A novel terbium composite nanoparticles: Preparation and selective fluorescence determination of chromium(VI)

A highly efficient ultrasonic-assisted method was successfully applied to prepare the strong fluorescence Tb/acetyl acetone (acac)/poly (2-Acrylamidoglycolic acid monohydrate) (PAAM) composite nanoparticles. Based on the fluorescence quenching of Tb/acac/PAAM by Cr(VI), an assay for the selective determination of Cr(VI), without separation of Cr(III), was developed. It is characteristic of very few interferences, stable fluorescence signals (at least 2 h), simple instrument (common spectrofluorometer) and simple step. Under optimal experimental conditions, the fluorescence intensity of the system is linearly proportional to the concentration of Cr(VI) in concentration range of 5-800 ng mL⁻¹ with a correlation coefficient of 0.9983. The limit of detection was found to be 0.5 ng mL⁻¹.The proposed method has been applied to the selective quantification of Cr(VI) in synthetic samples with satisfactory results.     

A study of energy dissipation and critical speed of granular flow in a rotating cylinder

Tuned vibration absorbers may improve the safety of flexible structures which are prone to excessive oscillation magnitudes under dynamic loads. A novel absorber design proposes sloshing of granular material in a rotating cylinder where the granular material is the energy dissipating agent. As the conventional dissipative elements require maintenance due to the nature of their function, the new design may represent a virtually maintenance free alternative.     

基于晶体旋光效应的近场光学空间滤波

 在激光传输与放大系统中,激光束的空间滤波是光束质量控制的重要环节。利用各向同性晶体的旋光性,采用偏振光检偏法选择不同空间频率光束的通过与阻挡,实现激光光束的近场空间滤波。用多个滤波器串接构成滤波器组,可提高光束空间窄带滤波性能。该方法有利于克服激光工程中采用4f滤波带来的空间滤波器体积庞大与抽空耗能的缺点。     

Experimental and numerical examination of eddy (Foucault) currents in rotating micro-coils: Generation of heat and its impact on sample temperature

The application of nuclear magnetic resonance (NMR) to systems of limited quantity has stimulated the use of micro-coils (diameter <1 mm). One method recently proposed for the union of micro-coils with Magic Angle sample Spinning (MAS), involves the integration of a tuned micro-coil circuit within standard MAS rotors inductively coupled to the MAS probe coil, termed “magic-angle coil spinning” (MACS). The spinning of conductive materials results in the creation of circulating Foucault (eddy) currents, which generate heat. We report the first data acquired with a 4 mm MACS system and spinning up to 10 kHz. The need to spin faster necessitates improved methods to control heating. We propose an approximate solution to calculate the power losses (heat) from the eddy currents for a solenoidal coil, in order to provide insight into the functional dependencies of Foucault currents. Experimental tests of the dependencies reveal conditions which result in reduced sample heating and negligible temperature distributions over the sample volume.     

A theoretical and numerical consideration of the longitudinal and transverse relaxations in the rotating frame

We previously derived a simple equation for solving time-dependent Bloch equations by a matrix operation. The purpose of this study was to present a theoretical and numerical consideration of the longitudinal (R_1ρ = 1/T_1ρ) and transverse relaxation rates in the rotating frame (R_2ρ = 1/T_2ρ), based on this method. First, we derived an equation describing the time evolution of the magnetization vector (M(t)) by expanding the matrix exponential into the eigenvalues and the corresponding eigenvectors using diagonalization. Second, we obtained the longitudinal magnetization vector in the rotating frame (M_1ρ(t)) by taking the inner product of M(t) and the eigenvector with the smallest eigenvalue in modulus, and then we obtained the transverse magnetization vector in the rotating frame (M_2ρ(t)) by subtracting M_1ρ(t) from M(t). For comparison, we also computed the spin-locked magnetization vector. We derived the exact solutions for R_1ρ and R_2ρ from the eigenvalues, and compared them with those obtained numerically from M_1ρ(t) and M_2ρ(t), respectively. There was excellent agreement between them. From the exact solutions for R_1ρ and R_2ρ, R_2ρ was found to be given by R_2ρ = (2R₂ + R₁)/2 − R_1ρ/2, where R₁ and R₂ denote the conventional longitudinal and transverse relaxation rates, respectively. We also derived M_1ρ(t) and M_2ρ(t) for bulk water protons, in which the effect of chemical exchange was taken into account using a 2-pool chemical exchange model, and we compared the R_1ρ and R_2ρ values obtained from the eigenvalues and those obtained numerically from M_1ρ(t) and M_2ρ(t). There was also excellent agreement between them. In conclusion, this study will be useful for better understanding of the longitudinal and transverse relaxations in the rotating frame and for analyzing the contrast mechanisms in T_1ρ- and T_2ρ-weighted MRI.     

Photocatalytic reduction of chromium(VI) in aqueous solution using dye-sensitized nanoscale ZnO under visible light irradiation

Photocatalytic removal of Cr⁶⁺ from aqueous solution using dye-sensitized nanoscale ZnO under visible light irradiation was studied in this work. First, nanoscale ZnO was prepared by the co-precipitation method. Then, sensitization of nanoscale ZnO by Alizarin Red S dye followed. Further, nanoscale ZnO and dye-sensitized nanoscale ZnO (designated nanoZnO and nanoZnO*, respectively) were both characterized by various photospectrometry methods, such as scanning electron microscopy (SEM), scanning electron microscopy-energy dispersive X-ray spectrometry (SEM-EDS), EDS-mapping, transmission electron microscopy (TEM), and X-ray diffractometry (XRD). It was found that both types of prepared particles are spherical in shape with a size range of 20 to 50 nm. XRD patterns showed that both nanoZnO and nanoZnO* had the same crystalline structure of zincite. In the photocatalytic reduction aspect, effects of different light sources and dosage of nanoZnO* on Cr⁶⁺ reduction ([Cr⁶⁺]_initial = 20 mg/L) were evaluated in this work. Treatment of chromium(VI)-bearing wastewater under the conditions of using 1.0 g/L of nanoZnO*, neutral pH, irradiation of household fluorescence lamps for 6 h and 17 h would yield Cr⁶⁺ removal efficiencies of about 68% and 90%, respectively. When the household fluorescence lamps were replaced by visible-light lamps of 400–500 nm in wavelength, the corresponding removal efficiencies dropped to about 50% and 75%, respectively. When nanoZnO* was irradiated by sunlight under almost the same experimental conditions, the Cr⁶⁺ reduction efficiency increased up to 90%. In summary, sensitizing nanoscale ZnO with Alizarin Red S dye for photocatalytic applications using visible light is feasible. The relevant reaction mechanism and pathways were also proposed in this work.     

Theoretical study of core ionized Cr(CO)6

The satellite structure of the C1s and O1s photoelectron spectra of chromium hexacarbonyl Cr(CO)₆ has been calculated by the INDO/CI method and compared with available high resolution core level photoelectron spectra. A reassignment of some of the lines is made. It is found that the satellite structure in both cases is dominated by excitations from metal-ligand bonding to metal-ligand antibonding Me(3d)-π^* orbitals, and that these shake-up excitations involve a significant charge transfer to the core ionized ligand from the rest of the molecule.     

Influence of Mixing Technique on Microstructure and Impact Properties of Isotactic Polypropylene/ Poly(Cis-Butadiene) Rubber Blends

Isotactic polypropylene/poly(cis-butadiene) rubber (iPP/PcBR vol%: 80/20) blends were prepared by melt mixing with various mixing rotation speeds. The effect of mixing technique on microstructure and impact property of blends was studied. Phase structure of the blends was analyzed by scanning electron microscopy (SEM). All of the blends had a heterogeneous morphology. The spherical particles attributed to the PcBR-rich phase were uniformly dispersed in the continuous iPP matrix. With increase of the mixing rotation speed, the dispersed phase particle's diameter distribution became broader and the average diameter of the separated particles increased. The spherulitic morphology of the blends was observed by small angle light scattering (SALS). Higher mixing rotation speed led to a more imperfect spherulitic morphology and smaller spherulites. Crystalline structure of the blends was measured by wide angle X-ray diffraction (WAXD) and small angle X-ray scattering (SAXS). The introduction of 20 vol% PcBR induced the formation of iPPβ crystals. Higher rotation speed led to a decrease in microcrystal dimensions. However, the addition of PcBR and the increase of mixing rotation speed did not affect the interplanar distance. The long period values were the same within experimental error as PcBR was added or the mixing rotation speed quickened. The normalized relative degree of crystallinity of the blends slightly increased under lower rotation speeds (30 and 45 rpm) and decreased under higher rotation speeds. The notched Izod impact strength of the blends was enhanced as a result of the increase of mixing rotation speed.     

Influence of Cu electroplating solutions on boron carbon nitride (BCN) film

Cu electroplating is required for the fabrication of Cu/low-k interconnections. The permeation of a plating solution into low-k films during Cu electroplating is a serious challenge for 45-nm nodes and more complex devices. We investigated the influence of Cu electroplating solutions on boron carbon nitride (BCN) as a low-k film. After dipping it into a Cu electroplating solution that contained additives, the BCN film's hydrophilic surface changed to a hydrophobic surface, and the incorporation of water into the BCN film was suppressed by surfactant adsorption. Sulfuric residue was detected on the BCN sample by thermal desorption spectroscopy after treatment in the Cu electroplating solution with additives; however, it was found through electrical measurements that this solution did not affect the leakage current or the dielectric constant of the BCN film. We successfully fabricated an electroplating Cu layer on a BCN film with good adhesion, and we believe that this BCN film is a sufficiently useful material for Cu/BCN integration in LSI.     

Theoretical study of the electronic structure of a tetragonal chromium(III) complex

The low-temperature single-crystal polarized absorption and the luminescence spectra of Cs₂[CrCl₂(H₂O)₄]Cl₃ are theoretically analyzed in order to determine the electronic structure of the trans-[CrCl₂(H₂O)₄]⁺ complex. This study, based on the Racah theory, leads to a good agreement between the theoretical and experimental energy levels. The electronic-exited state ⁴T_2g(O_h) is split into ⁴E_g and ⁴B_2g components due to the lowering of the symmetry from O_h to D_4h. The polarized absorption spectrum and the theoretical energies show that the ⁴E_g(D_4h) state is lower in energy than the ⁴B_2g(D_4h) state. The resolved vibronic structure in the luminescence spectrum reveals a progression in a non-totally symmetric b_1g mode, a manifestation of a Jahn-Teller effect in the emitting state ⁴T_2g(O_h). Both Jahn-Teller and spin-orbit coupling in the orbitally degenerated ⁴E_g(D_4h) state are necessary to account for the spectroscopic observations.     

Growth of fcc(111) on bcc(110): Influence of growth and annealing temperature on epitaxy and surface morphology for Pd on Cr

The effects of growth versus annealing temperature on epitaxial relationship and surface morphology were studied for Pd(111) films on Cr(110) surfaces. While the epitaxial orientation of the Pd films depends on film thickness as well as on growth temperature, subsequent annealing has no effect on the epitaxial orientation. Instead, additional annealing of room temperature grown films takes the surface morphology from an island to a terrace shape, which was not observed for samples directly grown at elevated temperatures. These different effects that growth and annealing temperature have, help understanding the resulting structure and morphology of the heteroepitaxial system.     

Effects of chromium on structure and mechanical properties of vanadium:A first-principles study

Stability and diffusion of chromium （Cr） in vanadium （V）, the interaction of Cr with vacancies, and the ideal me- chanical properties of V are investigated by first-principles calculations. A single Cr atom is energetically favored in the substitution site. Vacancy plays a key role in the trapping of Cr in V. A very strong binding exists between a single Cr atom and the vacancy with a binding energy of 5.03 eV. The first-principles computational tensile test （FPCTT） shows that the ideal tensile strength is 19.1 GPa at the strain of 18% along the [100] direction for the ideal V single crystal, while it decreases to 16.4 GPa at a strain of 12% when one impurity Cr atom is introduced in a 128-atom V supercell. For shear deformation along the most preferable { 110} （111） slip system in V, we found that one substitutional Cr atom can decrease the cleavage energy （7cl） and simultaneously increase the unstable stacking fault energy （]＇us） in comparison with the ideal V case. The reduced ratio of ]＇cl/]＇us in comparison with pure V suggests that the presence of Cr can decrease the ductility of V.     

Morphology and crystallographic properties of rubrene thin films grown on muscovite(0 0 1)

Thin films of the organic semiconductor rubrene were deposited on muscovite (0 0 1) substrates by hot wall epitaxy. The morphology of rubrene thin films in combination with their crystallographic properties was characterized by transmission electron microscopy. The initial growth proceeds in a partially wetting regime where amorphous droplets are formed. Through diffusive interactions the droplets merge together in partially crystalline open networks. At a more advanced growth stage, spherulites are formed and a variety of crystalline morphologies appears. Platelet- and needle-like morphologies can be assigned to the orthorhombic phase of rubrene with the [3 0 1] and [1 1 0] zone axes, respectively.     

Effect of Hydrogenation and Chlorination Reactions on the β Relaxation of Poly(Vinyl Chloride)

Abstract

The relaxation phenomena of polymers are very important because they play an important role in their physical properties. Dynamic mechanical analysis was used in this work in order to study the effect of tactic and compositional sequences on the relaxation processes observed in poly(vinyl chloride) (PVC). The polymers studied in this work were PVC modified by means of reductive hydrogenation and chlorination reactions at low degrees of modification. The results obtained with hydrogenated poly(vinyl chloride) indicated that the decrease in mmr tetrads at the end of the isotactic sequences in the chain by stereospecific hydrogenation led to concomitant decreases in intensity and temperature of the maximum of the β relaxation. This effect seemed to be stronger the longer the isotactic sequence associated with the said structure. On the other hand, in the case of chlorinated poly(vinyl chloride) (CPVC), the results of the evolution of the β relaxation with the degree of chlorination showed that the predominant factor was the compositional microstructure (substitution of hydrogen atoms by chlorine atoms, increasing the possibility of inter-chain interactions leading to a stiffening of the chain, with the consequent increase in the β temperature).     

Comparative study of epitaxial growth of Pt and Ir electrode films grown on MgO-buffered Si(100) by PLD

(200)-oriented Pt and Ir electrode films have been epitaxially grown on MgO/Si(100) by in situ pulsed-laser deposition (PLD). A comparison of crystallinity and surface morphology of both electrode films was made. It was found that both electrode films featured remarkable atomic-scale smooth surfaces and had the same epitaxial relationship with substrates. Different from the noncompact surface morphology of the Pt film, the morphology of the Ir film offers a rectangular grain shape and the grains are arrayed regularly and compactly. The difference in the surface morphology of both electrode films is briefly explained in terms of the degree of species saturation. PACS 81.15.Fg; 68.55.Jk; 61.14.Hg; 68.55.-a; 81.15.-z; 77.55.+f     

Molecular beam epitaxy growth and characterization of self-assembled InAs quantum dots on (1 0 0) InAlAs/InP substrates

Self-assembled InAs quantum dots (QDs) on In_0.52Al_0.48As layer lattice matched to (1 0 0) InP substrates have been grown by molecular beam epitaxy (MBE) and evaluated by transmission electron microscopy (TEM) and photoluminescence (PL). TEM observations indicate that defect-free InAs QDs can be grown to obtain emissions over the technologically important 1.3–1.55 μm region. The PL peak positions for the QDs shift to low energy as the InAs coverage increases, corresponding to increase in QD size. The room temperature PL peak at 1.58 μm was observed from defect-free InAs QDs with average dot height of 3.6 nm.     

An electron diffraction study of the misfit layer compound (NdS)nNbS2

Misfit layer compounds of the type (NdS)_nNbS₂ have been made by iodine vapour transport. They have been characterised by energy dispersive X-ray analysis, transmission electron microscopy and electron diffraction. An orthorhombic form with Am2m symmetry has been observed. The unit cell contains two layers of NdS and two layers of NbS₂. The layers have rectangular symmetry and are stacked alternately with their planes perpendicular to the c-axis. A curious feature of the structure is that the layers have a common b unit cell parameter but the a values, which depend on the metal element in a given layer, are incommensurate. The lattice parameters for the material are a = 0.5625 nm for the NdS layer, a = 0.331 nm for the NbS₂ layer, b = 0.5733 nm and c = 2.266 nm. The symmetry of the material observed in the present work is Am2m which differs from the Fm2m reported by others. It is argued that the lower symmetry occurs because of a displacement of Nb atoms in one of the layers in the unit cell. A comparison between calculated and observed electron diffraction patterns and energy arguments are used to support the proposed explanation.     

基于线变换的椭圆柱外隐身斗篷的设计研究

基于线变换方法与互补媒质理论提出了线变换下的椭圆柱外隐身斗篷,并得到了相应外隐身斗篷材料本构参数张量的表达式.根据导出的本构参数张量,利用电磁仿真软件分别对不同长度线段的外斗篷进行了仿真验证,仿真结果证实了所得到的本构参数张量的正确性.这种外斗篷的材料参数只在轴向变化,横向参数为常数,易于用超介质制备.考虑到损耗对隐身效果的影响,得到了引入损耗后的外斗篷磁场分布.最后给出了本构参数的分布.本文的研究为利用超介质制备外隐身斗篷提供了一种新的可行的方法.     

Atomic Structure and Properties of the (310) Symmetrical Tilt Grain Boundary (STGB) in SrTiO3 Part II: Comparison with Experimental Studies

The atomistic simulation results presented in Part I for SrTiO₃ (310) symmetrical tilt grain boundary (STGB, the so-called = 5 GB with 36.8° symmetrical misorientation about [001]) are analyzed in the context of available experimental studies. In particular, atomic imaging studies of SrTiO₃ GBs via high resolution TEM and incoherent Z-contrast STEM imaging; and determination of oxygen positions by combining electron energy loss spectroscopy (EELS) and bond-valence-sum rules, are compared with simulation results. The atomistic simulation data on the GB energies are compared with relative experimental estimates obtained via a novel approach of faceting of focused ion beam (FIB) induced microvoids.While there are considerable differences in details of simulation and experimental results, some basic trends seem to emerge about the core structural framework of GBs in SrTiO₃. The paper highlights the limitations of both, experimental and simulation techniques, and argues in favor of synergistic use of diverse experimental and simulation approach to determine the atomic structure and properties of GBs.     

Characterization of the “native” surface thin film on pure polycrystalline iron: A high resolution XPS and TEM study

The characterization of the “native” surface thin film on pure polycrystalline iron has been studied by high resolution X-ray photoelectron (XP) spectroscopy of Fe 2p and O 1s regions. The film was allowed to form by exposing the sample to atmosphere at ambient conditions for a period of 1 h. The systematic approach used here includes the determination of curve fitting parameters from external standards and their use in fitting the raw data for the surface thin film. The quantitative high resolution XPS analysis involved an angle resolved study of the surface to determine the chemical composition and thickness of this native film. The film was found to be a mixture of Fe₃O₄ and Fe(OH)₂ with a thickness of 1.2 ± 0.3 nm. This conclusion is consistent with thermodynamics as indicated by the Pourbaix diagram for the Fe-H₂O system and the phase diagram for the Fe-oxygen system. A detailed TEM study of the native surface film also supports this conclusion.