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.     

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.     

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.     

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.     

Formation of Polymeric Lewis Acid–Lewis Base Complexes with Well-defined Organoboron Polymers

The binding of Lewis bases to organoboron polymeric Lewis acids has been studied and the parameters that determine the complexation equilibrium have been investigated, which include (i) the strength of the individual Lewis acids and Lewis bases, (ii) concentration, and (iii) temperature. While the strongly Lewis acidic borane polymers poly(4-bis(pentafluorophenyl)borylstyrene) (PS-BPf) and poly(4-(di-2-thienylboryl)styrene) (PS-BTh) form isolable complexes with strong Lewis bases such as 4-t-butylpyridine (^tPy), a temperature dependent equilibrium is established with weaker bases such as THF. Similarly, the weakly Lewis acidic boronate polymer poly(4-diethoxyborylstyrene) (PS-BOEt) undergoes a temperature dependent equilibrium with the strong Lewis base 4-dimethylaminopyridine (DMAP), while poly(4-pinacolatoborylstyrene) (PS-BPin) does not significantly bind to pyridine bases. Decomplexation of PS-BTh· ^t Py is achieved by treatment with the stronger Lewis acid, B(C₆F₅)₃, thereby confirming the reversible nature of the polymeric Lewis acid–base adducts. This paper is dedicated to Professor Ian Manners in gratitude of his guidance throughout the years and recognition of his scientific accomplishments     

Sterol metabolism in the opportunistic pathogen <Emphasis Type="Italic">Pneumocystis</Emphasis>: Advances and new insights

Pneumocystis can transiently colonize healthy individuals without causing adverse symptoms, and most people test positive for exposure to this organism early in life. However, it can cause Pneumocystis pneumonia (PcP) in people with impaired immune systems and is a major cause of death in HIV/AIDS. Although it has close affinities to the Ascomycetes, Pneumocystis has features unlike those of any single group of fungi. For example, Pneumocystis does not synthesize ergosterol, which is consistent with the inefficacy of amphotericin B and some triazoles in clearing PcP. Pneumocystis sterols include distinct Δ⁷ 24-alkylsterols. Metabolic radiolabeling experiments demonstrated that P. carinii synthesizes sterols de novo. Cholesterol is the most abundant sterol in Pneumocystis; most, if not all, is scavenged from the mammalian host lung by the pathogen. The P. carinii erg7, erg6, and erg11 genes have been cloned, sequenced, and expressed in heterologous systems. The recombinant P. carinii S-adenosyl-l-methionine:C-24 sterol methyl transferase (SAM:SMT) has a preference for lanosterol over zymosterol as substrate, and the enzyme can catalyze the transfer of either one or two methyl groups to the C-24 position of the sterol side chain. Two different sterol compositions were detected among human-derived P. jirovecii; one was dominated by C₂₈ and C₂₉ sterols, and the other had high proportions of higher molecular mass components, notably the C₃₂ sterol pneumocysterol. The latter phenotype apparently represents organisms blocked at 14α-demethylation of the sterol nucleus. These studies suggest that SAM:SMT is an attractive drug target for developing new chemotherapy for PcP.     

Terpolymers. II. Mechanical properties and transition temperatures of terpolymers of vinyl stearate,vinyl acetate,and vinyl chloride

Vinyl stearate was studied as a major internal plasticizer in terpolymers containing vinyl acetate and vinyl chloride. The terpolymers were prepared by systematically replacing vinyl acetate by close increments of vinyl stearate starting with combinations of vinyl acetate and vinyl chloride, in increments, over all compositions. For comparison of properties, a complete range of copolymers of vinyl stearate and vinyl chloride, as well as mixtures of poly(vinyl chloride) and di-2-ethylhexyl phthalate (DOP) were also made. The external plasticizer was more efficient in reducing the glass temperature than was vinyl stearate. The decline in T_g with weight fraction of plasticizer was linear for the copolymers and terpolymers but concave downward with the liquid diluent. The linear decline was shown to involve mere additivity of the free volume contributed by each side-chain methylene (or methyl) group in both vinyl esters to reducing T_g. The mechanism of the diluent system was more complex. However, the magnitude of the reduction of tensile modulus at a given weight fraction of DOP could be equaled or exceeded by the same amount of vinyl stearate, by increasing the vinyl acetate content of the base copolymer to 40 mole-% or more. Unfortunately, the ultimate strengths and elongations of internally plasticized systems were reduced more than those of the mixtures at comparable compositions. Vinyl stearate was found to markedly retard photolytic degradation compared to both vinyl acetate and the external plasticizer in unstabilized samples having nearly the same thermal treatment. The effect was greater than could be ascribed to dilution by the long alkyl group. The production of a stearoyl radical more stable than the radicals initiating dehydrochlorination is suggested as a possible mechanism.     

Cycling hardening and serration yielding of Fe-Ni-Cr alloy at high temperature under out-phase TMF

Behaviour of hardening and serration yield of a Fe-Ni-Cr alloy under isothermal cycling (ISC) and out-phase TMF was studied on the basis of varied hysteresis loops. Cycling hardening and serrated yielding for ISC depend on the temperature and the total strain range, stronger hardening with serrated yielding at higher strain range under ISC at 600 °C, but no hardening and serrated yielding occurred under ISC at 800 °C. Stronger hardening with stress serration occurred at the thermal path going to the lowest temperature, no stress serration occurred at the highest temperature under the out-phase. The hardening also depends on the total strain range, higher total strain range with lower cycling temperature resulted in a stronger hardening and remarkable serration yielding behavior. Weaker hardening without serrated yielding occurred at near 800 °C may due to an obvious cycling stress drop under out-phase TMF. Change in the shape of the hysteresis loops also expresses the degree of the damage of the tested alloy under out-phase and ISC.