Improved corrosion protection of aluminum alloys by electrodeposited silanes

Organofunctional silanes recently have emerged as outstanding, environmentally friendly corrosion protectors for metal substrates, compared with conventional chromate treatments. A simple immersion technique is typically used to coat the metal surface with silane films. However, the thickness and uniformity of the films are uncontrolled in this process. This paper proposes a new deposition technique for the silane films on the metal surface, i.e., by electrodeposition. Hydrolyzed silanes are water-soluble, ionized molecules, so they can be deposited on metals by electrodeposition. Various combinations of silane mixtures were tested at different voltages, pH values, bath concentrations, and exposure times on panels of alloy aluminum and mirror-polished ferro-plate. The surface structure was characterized by scanning electron microscopy (SEM) and ellipsometry. The resistance of the film to corrosion was investigated by direct current (DC) polarization and electrochemical impedance spectroscopy (EIS) techniques. Electrodeposition results in a more organized and uniform film with fewer pores, compared with immersed or dipped films. This paper was presented at the 2nd International Surface Engineering Congress sponsored by ASM International, on September 15–17, 2003, in Indianapolis, Indiana, and appears on pp. 320–26 of the Proceedings.     

The distribution of grain boundary planes in polycrystals

During the last ten years, techniques have been developed to measure the distribution of grain boundaries in polycrystals as a function of both lattice misorientation and grain boundary plane orientation. This paper presents a brief overview of the techniques used for these measurements and the principle findings of studies implementing these techniques. The most significant findings are that grain boundary plane distributions are anisotropic, that they are scale invariant during normal grain growth, that the most common grain boundary planes are those with low surface energies, that the grain boundary populations are inversely correlated with the grain boundary energy, and that the coincident site lattice number is a poor predictor of the grain boundary energy and population.     

DRY-RO membranes from cellulose acetate carbamates

Cellulose acetate carbamates (CACs) are the polymers which result when organic isocyanates are reacted with the free hydroxyl groups of cellulose acetate (CA). CACs are more hydrolytically stable and exhibit physical properties which are superior to those of their CA mixed ester analogs. Two synthetic approaches to CACs have been utilized in this study: (1) preformation, i.e., separate synthesis of such polymers prior to their inclusion in solutions for membrane casting; and (2) in situ formation, i.e., the inclusion of blocked isocyanates in standard dry process casting solutions of CA followed by thermal activation of the resultant dry membranes leading to regeneration of free isocyanate and subsequent CAC formation. Preformed CAC polymers have been prepared utilizing phenyl-, 3-chloropropyl-, 3-bromopropyl-, and 3-bromopropyl-(isothio)-, isocyanates. Polymers containing omega-halocarbamate moieties were quaternized with dimethylbenzylamine to produce ionogenic (QCAC) polymers containing quaternary ammonium groups. DRY-RO membranes from the QCACs exhibit flux/rejection values varying between 6–8 gfd at 98% rejection and 20 gfd at 90% rejection (0.5% NaCl feed at 400 psi and 25°C). In situ formation of CAC membranes has been effected with tolylene- and hexamethylene-diisocyantes, with quaternized isocyanate monomers employed for the preformed CAC polymers, and with specially tailored diisocyanates containing ionogenic groups. Crosslinking rendered all of the membranes acetone insoluble. Inasmuch as in situ formation substitutes the easy synthesis of blocked isocyanate monomers for the more difficult separate synthesis of preformed CAC polymers, it is anticipated that the former will replace the latter.     

Preparation of Protein-Stabilized β-Carotene Nanodispersions by Emulsification–Evaporation Method

This work was initiated to prepare protein-stabilized β-carotene nanodispersions using emulsification–evaporation. A pre-mix of the aqueous phase composed of a protein and hexane containing β-carotene was subjected to high-pressure homogenization using a microfluidizer. Hexane in the resulting emulsion was evaporated under reduced pressures, causing crystallization and precipitation of β-carotene inside the droplets and formation of β-carotene nanoparticles. Sodium caseinate (SC) was the most effective emulsifier among selected proteins in preparing the nanodispersion, with a monomodal β-carotene particle-size distribution and a 17-nm mean particle size. The results were confirmed by transmission-electron microscopy analysis. SC-stabilized nanodispersion also had considerably high ζ-potential (−27 mV at pH 7), suggesting that the nanodispersion was stable against particle aggregation. Increasing the SC concentration decreased the mean particle size and improved the polydispersity of the nanodispersions. Nanodispersions prepared with higher β-carotene concentrations and higher organic-phase ratios resulted in larger β-carotene particles. Although increased microfluidization pressure did not decrease particle size, it did improve the polydispersity of the nanodispersions. Repeating the microfluidization process at 140 MPa caused the nanodispersions to become polydisperse, indicating the loss of emulsifying capacity of SC due to protein denaturation.     

Informational Entropy: a Failure Tolerance and Reliability Surrogate for Water Distribution Networks

Evolutionary algorithms are used widely in optimization studies on water distribution networks. The optimization algorithms use simulation models that analyse the networks under various operating conditions. The solution process typically involves cost minimization along with reliability constraints that ensure reasonably satisfactory performance under abnormal operating conditions also. Flow entropy has been employed previously as a surrogate reliability measure. While a body of work exists for a single operating condition under steady state conditions, the effectiveness of flow entropy for systems with multiple operating conditions has received very little attention. This paper describes a multi-objective genetic algorithm that maximizes the flow entropy under multiple operating conditions for any given network. The new methodology proposed is consistent with the maximum entropy formalism that requires active consideration of all the relevant information. Furthermore, an alternative but equivalent flow entropy model that emphasizes the relative uniformity of the nodal demands is described. The flow entropy of water distribution networks under multiple operating conditions is discussed with reference to the joint entropy of multiple probability spaces, which provides the theoretical foundation for the optimization methodology proposed. Besides the rationale, results are included that show that the most robust or failure-tolerant solutions are achieved by maximizing the sum of the entropies.     

Correlation of reactivity with chemical structure: Thermal hydrogenation of gas oils

The relationship between chemical structure and reactivity for thermal hydroprocessing was studied for five gas oils derived from Alberta bitumens. Chemical structure was characterized by combining data from ¹ H and ¹³ C nuclear magnetic resonance spectroscopy, class fractionation, and elemental analysis to calculate structural parameters. Thermal hydrotreating was performed in a continuous-flow stirred reactor at 420 and 440°C, 13.9 MPa hydrogen pressure, and 1.5 h¹ LHSV. Conversion of the 343–525°C boiling fraction of the gas oils was correlated with the concentration of naphthenic methylene groups in the feed. Formation of methane and ethane was dependent on the degree of condensation of the aromatic rings in the feed oils. Thermal desulfurization was highly correlated with the amount of saturates in the feed, and the aromaticity of the resin fraction. Hydrogen consumption increased with the aromaticity of the gas oil…     

Use of cascade reduction potential for selective precipitation of Au,Cu, and Pb in hydrochloric acid solution

Optimization of reduction potential for electroseparation was studied for the recovery of gold, copper, and lead from acidic solution. A linear sweep voltammetric method enabled us to determine characteristic reduction potentials for each metal and the kinetics of the metal deposition indicated by current-voltage curves. In order to precipitate the metal species sequentially, reduction potentials were examined for the individual and mixed solutions of Au(III), Cu(II), and Pb(II). The three metals were reasonably well isolated from the mixed solutions such as Cu(II)/ Pb(II) and Au(III)/Cu(II)/Pb(II) in the order of the corresponding reduction potentials, in particular, the mass transfer controlled reduction potentials, obtained from linear sweep voltammetry (LSV) measurement.     

Factors influencing the efficacy of an interfacial modifier for the interface in an immiscible polymer blend

The modification of the interface in immiscible polymer blends is critical in order to optimize physical properties. Despite the great commercial importance of polymer blends, many aspects of the emulsification process remain unclear In this paper, it will be shown that an emulsification curve can be used to estimate the influence of the architecture molar mass of styrene/hydrogenated butadiene block copolymer interfacial modifiers on the emulsifion of polystyrene/ethylene-propylene rubber blends under melt processing conditions. An expression for eing the critical amount of copolymer to saturate the interface, as well as aspects concerning the localisation of the modifier in the blend system will also be addressed.     

Hydrodynamic characteristics of a FCC regenerator

The hydrodynamic and gas mixing characteristics have been determined in a FCC regenerator (0.48 m I.D.x3.4 m high) with FCC particles. Solids holdup in the dense bed decreases with increasing gas velocity, but it increases in the freeboard region. The bubble/void fraction increases with an increase along the bed height at a given gas velocity and increases with increasing gas velocity at a constant bed height. Backmixed tracer gas at the wall region is higher than that at the center region of the bed. The gas backmixing coefficient decreases with increasing gas velocity.     

Substrate-mediated interactions and intermolecular forces between molecules adsorbed on surfaces

Adsorbate interactions and reactions on metal surfaces have been investigated using scanning tunneling microscopy. The manners in which adsorbates perturb the surface electronic structure in their vicinity are discussed. The effects these perturbations have on other molecules are shown to be important in overlayer growth. Interactions of molecules with surface steps are addressed, and each molecule's electron affinity is shown to dictate its adsorption sites at step edges. Standing waves emanating from steps are demonstrated to effect transient molecular adsorption up to 40 A away from the step edge. Halobenzene derivatives are used to demonstrate how the surface is important in aligning reactive intermediates.