Electrochemical characterization of 8-hydroxyquinoline-5-sulphonate/aluminium(III) aqueous solutions

8-Hydroxyquinoline-5-sulphonate/Al(III) aqueous solutions were studied both by potentiometric titrations and voltammetric measurements, in order to obtain the number, the stoichiometry and the stability constants of the complexes formed at equilibrium, and to evaluate the redox and (electro)kinetic properties of the free ligand and of the metal/ligand complexes. The complexes formed in 0.2 m (Na)Cl aqueous solution (stability log beta values ± standard deviation) are AlL⁺ (8.95 ± 0.05), AlL₂⁻ (17.43 ± 0.03) and AlL₃³⁻ (24.58 ± 0.05), where “L” denotes the free ligand in the completely deprotonated form (L²⁻, pK_a1 = 3.910 ± 0.008, pK_a2 = 8.319 ± 0.004). AlL₃³⁻ is the predominant Al(III) species in a very wide range of pH, metal and ligand concentrations and metal-to-ligand ratios. The free ligand shows an oxidation wave at 0.62 V versus SCE. The proposed oxidation mechanism includes a first reversible one-electron oxidation of the ligand, followed by a coupling reaction and by a second reversible one-electron oxidation, and finally by a decomposition reaction. The addition of Al(III) lowers the intensity of the oxidation wave due to the formation of the redox-inactive complex AlL₃³⁻. A residual low signal was attributed to the free ligand produced by the complex dissociation, AlL₃³⁻ = AlL₂⁻ + L²⁻. All the kinetic parameters involved in the ligand oxidation and in the complex disruption were calculated on the basis of the agreement between experimental and simulated linear sweep and cyclic voltammetries. Correctness of the mechanisms proposed was further confirmed “a posteriori” by the agreement between potentiometric and linear sweep voltammetric results. The low residual signal observed in the presence of fully formed complex was attributed to the free ligand produced by the complex dissociation, having a kinetic constant estimated 0.2 s⁻¹.     

Cholesterol transport and uptake in miniature swine fed vegetable and animal fats and proteis. 1. Plasma lipoproteins and LDL clearance

In a 2×2 factorial arrangement, miniature pigs were fed four diets containing vegetable protein/fat (soybean) and animal protein (egg white)/fat (beef tallow) to demonstrate the effects of protein and fat source on total plasma cholesterol, lipoprotein distribution, low density lipoprotein (LDL) composition, and plasma clearance of LDL-cholesterol and protein. Beef tallow consumption resulted in greater plasma cholesterol concentration, decreased LDL-cholesterol concentration, and a lower LDL-cholesterol to LDL-protein ratio than did consumption of soybean oil. High density lipoprotein (HDL)-cholesterol concentration was increased by beef tallow consumption. Cholesterol percentage by weight in LDL was significantly greater in pigs consuming soybean oil than those consuming beef tallow. Percentages by weight of protein, triglyceride and phospholipid in LDL were not significantly different in any group. Dietary protein source had no significant effect on total plasma cholesterol concentration, lipoprotein concentration or LDL composition. Egg white consumption decreased fractional catabolic rate and irreversible loss of LDL-cholesterol and LDL-protein when compared with consumption of soy protein. Dietary fat source had no consistent effect on LDL clearance from plasma. Dietary fat and protein seemed to influence lipoprotein metabolism by different mechanisms. Fat source altered lipoprotein concentration and LDL composition, whereas protein source affected the removal rate of LDL from plasma. Data taken from a dissertation submitted to Iowa State University by L. S. Walsh Hentges as partial fulfillment of the requirements for the Ph.D. degree. A preliminary paper, was presented at the meeting of the American Oil Chemists' Society in Dallas, Texas, May, 1984.     

Chemical Stability of the Fiber Coating Matrix Interface in Silicon-Based Ceramic Matrix Composites

Carbon and boron nitride are used as fiber coatings in silicon-based composites. In order to assess the long-term stability of these materials, reactions of carbon/Si₃N₄ and BN/SiC were studied at high temperatures with Knudsen effusion, coupon tests, and by microstructural examination. In the carbon/Si₃N₄ system, carbon reacted with Si₃N₄ to form gaseous N₂ and SiC. The formation of SiC limited further reaction by physically separating the carbon and Si₃N₄. Consequently, the development of high p (N₂) at the interface, predicted from thermochemical calculations, did not occur, thus limiting the potential deleterious effects of the reaction on the composite. Strong indications of a reaction between BN and SiC were shown by TEM and SIMS analysis of the BN/SiC interface. In long-term exposures, this reaction can lead to a depletion of a BN coating and/or an unfavorable change of the interfacial properties, limiting the beneficial effects of the coating.     

Rheology,structure, and properties of ethylene–vinyl acetate/metallocene‐catalyzed ethylene–α‐olefin copolymer blends

The rheology, morphology, thermal, mechanical, and adhesive properties of blends containing ethylene–vinyl acetate and metallocene‐catalyzed ethylene–α‐olefin copolymers, containing butene and octene comonomers, were investigated. On the basis of the thermal and rheological properties and scanning electron microscopy observations, we deduced that these blends were immiscible, both in the solid and melt states over the whole range of compositions. Rheological properties were correlated to blend morphology with the Palierne emulsion model. The butene‐based blends had better mechanical properties, which was attributed to their finer morphology, lower interfacial tension, and better adhesive properties. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 881–889, 2004     

Solvent-free oxidation of benzyl alcohol using titania-supported gold–palladium catalysts: Effect of Au–Pd ratio on catalytic performance

The oxidation of benzyl alcohol with molecular oxygen under solvent-free conditions has been investigated using a range of titania-supported Au–Pd alloy catalysts to examine the effect of the Au–Pd ratio on the conversion and selectivity. The catalysts have been compared at high reaction temperature (160 °C) as well as at 100 °C, to determine the effect on selectivity since at lower reaction temperature the range of by-products that are formed are limited. Under these conditions the 2.5 wt.% Au–2.5 wt.% Pd/TiO₂ was found to be the most active catalyst, whereas the Au/TiO₂ catalyst demonstrated the highest selectivity to benzaldehyde. Toluene, formed via either a hydrogen transfer process or an oxygen transfer process, was observed as a major by-product under these forcing conditions.     

Ractions of SiC with H2/H2O/Ar Mixtures at 1300°C

The reactions of a sintered α-SiC with 5% H₂/H₂O/Ar at 1300°C were studied. Thermomchemical modeling indicates that three reaction regions are expected, depending on the initial water vapor or equivalently oxygen content of the gas stream. A high oxygen content ( P (O₂) > 10⁻²² atm) leads to a SiO₂ formation. This generally forms as a protective film and limits consumption of the SiC (passive oxidation). An intermediate oxygen content (10⁻²² atm > P (O₂) > 10⁻²⁶ atm) leads to SiO and CO formation. These gaseous products can lead to rapid consumption of the SiC (active oxidation). Thermogravimetric studies in this intermediate region gave reaction rates which appear to be controlled by H₂O gas-phase transport to the sample and reacted microstructures showed extensive grain-boundary attack in this region. Finally, a very low oxygen content ( P (O₂) < 10⁻²⁶ atm) is thermochemically predicted to lead to selective removal of carbon and formation of free silicon. Experimentally low weight losses and iron silicides are observed in this region. The iron silicides are attributed to reaction of free silicon and iron impurities in the system.     

Altered arachidonic acid content in polymorphonuclear and mononuclear cells from patients with allergic rhinitis and/or asthma

We previously have found that monocytes from patients with allergic rhinitis and/or asthma produce less PGE₂ than cells from normal subjects in response to a histamine-induced lymphokine. In order to investigate this observation further, we measured the fatty acid content in the total phospholipids derived from the plasma, red cells, buffy coat cells, neutrophils, monocytes and lymphocytes of 27 allergic patients and 21 normal controls. There were no substantial differences between atopics and normals in the fatty acid analyses carried out for plasma and red cells. However, linoleic acid (18∶2n−6) levels were elevated significantly in the buffy coat fraction, while arachidonic acid (20∶4n−6) levels were reduced. Measurement of fatty acid levels after fractionation of the buffy coat population into neutrophils and monocytes yielded similar elevations in 18∶2n−6 and reduced 20∶4n−6. In contrast, lymphocytes appeared to have the reverse pattern, i.e., significantly reduced 18∶2n−6 and elevated 20∶4n−6 levels. These data suggest that atopic leukocytes may have altered essential fatty acid metabolism.     

Novel polyurethane coating technology through glycidyl carbamate chemistry

Glycidyl carbamate chemistry combines the excellent properties of polyurethanes with the crosslinking chemistry of epoxy resins. Glycidyl carbamate functional oligomers were synthesized by the reaction of polyfunctional isocyanate oligomers and glycidol. The oligomers were formulated into coatings with several amine functional crosslinkers at varying stoichiometric ratios and cured at different temperatures. Properties such as solvent resistance, hardness, and impact resistance were dependent on the composition and cure conditions. Most coatings had an excellent combination of properties. Studies were carried out to determine the kinetics of the curing reaction of the glycidyl carbamate functional oligomers with multifunctional and model amines. Detailed kinetic analysis of the curing reactions was also undertaken. The results indicated that the glycidyl carbamate functional group is more reactive than a glycidyl ether group. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, on October 27–29, 2004, in Chicago, IL.     

Measurement of intrinsic rates for homogeneous gas‐phase reactions at high temperatures

A coiled quartz tubular reactor has been designed to measure the intrinsic reaction kinetics for homogeneous reactions at high temperatures up to 1100°C. Actual gas residence times were less than 100 ms. A simple and well‐studied test reaction (i.e., the decomposition of nitrous oxide, N₂O), with published intrinsic kinetics, was used to verify the operation of the experimental reactor. For this system, Peclet numbers (Pe = uL/DL) computed from experimental conversion data were greater than 1000, indicating that the plug flow assumption could be used with this reactor system to determine intrinsic rate expressions with errors of less than 5% for the conditions studied.     

What localizes beneath: A metric multisensor localization and mapping system for autonomous underground mining vehicles

Robustly and accurately localizing vehicles in underground mines is particularly challenging due to the unavailability of GPS, variable and often poor lighting conditions, visual aliasing in long tunnels, and airborne dust and water. In this paper, we present a novel, infrastructure‐less, multisensor localization method for robust autonomous operation within underground mines. The proposed method integrates with existing mine site commissioning and operation procedures and includes both an offline map‐building process and an online localization algorithm. The approach combines the strengths of visual‐based place recognition, LIDAR‐based localization, and odometry in a particle filter fusion process. We provide an extensive experimental validation using new large data sets acquired in two operational Australian underground hard‐rock mines (including a 600m‐deep multilevel mine with approximately 33 km of mapping data and 7 km of vehicle localization) by actual mining vehicles during production operations. We demonstrate a significant increase in localization accuracy over prior state‐of‐the‐art SLAM research systems and real‐time operation, with processing times in the order of 10 Hz. We present results showing a mean error of 0.68 m from the Queensland Mine data set and 1.32 m from the New South Wales Mine data set and at least 86% reduction in error compared with prior state of the art. We also analyze the impact of the particle filter parameters with respect to localization accuracy. Together this study represents a new approach to positioning systems for currently deployed autonomous vehicles within underground mine environments.