Precise determination of Mg/Fe ratios applicable to terrestrial olivine samples using Raman spectroscopy

The relationship between Mg# [ = 100 Mg/(Mg + Fe) in mol] and the Raman shift was analyzed precisely for olivine [(Mg, Fe)₂SiO₄] samples with Mg# between 100 and 62.8. Two prominent peaks at 826–820 cm⁻¹ (peak 1) and 858–849 cm⁻¹ (peak 2) and three subordinate peaks at 883–881 cm⁻¹ (peak 3), 920–914 cm⁻¹ (peak 4), and 967–951 cm⁻¹ (peak 5) were observed to shift monotonously to lower wavenumbers with decreasing Mg#. The ΔMg#( = Mg#_ref − Mg#) versus Δν(= ν_ref − ν) can be linearly regressed for each peak as ΔMg# = A Δν, where ν is a peak wavenumber of olivine with Mg# ranging from 100 to 62.8, and ν_ref is that of olivine with a reference value of Mg#, namely, Mg#_ref. We set Mg#_ref as 100 (i.e.pure forsterite Mg₂SiO₄) whereas A is a regression parameter (5.789, 4.294, 12.34, 6.348, and 2.09, respectively,for peaks 1, 2, 3, 4, and 5). This equation enables us to avoid small inter‐laboratory differences of wavenumber calibration. The equation for peak 2 yields estimations of Mg# in geologically satisfactory precision, ± 1 Mg# (1σ) in the Mg# range of 100–62.8. Copyright © 2011 John Wiley & Sons, Ltd.     

Electroluminescence properties of In-doped Zn2SiO4 thin films prepared by sol–gel process

The effect of In doping on the electroluminescence (EL) properties of Zn₂SiO₄:In thin films was investigated. In-doped Zn₂SiO₄ thin films were deposited on BaTiO₃ substrates and their EL properties were characterized in this study. X-ray powder diffraction patterns of In-doped Zn₂SiO₄ powders revealed a single phase of Zn₂SiO₄ for In concentrations up to approximately 1.5 mol%, whereas a secondary phase of In₂O₃ was observed for In concentrations in the range of 2–10 mol%. The maximum luminance of thin film electroluminescent (TFEL) devices varied significantly with the amount of In doping. The highest luminance with blue emission was obtained when 2 mol% In was doped. The blue emission of In-doped Zn₂SiO₄ thin film may be related to the In substitution for Zn. The 2 mol% In-doped Zn₂SiO₄ thin film exhibited blue emission with CIE color coordinates of x=0.208 and y=0.086.     

Bifurcation structure of chaotic attractor in switched dynamical systems with spike noise

High-frequency ripple (spike noise) effects in the qualitative properties of DC/DC converter circuits. This study investigates the bifurcation structure of a chaotic attractor in a switched dynamical system with spike noise. First, we introduce the system dynamics and derive the associated Poincaré map. Next, we show the bifurcation structure of the chaotic attractor in a system with spike noise. Finally, we investigate the dynamical effect of spike noise in the existence region of the chaotic attractor compare with that of a chaotic attractor in a system with ideal switching. The results suggest that spike noise enlarges an invariant set and generates a new bifurcation structure of the chaotic attractor.     

Star-shaped trimeric quaternary ammonium bromide surfactants: adsorption and aggregation properties

Novel star-shaped trimeric surfactants consisting of three quaternary ammonium surfactants linked to a tris(2-aminoethyl)amine core were synthesized. Each ammonium had two methyls and a straight alkyl chain of 8, 10, 12, or 14 carbons. The adsorption and aggregation properties of these tris(N-alkyl-N,N-dimethyl-2-ammoniumethyl)amine bromides (3C(n)trisQ, in which n represents alkyl chain carbon number) were characterized by equilibrium and dynamic surface tension, rheology, small-angle neutron scattering (SANS), and cryogenic transmission electron microscopy (cryo-TEM) techniques. 3C(n)trisQ showed critical micelle concentrations (CMC) 1 order of magnitude lower than that of the corresponding gemini surfactants with an ethylene spacer and the corresponding monomeric surfactants. The logarithm of the CMC decreased linearly with increasing hydrocarbon chain length for 3C(n)trisQ. The slope of the line, which is well-known as Klevens equation, was larger than those of the monomeric and gemini surfactants; however, considering the total carbon number in the chains, the slope was shallower than the monomeric and was close to the gemini. Through the results such as surface tensions at the CMC (32-34 mN m(-1)) and the parameters of standard free energy, CMC/C(20) and pC(20), it was found that 3C(n)trisQ could adsorb densely at the air/water interface despite the strong electrostatic repulsion between multiple quaternary ammonium headgroups. Moreover, dynamic surface tension measurements showed that the kinetics of adsorption for 3C(n)trisQ to the air/water interface was slow because of their bulky structures. Furthermore, the results of rheology, SANS, and cryo-TEM determined that 3C(n)trisQ with n = 10 and 12 formed ellipsoidal micelles at low concentrations in solution and the structures transformed to threadlike micelles with very few branches for n = 12 as the concentration increased, but for n = 14 threadlike micelles formed at relatively low concentrations.     

Polypyrrole-palladium nanocomposite coating of micrometer-sized polymer particles toward a recyclable catalyst

A range of near-monodisperse, multimicrometer-sized polymer particles has been coated with ultrathin overlayers of polypyrrole-palladium (PPy-Pd) nanocomposite by chemical oxidative polymerization of pyrrole using PdCl(2) as an oxidant in aqueous media. Good control over the targeted PPy-Pd nanocomposite loading is achieved for 5.2 μm diameter polystyrene (PS) particles, and PS particles of up to 84 μm diameter can also be efficiently coated with the PPy-Pd nanocomposite. The seed polymer particles and resulting composite particles were extensively characterized with respect to particle size and size distribution, morphology, surface/bulk chemical compositions, and conductivity. Laser diffraction studies of dilute aqueous suspensions indicate that the polymer particles disperse stably before and after nanocoating with the PPy-Pd nanocomposite. The Fourier transform infrared (FT-IR) spectrum of the PS particles coated with the PPy-Pd nanocomposite overlayer is dominated by the underlying particle, since this is the major component (>96% by mass). Thermogravimetric and elemental analysis indicated that PPy-Pd nanocomposite loadings were below 6 wt %. The conductivity of pressed pellets prepared with the nanocomposite-coated particles increased with a decrease of particle diameter because of higher PPy-Pd nanocomposite loading. "Flattened ball" morphologies were observed by scanning/transmission electron microscopy after extraction of the PS component from the composite particles, which confirmed a PS core and a PPy-Pd nanocomposite shell morphology. X-ray diffraction confirmed the production of elemental Pd and X-ray photoelectron spectroscopy studies indicated the existence of elemental Pd on the surface of the composite particles. Transmission electron microscopy confirmed that nanometer-sized Pd particles were distributed in the shell. Near-monodisperse poly(methyl methacrylate) particles with diameters ranging between 10 and 19 μm have been also successfully coated with PPy-Pd nanocomposite, and stable aqueous dispersions were obtained. The nanocomposite particles functioned as an efficient catalyst for the aerobic oxidative homocoupling reaction of 4-carboxyphenylboronic acid in aqueous media for the formation of carbon-carbon bonds. The composite particles sediment in a short time (相似文献   

Site-selective assembly and reorganization of gold nanoparticles along aminosilane-covered nanolines prepared on indium-tin oxide

We have fabricated gold nanoparticle (AuNP) arrays on indium-tin oxide (ITO) substrates in a nearly one-dimensional fashion. AuNPs were site-selectively immobilized on ITO of which the surface had been patterned by a nanolithography process based on scanning probe microscopy. The fabricated nanoscale lines covered with aminosilane self-assembled monolayer served as chemisorption sites for citrate-stabilized AuNPs of 20 nm in diameter, accordingly, AuNP nanolines with a thickness of single nanoparticle diameter were spontaneously assembled on the lines. In this 1D array, the AuNPs were almost separated from each other due to the electrostatic repulsion between their negatively charged surface layers. Furthermore, a reorganization process of the immobilized AuNP arrays has been successfully demonstrated by replacing each AuNP's surface layer from citric acid to dodecanethiol. By this process, the AuNPs lost their electrostatic repulsion and became hydrophobic so as to be attracted to each other through hydrophobic interaction, resulting in reorganization of the AuNP array. By repeating the deposition and reorganization cycle, AuNPs were more densely packed. The optical absorption peak of the arrays due to their plasmonic resonance was found to shift from 526 to 590 nm in wavelength with repeating cycles, indicating that the resonance manner was changed from the single nanoparticle mode to the multiple particle mode with interparticle coupling.     

Optical rectification effect due to surface plasmon polaritons at normal incidence in a nondiffraction regime

We carried out an experimental and numerical investigation of photoinduced voltage at normal incidence in the nondiffraction regime, which was not predicted to occur by the simple momentum conservation model. We prepared two samples: one having space inversion symmetry and the other without this feature. At normal incidence in the nondiffraction regime, we observed a finite signal only for the asymmetric structure. We found that surface plasmon polaritons (SPPs) are excited by the signal and are attributed to the origin of the voltage. We also evaluated the radiation force of light by using the Maxwell stress tensor and found that pressure of light and not shear force is mainly induced in the structure due to the asymmetric excitation of SPPs.     

Effects of L-Aspartic acid on the step retreat kinetics of calcite

Effects of L-Aspartic acid (L-Asp) on step retreat kinetics in the dissolution of calcite were investigated. The step retreat velocities under surface-controlled kinetics were determined from in-situ atomic force microscopic observations using an improved flow-through system. Comparison of the present results with those obtained under a mixed kinetics condition revealed that the addition of L-Asp promotes the transport process in the calcite dissolution through acid–base and/or complex forming reactions in the diffusion boundary layer. Additionally, promotion of the acute and obtuse step retreats by the L-Asp additive was observed under surface-controlled kinetics. This report is the first to clarify that L-Asp promotes surface processes in the dissolution of calcite.