Interfacial impregnation chemistry in the synthesis of nickel catalysts supported on titania

The interfacial chemistry of the impregnation step involved in the preparation of nickel catalysts supported on titania is presented. Several methodologies based on deposition data, pH measurements, potentiometric mass titrations, and microelectrophoresis have been used in conjunction with diffuse reflectance UV/Vis/NIR spectroscopy, simulations, and semiempirical quantum chemical calculations. Three mononuclear inner-sphere complexes were formed at the compact layer of the "titania/electrolyte solution" interface: A monosubstituted, dihydrolyzed complex above a terminal oxo group, a disubstituted, dihydrolyzed complex above two terminal adjacent oxo groups, and a disubstituted, nonhydrolyzed complex above one terminal and one bridging adjacent oxo groups. The monosubstituted, dihydrolyzed complex predominates. The contribution of the disubstituted configurations is also important at very low Ni(II) surface concentration, but it decreases as the Ni(II) surface concentration increases. In addition, bi- and trinuclear inner-sphere complexes were formed. The receptor site involves one bridging and two terminal oxo groups in the first case and two bridging and three terminal oxo groups in the second case. The relative surface concentrations of these configurations increase initially with Ni(II) surface concentration and then remain practically constant. The understanding of these interfacial processes at a molecular level is very important to shift the catalytic synthesis from an art to a science as well as to obtain strict control of the impregnation step and, to some extent, of the whole preparative sequence. This study is very relevant to the synthesis of submonolayer/monolayer nickel catalysts supported on TiO(2) following equilibrium deposition filtration (otherwise called equilibrium adsorption).     

Resale price maintenance in supply chains with general multiplicative demand

We analyze a supply chain with a Resale Price Maintenance (RPM) contract in which the manufacturer sets the retail price with a general multiplicative price–demand function and prove the existence/uniqueness of an equilibrium. We also compare the equilibrium prices and quantities, consumer surplus and total system welfare for the RPM and wholesale price contracts. We conclude that a manufacturer may capture a smaller share of the total supply chain profit despite her ability to set the retail price.     

A singular function boundary integral method for elliptic problems with singularities

In this work we present a singular function boundary integral method for elliptic problems with boundary singularities. In this method, the approximation is constructed from the truncated asymptotic expansion for the solution near the singular point and the Dirichlet boundary conditions are weakly enforced by means of Lagrange multiplier functions. The resulting discrete problem is posed and solved on the boundary of the domain, away from the point of singularity. We are able to show that the method approximates the generalized stress intensity factors, i.e. the coe cients in the asymptotic expansion, at an exponential rate. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Ruled submanifolds with finite type Gauss map

We show that a ruled submanifold with finite type Gauss map in a Euclidean space is a cylinder on a curve of finite type or a plane.Dedicated to Professor N.K. Stephanidis on the occasion of his 65th birthday.     

Novel desilylation of alpha-dimethylsilyl esters by electrochemically generated superoxide ion

Electrochemical reduction of oxygen in the presence of an alpha-dimethylsilyl ester results in removal of the dimethylsilyl group. The reaction presumably proceeds by a mechanism involving electrochemically-generated superoxide ion.     

Pore Network Analysis of Resistivity Index for Water-Wet Porous Media

Pore network analysis is used to investigate the effects of microscopic parameters of the pore structure such as pore geometry, pore-size distribution, pore space topology and fractal roughness porosity on resistivity index curves of strongly water-wet porous media. The pore structure is represented by a three-dimensional network of lamellar capillary tubes with fractal roughness features along their pore-walls. Oil-water drainage (conventional porous plate method) is simulated with a bond percolation-and-fractal roughness model without trapping of wetting fluid. The resistivity index, saturation exponent and capillary pressure are expressed as approximate functions of the pore network parameters by adopting some simplifying assumptions and using effective medium approximation, universal scaling laws of percolation theory and fractal geometry. Some new phenomenological models of resistivity index curves of porous media are derived. Finally, the eventual changes of resistivity index caused by the permanent entrapment of wetting fluid in the pore network are also studied.Resistivity index and saturation exponent are decreasing functions of the degree of correlation between pore volume and pore size as well as the width of the pore size distribution, whereas they are independent on the mean pore size. At low water saturations, the saturation exponent decreases or increases for pore systems of low or high fractal roughness porosity respectively, and obtains finite values only when the wetting fluid is not trapped in the pore network. The dependence of saturation exponent on water saturation weakens for strong correlation between pore volume and pore size, high network connectivity, medium pore-wall roughness porosity and medium width of the pore size distribution. The resistivity index can be described succesfully by generalized 3-parameter power functions of water saturation where the parameter values are related closely with the geometrical, topological and fractal properties of the pore structure.     

An Interpenetrated Framework Material with Hysteretic CO2 Uptake

A new, twofold interpenetrated metal–organic framework (MOF) material has been synthesized that demonstrates dramatic steps in the adsorption and hysteresis in the desorption of CO₂. Measurement of the structure by powder X‐ray diffraction (PXRD) and pair distribution function (PDF) analysis indicates that structural changes upon CO₂ sorption most likely involve the interpenetrated frameworks moving with respect to each other.     

On Legendre curves in contact 3-manifolds

It is first observed that on a 3-dimensional Sasakian manifold the torsion of a Legendre curve is identically equal to +1. It is then shown that, conversely, if a curve on a Sasakian 3-manifold has constant torsion +1 and satisfies the initial conditions at one point for a Legendre curve, it is a Legendre curve. Furthermore, among contact metric structures, this property is characteristic of Sasakian metrics. For the standard contact structure onR ³ with its standard Sasakian metric the curvature of a Legendre curve is shown to be twice the curvature of its projection to thexy-plane with respect to the Euclidean metric. Thus this metric onR ³ is more natural for the study of Legendre curves than the Euclidean metric.This work was done while the first author was a visiting scholar at Michigan State University.     

Optimal Lot-sizing and Machining Economics

This paper presents a queueing model with the service station subject to breakdown while it is busy, in order to determine analytically the optimal batch size in a machining economics problem. It is shown that departures from the optimal batch size result in moderate waiting-time increases when the batch size is scaled up and in significant waiting-time increases when the batch size is scaled down. It is also shown, through the use of a simulation model with normally distributed tool lives, that the analytical results obtained with exponentially distributed tool lives are quite robust. In the multiple-item case, simulation results show that the time in the system for each item and the average time in the system across all items behave exactly like the time in the system in the single-item case.