Highly Cooperative Tetrametallic Ruthenium-mu-Oxo-mu-Hydroxo Catalyst for the Alcohol Oxidation Reaction

The tetrametallic ruthenium-oxo-hydroxo-hydride complex {[(PCy(3))(CO)RuH](4)(mu(4)-O)(mu(3)-OH)(mu(2)-OH)} (1) was synthesized in two steps from the monomeric complex (PCy(3))(CO)RuHCl (2). The tetrameric complex 1 was found to be a highly effective catalyst for the transfer dehydrogenation of alcohols. Complex 1 showed a different catalytic activity pattern towards primary and secondary benzyl alcohols, as indicated by the Hammett correlation for the oxidation reaction of p-X-C(6)H(4)CH(2)OH (rho = -0.45) and p-X-C(6)H(4)CH(OH)CH(3) (rho = +0.22) (X = OMe, CH(3), H, Cl, CF(3)). Both a sigmoidal curve from the plot of initial rate vs [PhCH(OH)CH(3)] (K(0.5) = 0.34 M; Hill coefficient, n = 4.2+/-0.1) and the phosphine inhibition kinetics revealed the highly cooperative nature of the complex for the oxidation of secondary alcohols.     

Vanishing point detection without any a priori information

Even though vanishing points in digital images result from parallel lines in the 3D scene, most of the proposed detection algorithms are forced to rely heavily either on additional properties (like orthogonality or coplanarity and equal distance) of the underlying 3D lines, or on knowledge of the camera calibration parameters, in order to avoid spurious responses. In this work, we develop a new detection algorithm that relies on the Helmoltz principle recently proposed for computer vision by Desolneux et al (2001; 2003), both at the line detection and line grouping stages. This leads to a vanishing point detector with a low false alarms rate and a high precision level, which does not rely on any a priori information on the image or calibration parameters, and does not require any parameter tuning.     

A Sampling Approach for Intentional Islanding of Distributed Generation

This paper proposes an innovative way of making a decision to island (or synchronize) distributed generators when operating conditions of a distribution system are varied. Islanding decisions are made when a network undergoes disturbances. In this approach, there is a decision-making mechanism, which samples states of the network operating condition to either synchronize or island in an identified period of time. Decision making is achieved through extended sequential sampling, which manages generator states within specific time periods. The approach can minimize the duration of islanded operation and manage generators' re-connection to the grid. Use of the proposed mechanism and sampling approach offer benefits over conventional relays; incorrect operations due to errors in measurements are reduced because the operational actions are not based on a single decision sample, but instead rely on extended sequential sampling over a number of samples. A case study is investigated using the IEEE 30-bus test system and the results are presented for this new approach     

PIK-2 Reactor with a Low Consumption of High-Enrichment Uranium

Calculations of the possibility of switching the matrix of the fuel-element cores and the vessel with the reactor envelope to weakly neutron-absorbing aluminum and lowering at the same time the fuel content in the fuel elements by 40% are performed for the high-flux PIK reactor which is under construction in Gatchina. As a result, the flux density of the thermal neutrons in the heavy-water reflector increases by a factor of 1.4–1.5 and the maximum unperturbed flux reaches a world record value – 1.9·10¹⁵ sec^–1·cm^–2. The nonuniformity of the volume energy-release decreases to 2.3. The weight of the control rods and reactor safety increase. As a result of the decrease of the fuel content in the fuel elements and the increase of the run duration, about 60 kg of high-enrichment uranium ²³⁵U are saved annually, decreasing annual fuel costs by one third.     

Quantifying technological aspects of process sustainability: a thermodynamic approach

Thermodynamic analysis has greatly helped to compare and to improve the energy efficiency of all kinds of technological processes, and recently we have also attempted to analyse some important biochemical processes under intracellular conditions. This work has pointed to some key strategies on sustainable process operation, such as the exceptionally high thermodynamic efficiencies of chemical and solar energy conversion in living cells.From this it was expected that the sustainability strategies of specific biochemical processes and those of the ecosphere as a whole could be of guidance to current technological processes, especially now that there is a growing demand from government and industry to effectively deal with sustainability aspects in process analysis. Our focus on this issue has led to methodologies to quantify technological aspects of sustainability by making use of thermodynamic principles. Three indicators were constructed to express three technological aspects of process sustainability. First, an indicator for the sustainability of resource utilization considers the thermodynamic input and the availability the resources used in the process. Secondly, an efficiency indicator focuses on the conversion and loss of thermodynamic quantities in the process itself. Thirdly, an indicator for environmental compatibility takes into account the thermodynamic input required to prevent possible negative side effects of the process, such as global warming or water pollution. The three indicators are used to reflect on (un)sustainable characteristics of current technological processes compared to biochemical processes. Finally, we address the drawbacks of combining indicator values to express overall sustainability.     

Zero-valent iron treatment of RDX-containing and perchlorate-containing wastewaters from an ammunition-manufacturing plant at elevated temperatures.

The use of zero-valent iron for treating wastewaters containing RDX and perchlorate from an army ammunition plant (AAP) in the USA at elevated temperatures and moderately elevated temperature with chemical addition was evaluated through batch and column experiments. RDX in the wastewater was completely removed in an iron column after 6.4 minutes. Increasing the temperature to 75 degrees C decreased the required retention time to 2.1 minutes for complete RDX removal. Perchlorate in the wastewater was completely removed by iron at an elevated temperature of 150 degrees C in batch reactors in 6 hours without pH control. Significant reduction of perchlorate by zero-valent iron was also achieved at a more moderate temperature (75 degrees C) through use of a 0.2 M acetate buffer. Based on the evaluation results, we propose two innovative processes for treating RDX-containing and perchlorate-containing wastewaters: a temperature and pressure-controlled batch iron reactor and subsequent oxidation by existing industrial wastewater treatment plant; and reduction by consecutive iron columns with heating and acid addition capabilities and subsequent oxidation.     

A simplified method for modelling the effect of blinds on window thermal performance

An approximate method is presented for predicting the effect of a louvered blind on the centre‐glass thermal performance of a fenestration. The method combines a one‐dimensional heat transfer model with data from a numerical simulation of the window and blind. Sample results for a blind mounted on the indoor surface of a window show the effect of blind slat angle on heat transmission. Both summer and winter conditions are considered. The results show that a louvered blind can improve the U‐value of a standard double‐glazed window by up to 37%. Also, the radiation heat exchange with the room can be dramatically reduced (by up to 60%), which will improve the level of occupant comfort. However, there was found to be a trade‐off between U‐value and occupant comfort; placing the blind closer to the window improves the U‐value, but increases the radiation heat exchange with the room. The predictions from the present simplified method compare well with results from a full two‐dimensional computational fluid dynamics solution of the conjugate blind/window interaction. Copyright © 2005 John Wiley & Sons, Ltd.     

Matrix mediated alignment of single wall carbon nanotubes in polymer composite films

Alignment of single wall carbon nanotubes (SWNT) in liquid crystalline (LC) polymer matrix imparting orientation to the nanotubes along the nematic director was studied by atomic force microscopy, measurements of electrical conductivity and Raman spectroscopy of the composite in the directions parallel and perpendicular to the nematic director. The composites were prepared through dispersion of SWNT with LC monomer in a common solvent, their alignment in nematic monomer and consequent UV polymerization of the monomer. The anisotropy of electrical and optical properties of the system depends strongly on the concentration of the nanotubes in the range of 1-10% SWNT being especially strong for smaller concentrations and negligible at higher loads. A simple semi-quantitative model is suggested to account for the orientational behavior of nanotubes in nematic matrices. It successfully describes the observed anisotropy of physical properties at microscale (up to 200 μm) in terms of anchoring of the polymer chains to the nanotubes surface and adjustment of the nanotubes orientation to the nematic direction due to such coupling. The increasing disorientation of the nematic domains at higher nanotubes loads is explained as a development of larger number of LC defects induced by the nanotubes in the nematic matrix due to their intrinsic nature of aggregation. The anisotropy of physical properties at macro scale (several millimeters) is much smaller and less dependable on SWNT concentration because differently oriented LC domains effectively wash out the anisotropy.     

Influence of the deposition atmosphere on the characteristics of Pd–Mg thin films prepared by pulsed laser deposition

Bilayered palladium (30 nm thick)–magnesium (350 nm thick) thin films were prepared using the pulsed laser deposition technique in the presence of various background gases (Ar, He and a mixture He + H₂) under different partial pressures (47 and 27 Pa). According to the deposition atmosphere, the Pd/Mg interface shows either a sharp or an extended transition. The electrochemical hydriding properties and the mechanical stability upon cycling of the Pd/Mg film are greatly improved when an extended «intermixing» zone between the Pd and Mg layers is present. The Pd–Mg films prepared under pure helium fulfill these conditions.     

Statistical model of an undermoded reverberation chamber

Weibull distribution is adopted to model the electric field component of a Reverberation Chamber (RC). Its first property is to include the asymptotic laws, such as Rayleigh and exponential, and its main advantage lies in the fact that the Weibull shape parameter enables a model of the departure from overmoded to undermoded RC regime. Applications are given, such as an RC modal finite element modeling and a Monte Carlo simulation: they prove that the Weibull two-parameter distribution correctly models the quality factor influence. Moreover, the relevance of the use of this extreme value distribution is illustrated.