz1/2, a record value for such a low operation frequency. The magnetic-field detection limit of the laminated composite was found to be as low as 200 fT in direct measurements without any additional shielding from external noises.publishe

Magnetic properties of amorphous Co0.74Si0.26/Si multilayers with different numbers of periods

Two sets of [Co0.74Si0.26(5nm)∕Si(s)]n amorphous films were prepared by magnetron sputtering: one in the form of multilayers with the Si spacer thickness s fixed at 3nm, and the number n of periods varying from 1 to 10 and the other with only two periods and s varying from 3to24nm (trilayers). In both sets, the Co0.74Si0.26 layer thickness t was fixed at 5nm. All the samples except the one with s=24nm manifest antiferromagnetic coupling. Their magnetic properties at room temperature were probed using the magnetooptical transverse Kerr effect (MOTKE) and ferromagnetic resonance (FMR). The relative increase in the saturation magnetization Ms (for trilayers, relative to a structure with s=24nm; for multilayers, relative to the single-layer structure) determined from the FMR measurements was compared with the exchange coupling strength HAFJ obtained from the MOTKE studies. The dependences of HAFJ and Ms on n and s were found to be very similar to each other. Possible mechanisms of this similarity are discussed.This work was supported by MICINN of Spain (grants Nos. HP2008-0032, NAN2004-09087 and FIS2008-06249) and CRUP of Portugal (grant No. E41/09) in the framework of the Spanish-Portuguese Integrated Action. G.N.K acknowledges support from FCT of Portugal through the “Ciencia 2007” program. C.Q. acknowledges support from the Spanish Government and European Social Fund under the “Ramón y Cajal” program.Peer reviewe

Landscape science: a Russian geographical tradition

The Russian geographical tradition of landscape science (landshaftovedenie) is analyzed with particular reference to its initiator, Lev Semenovich Berg (1876-1950). The differences between prevailing Russian and Western concepts of landscape in geography are discussed, and their common origins in German geographical thought in the late nineteenth and early twentieth centuries are delineated. It is argued that the principal differences are accounted for by a number of factors, of which Russia's own distinctive tradition in environmental science deriving from the work of V. V. Dokuchaev (1846-1903), the activities of certain key individuals (such as Berg and C. O. Sauer), and the very different social and political circumstances in different parts of the world appear to be the most significant. At the same time it is noted that neither in Russia nor in the West have geographers succeeded in specifying an agreed and unproblematic understanding of landscape, or more broadly in promoting a common geographical conception of human-environment relationships. In light of such uncertainties, the latter part of the article argues for closer international links between the variant landscape traditions in geography as an important contribution to the quest for sustainability

Composition, crystallization conditions and genesis of sulfide-saturated parental melts of olivine-phyric rocks from Kamchatsky Mys (Kamchatka, Russia)

Highlights • Parental melts of sulfide-bearing KM rocks have near primary MORB-like composition. • Crystallization of these S-saturated melts occurred in near-surface conditions. • Extensive fractionation and crustal assimilation are not the causes of S-saturation. • S content in melts can be restored by accounting for daughter sulfide globules. Abstract Sulfide liquids that immiscibly separate from silicate melts in different magmatic processes accumulate chalcophile metals and may represent important sources of the metals in Earth's crust for the formation of ore deposits. Sulfide phases commonly found in some primitive mid-ocean ridge basalts (MORB) may support the occurrence of sulfide immiscibility in the crust without requiring magma contamination and/or extensive fractionation. However, the records of incipient sulfide melts in equilibrium with primitive high-Mg olivine and Cr-spinel are scarce. Sulfide globules in olivine phenocrysts in picritic rocks of MORB-affinity at Kamchatsky Mys (Eastern Kamchatka, Russia) represent a well-documented example of natural immiscibility in primitive oceanic magmas. Our study examines the conditions of silicate-sulfide immiscibility in these magmas by reporting high precision data on the compositions of Cr-spinel and silicate melt inclusions, hosted in Mg-rich olivine (86.9–90 mol% Fo), which also contain globules of magmatic sulfide melt. Major and trace element contents of reconstructed parental silicate melts, redox conditions (ΔQFM = +0.1 ± 0.16 (1σ) log. units) and crystallization temperature (1200–1285 °C), as well as mantle potential temperatures (~1350 °C), correspond to typical MORB values. We show that nearly 50% of sulfur could be captured in daughter sulfide globules even in reheated melt inclusions, which could lead to a significant underestimation of sulfur content in reconstructed silicate melts. The saturation of these melts in sulfur appears to be unrelated to the effects of melt crystallization and crustal assimilation, so we discuss the reasons for the S variations in reconstructed melts and the influence of pressure and other parameters on the SCSS (Sulfur Content at Sulfide Saturation)