Computational modeling of cathodic limitations on localized corrosion of wetted SS 316L at room temperature

The ability of a SS 316L surface wetted with a thin electrolyte layer to serve as an effective cathode for an active localized corrosion site was studied computationally. The dependence of the total net cathodic current, I_net, supplied at the repassivation potential E_rp (of the anodic crevice) on relevant physical parameters including water layer thickness (WL), chloride concentration ([Cl⁻]) and length of cathode (Lc) were investigated using a three-level, full factorial design. The effects of kinetic parameters including the exchange current density (i_o,c) and Tafel slope (β_c) of oxygen reduction, the anodic passive current density (i_p) (on the cathodic surface), and E_rp were studied as well using three-level full factorial designs of [Cl⁻] and Lc with a fixed WL of 25 μm. The study found that all the three parameters WL, [Cl⁻] and Lc as well as the interactions of Lc × WL and Lc × [Cl⁻] had significant impact on I_net. A five-factor regression equation was obtained which fits the computation results reasonably well, but demonstrated that interactions are more complicated than can be explained with a simple linear model. Significant effects on I_net were found upon varying either i_o,c, β_c, or E_rp, whereas i_p in the studied range was found to have little impact. It was observed that I_net asymptotically approached maximum values (I_max) when Lc increased to critical minimum values. I_max can be used to determine the stability of coupled localized corrosion and the critical Lc provides important information for experimental design and corrosion protection.     

INTEGRATING ALBEMARLE RESOLVE DESULFURIZATION TECHNOLOGY WITH NOVEL PETRO-CANADA PROCESS CONCEPTS IN COMMERCIAL FCCU OPERATIONS

The gasoline and distillate sulfur regulations promulgated throughout the world to reduce tail-pipe emissions are now strongly impacting refinery operations and investments. FCC gasoline is recognized as the principal contributor of sulfur to the gasoline pool and has become the focus for meeting the new specifications. The difficulty in removing sterically hindered sulfur species in the fluid catalytic cracking unit (FCCU) cycle oil drives up the hydrogen and investment costs for treating the distillates. Although installation of pre- and post-treatment facilities is planned by many refiners, other non-capital approaches such as undercutting are being evaluated to meet interim and future sulfur levels. Even when expensive treatment facilities are installed, operating costs can be lowered and the flexibility of the facility increased with improvements in the ability to remove sulfur in the FCCU. In this article, we detail Petro-Canada's experience in integrating Albemarle's RESOLVE sulfur reduction technology with a combination of innovative process ideas. These concepts include heavy naphtha recycle, coprocessing of hydrogen donor feeds, and recycle of light cycle oil (LCO) to a specially designed stripper reactor. Special attention is paid to the interaction of deep FCC feed hydrodesulfurization with the FCC performance. The results demonstrate that very low FCC gasoline sulfur levels can be achieved without significant capital investment through novel approaches to recycle, creative integration of cat feed hydrotreating unit (CFHTU)-FCCU designs and operations, and application of state-of-the-art sulfur reduction additive technology. An added benefit of the RESOLVE 950 sulfur reduction technology is the substantial elimination of sulfur oxides in the FCC flue gas. This has been observed in Petro-Canada operations and numerous other RESOLVE 950 applications around the world.     

Mutation of herpesvirus thymidine kinase to generate ganciclovir-specific kinases for use in cancer gene therapies

Understanding the functional and mechanistic properties of themulti-substrate herpes simplex virus type-1 thymidine kinase(HSV-1 TK) remains critical to defining its role as a majorpharmacological target in herpesvirus and gene therapies forcancer. An inherent limitation of the activity of HSV-TK isthe >70-fold difference in the K_ms for phosphorylation ofthymidine over the pro-drug ganciclovir (GCV). To engineer anHSV-1 TK isoform that is specific for GCV as the preferred substrate,16 site-specific mutants were generated. The mutations wereconcentrated at conserved residues involved in nucleoside basebinding, Gln125 and near sites 3 and 4 involved in catalysisand substrate binding. The substrate preferences of each mutantenzyme were compared with wild-type HSV-1 TK. One mutant, termedQ7530 TK, had a lower K_m for GCV than thymidine. Expressionof the Q7530 TK in tumor cells indicated comparable metabolismto and improved sensitivity to GCV over wild-type HSV-1 TK,with minimal thymidine phosphorylation activity. A molecularmodeling simulation of the different HSV-1 TK active-sites wasdone for GCV and thymidine binding. It was concluded that mutationsat Gln125 and near site 4, especially at Ala168, were responsiblefor loss of deoxypyrimidine substrate binding.     

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.     

Some novel polymer-supported optically active phase transfer catalysts: 2. Use in displacement,reduction, epoxidation and addition reactions

The performance of 27 novel polymer-supported chiral phase transfer catalysts in a range of phase separated reactions has been studied. The later include a number of displacement reactions, sodium borohydride reductions of prochiral ketones, the epoxidation of chalcone, the addition of nitromethane to chalcone and the addition of thiophenol to cyclohexenone. Some of the reactions were performed under liquid/liquid conditions and others using solid/liquid. No systematic difference emerged between these. In general many of the catalysts provided fast reactions and good chemical yields of products. However, in no case was any significant enantiomeric excess achieved. The latter observation is discussed in the light of the reported behaviour of analogous non-supported catalytic systems, and suggestions proposed to explain these differences.     

Effect of Composition on the Electromechanical Properties of (1-x)Pb(Mg1/3Nb2/3)O3−XPbTiO3 Ceramics

Ceramic lead magnesium niobate–lead titanate ((1-x)PMN_-xPT) of different compositions has been prepared by the columbite precursor method. This study discusses compositions ranging from 0.94PMN–0.06PT to 0.60PM–N0.40PT, focusing on two areas of the (1-x)PMN_xPT system: compositions that exhibit electrostrictive behavior, and those that show piezoelectric behavior. In electrostrictive compositions where x is in the range of 0.06–0.20, the dielectric constant and electromechanical coupling factor dependencies on the bias field are evaluated. The optimal electromechanical properties are obtained with the composition 0.82PMN–0.18PT, measured at temperature T = T_m (the temperature of maximum dielectric constant) = 80°C and with a dc bias of 5 kV/cm. X–ray diffractometry is used to show that the (1-x)PMN_-xPT system has a compositionally wide two–phase region and that 0.655PMN–0.345PT is the morphotropic phase boundary (MPB) composition. Electromechanical property evaluation shows that the optimal piezoelectric properties (piezoelectric charge coefficient ( d₃₃ ) value of 720 pC/N, dielectric constant ( K ) value of 5400, and electromechanical planar and thickness coupling coefficient ( k_p and k_t , respectively) values of 62% and 46%, respectively) are obtained at the MPB composition.     

Synthesis of Organotin Polyamine Ethers Containing Acyclovir and their Preliminary Anticancer and Antiviral Activity

Organotin polyamine ethers containing acyclovir in their backbone were synthesized in moderate to high yield employing the aqueous interfacial polycondensation system. The products are high molecular weight polymers. Infrared spectroscopy of the products shows new bands characteristic of the formation of Sn–N and Sn–O bonds consistent with the proposed structure. MALDI-TOF MS below 2000 Da shows the presence of organotin and acyclovir units containing these two moieties. The products show moderate inhibition of a number of cancer cell lines and exhibit the ability to inhibit a number of viruses, particularly the herpes simplex virus-1 and varicella zoster virus that are responsible for herpes, chicken pox and shingles.     

The Effects of Power Law Fluid Rheology on Coil Heat Transfer for Agitated Vessel in the Transitional Flow Regime

A CFD model of heat transfer from power‐law fluids to helical cooling coils in the transitional flow regime of a baffled tank mixed with a pitched blade turbine was developed with Fluent^TM. The model captured local temperature and velocity gradients. Simulations were run, varying Re, Pr, K and n. The results indicate that a Sieder‐Tate type correlation, with the exponent on and the coefficient in front of the Reynolds number being a function of n, is recommended for estimating ho. Also, a new two coil bank design was found to be more efficient when 450 < Re < 650.     

Talking with some directors of the U.S. national laboratories

JOM surveyed the leaders of the U.S. Department of Energy’s (DOE) national laboratories for perspectives on some of the U.S. science and engineering community’s most pressing issues regarding R&D, globalization, national security, and budget constraints. The journal posed the same five questions to each lab director. What follows are responses from six of the directors: Michael R. Anastasio, Lawrence Livermore National Laboratory; Dan Arvizu, National Renewable Energy Laboratory (NREL); John J. Grossenbacher, Idaho National Laboratory (INL); Thomas O. Hunter, Sandia National Laboratories; Robert Rosner, Argonne National Laboratory; and Jeffrey Wadsworth, Oak Ridge National Laboratory (ORNL). Kelly Roncone is news editor for JOM.     

Driving a Wedge Between Evidence and Beliefs: How Online Ideological News Exposure Promotes Political Misperceptions

This article has 2 goals: to provide additional evidence that exposure to ideological online news media contributes to political misperceptions, and to test 3 forms this media‐effect might take. Analyses are based on representative survey data collected during the 2012 U.S. presidential election (N = 1,004). Panel data offer persuasive evidence that biased news site use promotes inaccurate beliefs, while cross‐sectional data provide insight into the nature of these effects. There is no evidence that exposure to ideological media reduces awareness of politically unfavorable evidence, though in some circumstances biased media do promote misunderstandings of it. The strongest and most consistent influence of ideological media exposure is to encourage inaccurate beliefs regardless of what consumers know of the evidence.