M?ssbauer analysis of high-energy mechanical-milled sand fraction of a magnetic soil developing on basalt

A sample of the coarse sand fraction from the soil material of the A-horizon (0?C0.2 m from the soil surface) of a dusky red magnetic Oxisol was submitted to high-energy mechanical milling for different times. This assay aimed mainly at (a) monitoring the individualization of strongly aggregated mineral particles, and (b) measuring the effect of the milling pressure on the mineralogy changes of the material. These data are also intended to experimentally subside any physical model describing the mechanical behavior of the superficial soil layer that is subjected to intensive machine management, in agriculture fields. Powder X-ray data reveal that some mineralogical phases, notably gibbsite, disappear soon after the first few hours milling. The 298 K-transmission Mössbauer spectrum for the non-milled sand sample shows a qualitatively typical pattern for the sand fraction of basalt derived soils, with magnetically ordered sextets, assignable mainly to hematite and maghemite, and an intense central (super)paramagnetic Fe^3?+? doublet. For the milled samples, spectra revealed progressive spectral reduction of the magnetic hyperfine structure, with concomitant increase of relative subspectral areas due to (super)paramagnetic phases, as the milling time increased. This result is consistent with the reduction of measured saturation magnetization, from 4.96(8) J T^???1 kg^???1, for the non-milled sample, to 3.26(7) J T^???1 kg^???1, for the sample milled for 8 hours.     

Controls over spatial and seasonal variations on isotopic composition of the precipitation along the central and eastern portion of Brazil

Based on Global Network Isotopes in Precipitation (GNIP) isotopic data set, a review of the spatial and temporal variability of δ¹⁸O and δ²H in precipitation was conducted throughout central and eastern Brazil, indicating that dynamic interactions between Intertropical and South Atlantic Convergence Zones, Amazon rainforest, and Atlantic Ocean determine the variations on the isotopic composition of precipitation over this area. Despite the seasonality and latitude effects observed, a fair correlation with precipitation amount was found. In addition, Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) air mass back trajectories were used to quantify the factors controlling daily variability in stable isotopes in precipitation. Through a linear multiple regression analysis, it was observed that temporal variations were consistent with the meteorological parameters derived from HYSPLIT, particularly precipitation amount along the trajectory and mix depth, but are not dependent on vapour residence time in the atmosphere. These findings also indicate the importance of convective systems to control the isotopic composition of precipitation in tropical and subtropical regions.     

Micellar core-shell-type acrylic-polyurethane hybrid materials with self-polishing property

Abstract

Marine fouling can be a serious problem in the shipping industry, since it increases the surface roughness of the hull and hence its frictional resistance to its movement through water. Antifouling paint can be defined as preventing the attachment of marine organisms onto surfaces. However, the most commonly used antifouling coating which is the tributyltin-based self-polishing copolymer causes the severe pollution of marine environment. Ammonium salt-based paints include tertiary amines as biocides which have effective biocidal and biodegradable properties without accumulation in the sea environment. However, ammonium salt-based coatings were too sensitive to seawater and became swollen. In this study, polyurethane-acrylic copolymers were synthesized by radical polymerization. These hybrid materials were found to form core–shell structures in aqueous media. Synthesis and properties of copolymers were investigated by Fourier transform-infrared spectrometer, proton-nuclear magnetic resonance, transmission electron microscopy, and dynamic light scattering. The polishing rate of self-polishing copolymer was determined from the reduction in dry film thickness after artificial seawater immersion under a dynamic condition.     

Electric field control of nonvolatile four-state magnetization at room temperature

We find the realization of large converse magnetoelectric (ME) effects at room temperature in a magnetoelectric hexaferrite Ba0.52Sr2.48Co2Fe24O41 single crystal, in which rapid change of electric polarization in low magnetic fields (about 5 mT) is coined to a large ME susceptibility of 3200 ps/m. The modulation of magnetization then reaches up to 0.62μ(B)/f.u. in an electric field of 1.14 MV/m. We find further that four ME states induced by different ME poling exhibit unique, nonvolatile magnetization versus electric field curves, which can be approximately described by an effective free energy with a distinct set of ME coefficients.     

Self‐formed Schottky barrier induced selector‐less RRAM for cross‐point memory applications

We propose a selector‐less Pr_0.7Ca_0.3MnO₃ (PCMO) based resistive‐switching RAM (RRAM) for high‐density cross‐point memory array applications. First, we investigate the inhomogeneous barrier with an effective barrier height (Φ_eff), i.e., self‐formed Schottky barrier. In addition, a scalable 4F² selector‐less cross‐point 1 kb RRAM array has been successfully fabricated, demonstrating set, reset, and read operation for high cell efficiency and high‐density memory applications. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Multi-stacked organic light-emitting diodes using zinc oxide nanoparticle interfacial layers

Stacked organic light-emitting diodes (SOLEDs) with 30-nm nanoparticle (NP) interfacial layers were investigated. Zinc oxide (ZnO) was used as an interfacial layer between two green polymer (GP) layers. SOLEDs with NP interfacial layers had higher device efficiency than did a single-unit device due to the high probability of exciton recombination that originated from the Auger electron-assisted energy up-conversion process. Although the current density and luminance of SOLEDs with ZnO NP interfacial layers were smaller than those of the reference device, the efficiency was doubled because of the big band alignment difference and the large band gap between GP and ZnO NP interfacial layers, which induced more radiative-exciton recombination.     

Optimization of Verapamil Drug Analysis by Excitation-Emission Fluorescence in Combination with Second-order Multivariate Calibration

Excitation emission fluorescence matrices (EEMs) of Verapamil drug were obtained by direct and by derivatization fluorescence spectroscopy. The fluorescence excitation and emission wavelengths were displaced to longer wavelengths and the fluorescence intensity was enhanced upon derivation with respect to the native fluorescence of the drug. The complete EEM of the native fluorescence of the drug and of the derivatization product were rapidly acquired by using a charged-coupled device detector (CCD), which is advantageous in terms of speed in the analysis, with respect to the use of a conventional photomultiplier detector. The EEMs were analyzed by several second-order multivariate calibration methods exploiting the second order advantage. The three-dimensional decomposition methods used, based in different assumptions about the trilinearity of the three way data structure under analysis, were parallel factor analysis (PARAFAC), bilinear least squares (BLLS), parallel factor analysis 2 (PARAFAC2) and multivariate curve resolution—alternating least squares (MCR-ALS). The determination was performed by using the standard addition approach. The figures of merit of the PARAFAC and BLLS methods were calculated, obtaining a lower limit of detection with the derivatization procedure, when compared with the direct measurement of the fluorescence of the drug. In Verapamil drug the best estimations were found with the BLLS and the MCR-ALS models. In the quantification of Verapamil in a pharmaceutical formulation the best estimation, when compared with the result obtained by the US Pharmacopeia high performance liquid chromatography approach, was obtained by direct fluorescence spectroscopy with MCR-ALS and by derivatization fluorescence spectroscopy with the PARAFAC2 model.     

Structural and electronic effects in metallocene catalysts studied by x‐ray techniques

A series of metallocenes, namely, [Cp₂ZrCl₂], [(MeCp)₂ZrCl₂], [(nBuCp)₂ZrCl₂], [(iBuCp)₂ZrCl₂], [(tBuCp)₂ZrCl₂], [Et(Ind)₂ZrCl₂], [Et(IndH₄)₂ZrCl₂], and [MeSi₂(Ind)₂ZrCl₂)] were analyzed by extended x‐ray absorption fine structure (EXAFS) and x‐ray photoelectron spectroscopy (XPS). Complementary techniques, UV–vis spectroscopy and cyclic and differential pulse voltammetry, were employed to characterize the organometallic complexes. The catalysts were evaluated in ethylene polymerization, having methylaluminoxane (MAO) as the cocatalyst, and the resulting polymers were characterized by gel permeation chromatography. The structural and electronic effects caused by the coordination sphere around the metal center and their effects on the catalytic activity and polymer characteristics are discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

Electron irradiation-enhanced core/shell organization of Al(Cr,Fe, Mn)Si dispersoids in Al–Mg–Si alloys

The age hardening 6061-T6 aluminium alloy has been chosen as structural material for the core vessel of the material testing Jules Horowitz nuclear reactor. The alloy contains incoherent Al(Cr, Fe, Mn)Si dispersoids whose characterization by energy-filtered transmission electron microscopy (EFTEM) analysis shows a core/shell organization tendency where the core is (Mn, Fe) rich, and the shell is Cr rich. The present work studies the stability of this organization under irradiation. TEM characterization on the same particles, before and after 1 MeV electron irradiation, reveals that the core/shell organization is enhanced after irradiation. It is proposed that the high level of point defects, created by irradiation, ensures a radiation-enhanced diffusion process favourable to the unmixing forces between (Fe, Mn) and Cr. Shell formation may result in the low-energy interface segregation of Cr atoms within the (Fe, Mn) system combined with the unmixing of Cr, Fe and Mn components.