A few considerations on some catalysts for olefin polymerization

Among many precursors and catalysts for alpha-olefins polymerization, one seems to be particularly interesting, because it has not been completely clarified yet. We refer especially to precursors obtained via reaction between Mg-alkyls and SiCl₄. The products of this reaction are not well known; in fact, under some operating conditions, a special form of MgCl₂ is obtained, showing x-ray diffraction peaks in the angular region lower than 15° (2 theta), which corresponds to the 5.9 A interplanar spacing, characteristic of alpha-MgCl₂. Under other conditions, MgCl₂ is obtained in the well known and strongly disordered delta structure. By employing these precursors, some catalytic systems for alpha-olefins polymerization have been prepared. In this paper, the peculiar aspects of these precursors and catalysts are described, particularly focusing on the correlation between structure and performances in ethylene and propylene polymerization.     

Enrichment method for trace amounts of rare earth elements using chemofiltration and XRF determination

A preconcentration method for subsequent determination of rare earth elements (REE) by X-ray fluorescence (XRF) spectrometry was developed. The method is based on using (o-[3,6-disulfo-2-hydroxy-1-naphthylazo]-benzenearsonic acid) (Thorin) as a complexing agent which is retained on a polyamide membrane by a chemofiltration process. The pH dependence of the chemofiltration of these metal ions on the membrane and other variables, such as flow-rate, contact time, kinetic of complex formation, etc. were determined. The membrane containing the chemofiltrate formed a thin film, which eliminated the interelemental effects when measured by XRF. The detection limits were 23, 23 and 49 ng/mL for Sm(III), Eu(III) and Gd(III), respectively. High enrichment factors were obtained. The method was successfully applied to the preconcentration of Sm(III), Eu(III) and Gd(III) from different samples. Received: 8 March 2000 / Revised: 9 May 2000 / Accepted: 15 May 2000     

Supply chain cooperation in industrial districts: A simulation analysis

In the past few years the literature on supply chain management has widely emphasized that cooperation among supply chain (SC) firms is a key source of competitive advantage. This paper explores the topic in a particular context, i.e. the industrial district (ID), which constitutes a specific production model where complex SC networks can be identified. SC cooperation may take on several forms in IDs and may produce several benefits (e.g. upgrading quality and reducing costs) so this paper also analyzes the benefits of a specific form of SC cooperation in different competitive scenarios and for diverse ID organizational structures. An agent-based model of SC cooperation in IDs has been developed and a simulation analysis carried out.     

Mechanistic models for pool nucleate boiling heat transfer: input and validation

Correlations for nucleate boiling heat transfer should be improved, or in the long term possibly be replaced, by the development of mechanistic simulations that include the non-uniform spacing and variable characteristics of the nucleation sites and non-linear interactions between the sites. This paper discusses the interactions that should be included in simulations and some lessons from a first attempt to validate a particular simulation against experimental spatio-temporal data for wall temperature. Input data for nucleation site positions and characteristics are a particular problem and the prospects for obtaining this data from measurements that are independent of boiling are discussed.     

Study of the Ternary Complex Formation between Vanadium(III)-Cysteine and Small Blood Serum Bioligands

The complex species formed between vanadium(III) cysteine and small blood serum bioligands: lactic, oxalic, citric and phosphoric acids were studied in aqueous solution by means of electromotive force measurements, Emf(H), at 25 °C and 3.0 mol⋅dm⁻³ KCl as the ionic medium. The ternary complexes were studied by potentiometric measurements and the data analyzed using the least-squares computational program LETAGROP to obtain the respective stability constants and stoichiometric coefficients. The UV-Vis spectrophotometric measurements were done in order to make a qualitative characterization of the complexes formed in aqueous solution.     

Asymmetric synthesis of cyclopropanes from lithiated aryloxiranes and alpha,beta-unsaturated Fischer carbene complexes

A diastereo- and enantiospecific formation of tetrasubstituted cyclopropane carbene complexes and cyclopropanecarboxylates from lithiated aryloxiranes and alpha,beta-unsaturated Fischer carbene complexes is described.     

Diesel particulate abatement via wall-flow traps based on perovskite catalysts

It is probably redundant to stress how extensive are nowadays the attempts to reduce the diesel particulate emissions from automotive and stationary sources. The present paper looks into a technology relied on a catalytic trap based on a SiC wall-flow monolith lined with suitable catalysts for the sake of promoting a more complete and faster regeneration after particulate capture. All the major steps of the catalytic filter preparation are dealt with, including: the synthesis and choice of the proper catalyst and trap materials, the development of an in situ catalyst deposition technique, the bench testing of the derived catalytic wall-flow. The best catalyst selected was the perovskite La0.9K0.1Cr0.9O3-delta. The filtration efficiency and the pressure drop of the catalytic and non-catalytic monoliths were evaluated on a diesel engine bench under various operating conditions.     

Sur les dérivés de la fluorénone VII. Bifluorényles et bifluorénonyles

Starting from 3-bromo-, 1-iodo- and 4-iodo-9-oxo-fluorene three symmetrical bifluorenonyls and the corresponding hydrocarbons 3,3′-, 1,1′- and 4,4′-bifluorenyls are prepared. An attempt to obtain the non-symmetrical 1,2′-bifluorenyl is also described.     

Excess free energies and entropies of aqueous solutions of methyl-D-pyranosides at 25°C

The excess Gibbs free energies of four -methyl-D-aldopyranosides in water were determined at 25°C from isopiestic measurements. The excess entropies were obtained by subtracting the free energy values from the enthalpy data. The results show a remarkable enthalpy-entropy compensation. The positive sign of the excess free energies is interpreted as due to the favorable solute-solvent interactions that prevent the favorable solute-solute interaction. The signs and magnitudes of the pair interaction coefficients are attributed to the release of water from the hydration cospheres during the concentration process. The excess properties seem to depend, however, on the stereochemistry of the solutes. This effect is discussed and attributed to the different specific stabilities of the hydration shells.