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Ab initio calculations have been performed to study the methyl azidoformate (N3COOCH3) and the ethyl azidoformate (N3COOCH2CH3). Several molecular properties, such as conformational equilibrium, optimal geometry, and vibrational frequencies, have been computed for these molecules. Ionization energies based on Koopman's theorem were also computed.

The thermal decomposition and crystallization behaviour of a sol-gel precursor used for the preparation of c-axis oriented Al-doped ZnO thin films were investigated in the temperature range 20-600°C by TG-DTA, IR spectroscopy and XRD analysis. At low temperature, the formation of ZnO crystallites from the sol precursor, prepared by dissolving Zn(CH 3COO)2·2H2O and AlCl 3·6H2O in 2-methoxyethanol and monoethanol amine, takes place via zinc carbonate hydroxide (sclarite/hydrozincite) and occurs simultaneously with the decomposition of this intermediary compound, which occurs above 150°C. At 200°C, the crystalline structure is well defined in terms of ZnO hexagonal lattice parameters, although an important amount of residual organic compounds and water was not yet removed. Increasing the treatment temperature up to 300, 400 and 600°C leads to a gradual removal of the residual organic compounds and therefore to a small change of the ZnO crystalline structure in terms of lattice parameters and grain size.

The SiMe3 group (TMS), introduced as a substituent at the cyclopentadienyl ligand, is found to magnify the solubility of the corresponding metal complexes in supercritical carbon dioxide (scCO(2)). This is verified from comparative solubility measurements of the species (eta(5)-Me-3 SiC5H4)MoO2 Cl, 1a, (eta(5)-Me3SiC5H4)(2)ZrCl2, 2a, and (eta(5)-Me3SiC5H4)Co(CO)I-2.0.5(I-2), 3a (newly synthesised), and of their unsubstituted precursors 1b-3b, respectively. In spite of the increased solubility, the chemical, structural and reactivity properties of the TMS derivatives are scarcely affected. Confirmation comes from a detailed study of the cobalt complex 3a that includes X-ray structural determination. The geometry is most similar to that of the precursor 3b while an apparently different Co-CO interaction is observed in the carboxylated analogue [(eta(5)-PhCH2CO2C5H4)Co(CO) I-2, 3c]. The problem is computationally tackled by using the DFT B3LYP method. The optimised geometries of the simplified models of 3a-3c are all very similar. In particular, the computed stretching frequency of the unique CO ligand is consistent with the insignificant influence of the TMS group while it suggests a reduced amount of metal back-donation in 3c. It is inferred that the TMS complexes 1a-3a, while having higher solubility in scCO2, maintain almost unaltered the electronic and chemical features of their parent compounds. In particular, the role of 1a-3a as catalysts, that is well documented for homogeneous solutions, remains unaltered in the very different scCO(2) environment. The assumption is experimentally validated for 1a by performing with the latter two classic catalytic processes. The first process is the oxidation of PPh3 that is achieved by using molecular oxygen as an oxidant. The second example concerns the epoxidation of cyclohexene achieved in presence of tert-butyl hydroperoxide (TBHP).

Energies of two-electron one-photon transitions from initial double K-hole states and the transition energies of competing processes, namely K hyper-satellites, were computed for low-Z elements, using the multi-configuration Dirac–Fock method. Transition rates are also evaluated.

In this paper, we present the optical, electrical, structural and mechanical properties exhibited by aluminum-doped zinc oxide (ZnO:Al) thin films produced by RF magnetron sputtering on polymeric substrates (polyethylene terephthalate, PET; Mylar type D from Dupont®) with a standard thickness of 100 μm. The influence of the uniaxial tensile strain on the electrical resistance of these films was evaluated in situ for the first time during tensile elongation. In addition, the role of the thickness on the mechanical behavior of the films was also evaluated. The preliminary results reveal that the increase in electrical resistance is related to the number of cracks, as well as the crack width, which also depends on the film thickness. © 2002 Elsevier Science B.V. All rights reserved.

The relation between work organisation and technological practices in auto industry is analysed in this article. The concept of “technological practice” in this sector is used to describe the specific ways of embedding information and communication technology applications into the organizational forms and cultural patterns. This concept was developed with the Sowing project (TSER, DG XII) and that approach included either the shop floor co-operation up to the regionally based networks of companies and supporting institutions. The authors studied different sectors in the automotive firms of different European countries (Germany, Belgium and Portugal): shopfloor and production lines, design and management and the local inter-relationships. It was underlined some evidencies of the different alternatives in terms of technological practices for the same sector. Much of the litterature try to disseminate an idea of a single (and optimum) organisational model for the same type of product. And here, even with the same type of technology, and of product (medium-high range), one can find different models, different cultures, different ways of organising the industrial structure (firms, regional institutions, R&D centres) in the same sector (auto industry).

The reactivity of arylisocyanates in supercritical carbon dioxide (scCO(2)) was studied using the easily available complexes CpCo(CO)(2), CpCoPPh3Me2 and Ni(cod)(2) as catalysts. A study of the solubility of the catalysts in scCO(2) was undertaken in all cases. The complex CpCo(CO)(2) is very soluble, 1.7 x 10(-1) mol kg(-1), while CpCoPPh3Me2 has a lower solubility, 7.2 x 10(-3) mol kg(-1), and Ni(cod)(2) is insoluble in scCO(2). For comparison purposes, the reactions were performed in parallel in scCO(2), using toluene as a solvent and just with the neat liquid arylisocyanate. Reactions in scCO(2) either do not take place at all, when CpCo(CO), is used as catalyst, or occur with low yields affording the trimer of the corresponding arylisocyanate when CpCoPPh3Me2 or Ni(cod)(2) act as catalysts. No incorporation of CO2 into the organic substrate was observed. Better conversions to triarylisocyanate were obtained when the reactions were performed by direct mixture of the liquid arylisocyanate ArNCO (Ar = Ph, p-CH3C6H4, p-CH3OC6H4) and the catalyst. Using toluene as a solvent, the yields of the trimers were lower than those obtained in neat arylisocyanate, and in some cases they were not formed at all. For instance in the reaction of CpCo(CO), and tolylisocyanate either under stoichiometric or catalytic conditions the trimer is not obtained, instead the compound H2R3N3C2O2 (R = CH3C6H4), was isolated in low yield. In the reaction of Ni(cod)(2)/PPh3 with phenylisocyanate, the trimer was formed but in low yield. The lower yields of the trimers observed when the reactions were performed in scCO(2) or in toluene, compared to that observed in neat arylisocyanates, indicates that the decrease in reactivity is due to a decrease in concentration. (C) 2001 Elsevier Science B.V. All rights reserved.