Analysis of XANES for identification of highly dispersed transition metal oxides on supports

XANES of vanadium and niobium oxide on silica or alumina have been analyzed quantitatively by a deconvolution technique. Based on the results for reference compounds, local structures of supported vanadium and niobium species were identified. The composition was estimated from difference spectra for the samples which consisted of two kinds of species.     

Preparation of Aluminum Nitride Powder from Aluminum Polynuclear Complexes

AIN powder was synthesized from aluminum polynuclear complexes. Basic aluminum chloride and basic aluminum lactate were used as the aluminum polynuclear complexes. These starting materials and glucose were dissolved in water and mixed homogeneously. AIN powder was obtained by calcining after drying and precalcining at 800°C under nitrogen gas flow. Then excess carbon was removed by firing in air. Nitridation in the system was investigated and compared with that in the alumina–carbon black system. It was found that in our reaction system nitridation began and proceeded at lower calcination temperatures above 1200°C than in the alumina–carbon black system. Using aluminum polynuclear complexes, AIN was synthesized through the nitridation of γ-alumina and produced in a very fine and sharp particle size distribution.     

An Application of Silica‐Based Monolithic Membrane Emulsification Technique for Easy and Efficient Preparation of Uniformly Sized Polymer Particles

Summary: Uniformly sized polymer particles were prepared by an emulsification and polymerization technique utilizing a silica monolithic membrane, namely the “silica monolithic membrane emulsification technique”. In this paper, we utilized silica monolithic membrane as a device for the preparation of uniformly sized polymer particles. A mixture of monomers, diluents and oil‐soluble initiator was emulsified into a continuous medium through the silica monolithic membrane and polymerized. The particles obtained had a higher size uniformity than that of particles prepared by previously reported membrane emulsification techniques, such as the Shirasu Porous Glass (SPG) emulsification technique. Through the silica monolithic membrane emulsification technique, we could prepare particles having availability as a possible packing material for solid‐phase extraction (SPE) and high performance liquid chromatography (HPLC).

SEM photograph of silica particles prepared through capillary plate membrane.     

Effect of chloride ions on leaching rate of chalcopyrite

The effect of chloride on chalcopyrite leaching has been investigated by performing batch leaching tests with three kinds of leaching solutions and using Hiroyoshi’s model, which suggests that a zone of rapid leaching exists between the critical potential (E_c, equilibrium redox potential for the reduction of CuFeS₂ to Cu₂S) and the oxidation potential (E_ox, equilibrium redox potential for the oxidation of Cu₂S). The results of the leaching tests show that the leaching rate in hydrochloric acid solution is the fastest and that the relationship between the Cu leaching rate and oxidation–reduction potential (ORP) follows Hiroyoshi’s model. Thermodynamic calculations indicate that, with an increase in the chloride concentration, the concentration of cuprous ions increases as the chlorocuprate(I) complex ions are formed and the contribution of cuprous ions to the critical potential is greater than that of cupric ions, even though the concentration of cuprous ions is lower than that of cupric ions. This fact suggests that the formation of chlorocuprate(I) ions in a chloride solution may improve the chalcopyrite leaching rate by increasing the critical potential.     

Simple and comprehensive two-dimensional reversed-phase HPLC using monolithic silica columns

Simple and comprehensive two-dimensional (2D)-HPLC was studied in a reversed-phase mode using monolithic silica columns for second-dimension (2nd-D) separation. Every fraction from the first column, 15 cm long (4.6-mm i.d.), packed with fluoroalkylsilyl-bonded (FR) silica particles, was subjected to the separation in the 2nd-D using one or two octadecylsilylated (C(18)) monolithic silica columns (4.6-mm i.d., 3 cm). Monolithic silica columns in the 2nd-D were eluted at a flow rate of up to 10 mL/min with separation time of 30 s that meets the fractionation every 15-30 s at the first dimension (1st-D) operated at a flow rate of 0.4-0.8 mL/min. Three cases were studied. (1) In the simplest scheme of 2D-HPLC, effluent of the 1st-D was directly loaded into an injector loop of 2nd-D HPLC for 28 s, and 2 s was allowed for injection. (2) Two six-port valves each having a sample loop were used to hold the effluent of the 1st-D alternately for 30 s for one 2nd-D column to effect comprehensive 2D-HPLC without the loss of 1st-D effluent. (3) Two monolithic silica columns were used for 2nd-D by using a switching valve and two sets of 2nd-D chromatographs separating each fraction of the 1st-D effluent with the two 2nd-D columns alternately. In this case, two columns of the same stationary phase (C(18)) or different phases, C(18) and (pentabromobenzyloxy)propylsilyl-bonded (PBB), could be employed at the 2nd-D, although the latter needed two complementary runs. The systems produced peak capacity of approximately 1000 in approximately 60 min in cases 1 and 2 and in approximately 30 min in case 3. The three stationary phases, FR, C(18), and PBB, showed widely different selectivity from each other, making 2D separations possible. The simple and comprehensive 2D-HPLC utilizes the stability and high efficiency at high linear velocities of monolithic silica columns.     

Enhanced path smoothing based on conjugate gradient descent for firefighting robots in petrochemical complexes*

The firefighting robot system (FFRS) comprises several autonomous robots that can be deployed to fire disasters in petrochemical complexes. For autonomous navigation, the path planner should consider the robot constraints and characteristics. Specifically, three requirements should be satisfied for a path to be suitable for the FFRS. First, the path must satisfy the maximum curvature constraint. Second, it must be smooth for robots to easily execute the trajectory. Third, it must allow reaching the target location in a specific heading. We propose a path planner that provides smooth paths, satisfy the maximum curvature constraint, and allows a suitable robot heading. The path smoother is based on the conjugate gradient descent, and three approaches are proposed for this path planner to meet all the FFRS requirements. The effectiveness of these approaches is qualitatively and quantitatively evaluated by examining the generated paths. Finally, the path planner is applied to an actual robot to verify the suitability of the generated paths for the FFRS, and planning is applied to another type of robot to demonstrate the wide applicability of the proposed planner.     

Peel Test Using Nonstationary Peel Method

The cohesive peel spectra of pressure-sensitive adhesive (PSA) tapes have been measured using a non-stationary peel tester. The experimental evidence and a viscoelastic analysis based on a peel model indicate that there are no significant effects of acceleration in the normal rate region. The nonstationary peel tester can be regarded as a useful tool for testing and evaluating PSA tapes.     

In Situ Observation of Deformation in Semi-solid Fe-C Alloys at High Shear Rate

Synchrotron X-ray radiography at 125 frames per second was used to study deformation mechanisms in semi-solid Fe-C alloys at high solid fraction and shear strain rates of 10^?1/s. An image correlation approach was also used to quantify the shear strain fields and study shear-induced dilation and the origin of shear cracking. It was shown that, at high solid fraction (90 to 93 pct solid), rearrangement including rotation and translation of solid particles became restricted and shear strain localized into narrow liquid-filled channels/fissures. Shear cracking was shown to originate from inadequate liquid flow into the expanding spaces between solid particles caused by shear-induced dilation. At lower solid fraction (~85 pct solid), solid particles rearranged with a significantly higher component of rotation leading to more shear-induced dilation and a wider shear band.     

Hydrostatic Pressure Influences HIF-2 Alpha Expression in Chondrocytes

Hypoxia-inducible factor (HIF)-2α is considered to play a major role in the progression of osteoarthritis. Recently, it was reported that pressure amplitude influences HIF-2α expression in murine endothelial cells. We examined whether hydrostatic pressure is involved in expression of HIF-2α in articular chondrocytes. Chondrocytes were cultured and stimulated by inflammation or hydrostatic pressure of 0, 5, 10, or 50 MPa. After stimulation, heat shock protein (HSP) 70, HIF-2α, nuclear factor kappa B (NF-κB), matrix metalloproteinase (MMP)-13, MMP-3, and vascular endothelial growth factor (VEGF) gene expression were evaluated. The levels of all gene expression were increased by inflammatory stress. When chondrocytes were exposed to a hydrostatic pressure of 5 MPa, HIF-2α, MMP-13, and MMP-3 gene expression increased significantly although those of HSP70 and NF-κB were not significantly different from the control group. In contrast, HIF-2α gene expression did not increase under a hydrostatic pressure of 50 MPa although HSP70 and NF-κB expression increased significantly compared to control. We considered that hydrostatic pressure of 5 MPa could regulate HIF-2α independent of NF-κB, because the level of HIF-2α gene expression increased significantly without upregulation of NF-κB expression at 5 MPa. Hydrostatic pressure may influence cartilage degeneration, inducing MMP-13 and MMP-3 expression through HIF-2α.     

Structure and gas permeation properties of asymmetric polyimide membranes made by dry–wet phase inversion: Influence of the polyimide molecular weight

In this article, we report the influence of the polyimide molecular weight (1.2 × 10⁵, 2.6 × 10⁵, and 4.1 × 10⁵) on the structure and the gas permeation properties of asymmetric polyimide membranes made by the dry–wet phase‐inversion process. The apparent skin layer thickness of the asymmetric membrane increased with increasing molecular weight, and the thicknesses of the membranes prepared from the three polyimides with a casting polymer solution containing 8.0 wt % butanol were 132, 350, and 739 nm, respectively. That is, the gas permeance in the asymmetric membranes increased with decreasing molecular weight. In contrast, the gas selectivity of the asymmetric membranes did not depend on the skin layer thickness. The solvent evaporation in the dry phase‐inversion process and the nonsolvent diffusion in the dry process were important factors that determined the formation of the asymmetric membrane. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010