Stochastic optimization for blending problem in brass casting industry

A critical process in brass casting is blending of the raw materials in a furnace so that the specified metal ratios are satisfied. The uncertainties in raw material compositions may cause violations of the specification limits and extra cost. In this study, we proposed a chance-constrained stochastic programming approach for blending problem in brass casting industry to handle the statistical variations in raw material compositions. The proposed approach is a non-linear mathematical model that is solved global optimally by using GAMS/BARON solver. An application has been performed in MKEK brass factory in Kırıkkale, Turkey and the solution of the application has been compared with alternative solution approaches based on cost and specification violation risk conditions. This comparison demonstrates that the proposed model is the most effective solution approach for managing stochastic uncertainties in blending problems and successfully can be used other industries such as alloy steel or secondary aluminum production.     

Activating water: important effects of non-leaving groups on the hydrolysis of phosphate triesters

The high rate of spontaneous hydrolysis of tris-2-pyridyl phosphate (TPP) is explained by the activating effects of the non-leaving ("spectator") groups on P-OAr cleavage, and not by intramolecular catalysis. Previous work on phosphate-transfer reactions has concentrated on the contributions to reactivity of the nucleophile and the leaving group, but our results make clear that the effects of the non-leaving groups on phosphorus can be equally significant. Rate measurements for three series of phosphate triesters showed that sensitivities to the non-leaving groups are substantial for spontaneous hydrolysis reactions, although significantly smaller for reactions with good nucleophiles. There are clear differences between triaryl and dialkyl aryl triesters in sensitivities to leaving and non-leaving groups with the more reactive triaryl systems showing lower values for both β(LG) and β(NLG). Intramolecular catalysis of the hydrolysis of TPP by the neighbouring pyridine nitrogens is insignificant, primarily because of their low basicity.     

The chameleon-like nature of zwitterionic micelles: effect of cation binding

Addition of salts, especially perchlorates, to zwitterionic micelles of SB3-14, C(14)H(29)NMe(2)(+)(CH(2))(3)SO(3)(-), induces anionic character and uptake of H(3)O(+) by SB3-14 micelles. Thus, the addition of alkali metal perchlorates accelerates the acid hydrolysis of 2-(p-heptoxyphenyl)-1,3-dioxolane, HPD, in the presence of SB3-14 micelles, which depends on the local proton concentration at the micelle surface. The addition of metal chlorides to solutions of such perchlorate-modified SB3-14 micelles decreases both the negative zeta potential of the micelles and the observed rate constant for acid hydrolysis of HPD. The effect of the monovalent cations Li(+), Na(+), and K(+) is smaller than that of the divalent cations Be(2+), Mg(2+), and Ca(2+), and much smaller than that of the trivalent cations Al(3+), La(3+), and Er(3+). The major factor responsible for this cation valence dependence of these effects is shown to be electrostatic in nature, reflecting the strong dependence of the micellar surface potential on the cation valence. The fact that the salt effects are not identical after correction for the electrostatic effects indicates that additional secondary nonelectrostatic effects may contribute as well.     

Self-assembled polyelectrolyte multilayered films on Nafion with lowered methanol cross-over for DMFC applications

The paper is concerned with the deposition of self-assembled polyelectrolyte multilayer on Nafion membrane by layer-by-layer (LbL) technique with lowered methanol cross-over for direct methanol fuel cell (DMFC) applications. The formation of self-assembled multilayered film on Nafion was characterized by UV–vis spectroscopy and it was found that the polyelectrolyte layers growth on the Nafion surface regularly. Furthermore, the proton conductivity and methanol cross-over measurements were carried out for characterization of the LbL self-assembled composite membranes. The results showed that the concentration and pH of the polyelectrolytes significantly affect the proton conductivity and methanol barrier properties of the composite membranes. 10⁻¹ monomol polyelectrolyte concentration and pH 1.8 was found to be optimum deposition conditions considering proton conductivity and methanol permeation properties of the LbL self-assembled composite membranes. The methanol permeability of the 10 bi-layers of PAH1.8/PSS1.8 deposited LbL self-assembly composite membrane was significantly suppressed and found to be 4.41 × 10⁻⁷ cm²/s while the proton conductivity value is in acceptable range for fuel cell applications.     

Energy Fluctuation of Ideal Fermi Gas Trapped under Generic Power Law Potential U=Σ_(i=1)~d c_i|x_i/a_i|~(n_i) in d Dimensions

Energy fluctuation of ideal Fermi gas trapped under generic power law potential U=Σ_(i=1)~d c_i|x_i/a_i|~(n_i) has been calculated in arbitrary dimensions.Energy fluctuation is scrutinized further in the degenerate limit μK_B T with the help of Sommerfeld expansion.The dependence of energy fluctuation on dimensionality and power law potential is studied in detail.Most importantly our general result can not only exactly reproduce the recently published result regarding free and harmonically trapped ideal Fermi gas in d =3 but also can describe the outcome for any power law potential in arbitrary dimension.     

Non-isothermal Permeability Impairment by Fines Migration and Deposition in Porous Media including Dispersive Transport

Particle migration and deposition, and resulting permeability impairment occurring in porous media are described by a practical phenomenological model considering temperature variation and particle transport by advection and dispersion. Variation of the filter coefficient and permeability of porous matrix by temperature and particle deposition, and other essential factors are considered by means of the special correlations of the relevant variables and dimensionless numbers. Comparison of the numerical results, obtained using a finite-difference numerical scheme with and without considering the dispersion mechanism and temperature variation, reveals the significance of such effects on fines migration and deposition, and consequent permeability impairment in porous media. Improved model presented in this article can be instrumental for scientifically guided experimentation, analysis, and optimal design of processes involving in transport of colloidal and fine particles through geological subsurface formations.     

Can Moderately Rarefied Gas Transport Through Round and Flat Tight Channels of Fractured Porous Media be Described Accurately?

We study the generation and flow of foam through rough-walled, fractured marble rocks that mimic natural fracture systems in carbonate reservoirs. Flow was isolated to the fracture network because of the very low rock permeability of the marble samples and foam generated in situ during co-injection of surfactant solution and gas. The foam apparent viscosities were calculated at steady pressure gradients for a range of gas fractions, and similar to foam flow in porous media, we identified two flow regimes for foam flow in fractures: a high-quality flow regime only dependent on liquid velocity and a low-quality flow regime determined by the gas and liquid velocities. Variations in local fluid saturation during co-injection were visualized and quantified using positron emission tomography combined with computed tomography.

     

Intramolecular general acid catalysis of phosphate transfer. nucleophilic attack by oxyanions on the PO3 2- group

Phosphate transfer from the 8-dimethylammonium-naphthyl-1-phosphate monoanion 4m to water and to a range of nucleophiles shows general acid catalysis by the neighboring NH(+) group, through the strong intramolecular hydrogen bond. Reactivity is insensitive to the charge on the nucleophile, so that fluoride and oxyanions displace dimethylaminonaphthol from the PO3(2-) group as effectively as do amines of the same basicity. Reactivity is (predictably) relatively insensitive to the basicity of the nucleophile and to the alpha-effect. A strong intramolecular hydrogen bond is present in the product, but also in the reactant, as evidenced by major perturbations in the pK(a)'s of the phosphate and dimethylamino groups, to 3.94 and 9.31, respectively, and by ab initio calculations. Rate accelerations are of the order of 10(6)-fold despite this stabilization: the strength of the hydrogen bond is evidently significantly enhanced in the transition state. The evidence suggests that it also depends remarkably strongly on the degree of ionization of the reacting phosphate group and will be significantly reduced for the neutral PO(OH)2 group. Thus, the hydrolysis of the substrate cation 4+ shows a correspondingly greater, >10(8)-fold acceleration.     

Nucleophilic attack by oxyanions on a phosphate monoester dianion: the positive effect of a cationic general Acid

The two negative charges on a phosphate monoester RO-PO32- at neutral pH provide a considerable electrostatic barrier toward reactions with nucleophilic reagents with a negative charge on the attacking atom. Electrostatic repulsion disappears when the hydrolysis of an aryl phosphate monoester is catalyzed by a neighboring cationic general acid. The hydrolysis of 8-dimethylammonium-1-phosphate (1) is catalyzed by oxyanions, fluoride anion, and hydroxylamines at similar rates.     

Determination of environmentally important metal ions by fluorescence quenching in anionic micellar solution

This work describes the effect of a variety of metal ions as quenchers of the fluorescence of naphthalene, in aqueous micellar solutions of sodium dodecyl sulfate (SDS). The quenching by the metal ions can be adequately described by the Stern-Volmer equation and the best signal to noise ratios are obtained with low micellized detergent concentrations. Apparent Stern-Volmer constants decrease in the order: Fe3+ > Cu2+ > Pb2+ > Cr3+ > Ni2+ and directly reflect the relative sensitivity of the method for these ions. Detection limits (defined as three times the standard deviation of the blank for n= 10) for the fluorescence quenching of naphthalene by the metal ions in aqueous micellar SDS are in the range of 1.0 x 10(-6) to 1.0 x 10(-5) mol dm(-3). The proposed fluorescence quenching method shows good repeatibility for a variety of added quencher metal ions, indicating that anionic micelle-enhanced fluorescence quenching by metal ions constitutes an analytical method of rather general application.