The thermal decompositions of methyl azidoformate (N3COOMe), ethyl azidoformate (N3COOEt) and 2-azido-N,N-dimethylacetamide (N3CH2CONMe2) have been studied by matrix isolation infrared spectroscopy and real-time ultraviolet photoelectron spectroscopy. N2 appears as an initial pyrolysis product in all systems, and the principal interest lies in the fate of the accompanying organic fragment. For methyl azidoformate, four accompanying products were observed: HNCO, H2CO, CH2NH and CO2, and these are believed to arise as a result of two competing decomposition routes of a four-membered cyclic intermediate. Ethyl azidoformate pyrolysis yields four corresponding products: HNCO, MeCHO, MeCHNH and CO2, together with the five-membered-ring compound 2-oxazolidone. In contrast, the initial pyrolysis of 2-azido-N,N-dimethyl acetamide, yields the novel imine intermediate Me2NCOCHNH, which subsequently decomposes into dimethyl formamide (HCONMe2), CO, Me2NH and HCN. This intermediate was detected by matrix isolation IR spectroscopy, and its identity confirmed both by a molecular orbital calculation of its IR spectrum, and by the temperature dependence and distribution of products in the PES and IR studies. Mechanisms are proposed for the formation and decomposition of all the products observed in these three systems, based on the experimental evidence and the results of supporting molecular orbital calculations.

The thermal decompositions of methyl azidoformate (N3COOMe), ethyl azidoformate (N3COOEt) and 2-azido-N,N-dimethylacetamide (N3CH2CONMe2) have been studied by matrix isolation infrared spectroscopy and real-time ultraviolet photoelectron spectroscopy. N2 appears as an initial pyrolysis product in all systems, and the principal interest lies in the fate of the accompanying organic fragment. For methyl azidoformate, four accompanying products were observed: HNCO, H2CO, CH2NH and CO2, and these are believed to arise as a result of two competing decomposition routes of a four-membered cyclic intermediate. Ethyl azidoformate pyrolysis yields four corresponding products: HNCO, MeCHO, MeCHNH and CO2, together with the five-membered-ring compound 2-oxazolidone. In contrast, the initial pyrolysis of 2-azido-N,N-dimethyl acetamide, yields the novel imine intermediate Me2NCOCHNH, which subsequently decomposes into dimethyl formamide (HCONMe2), CO, Me2NH and HCN. This intermediate was detected by matrix isolation IR spectroscopy, and its identity confirmed both by a molecular orbital calculation of its IR spectrum, and by the temperature dependence and distribution of products in the PES and IR studies. Mechanisms are proposed for the formation and decomposition of all the products observed in these three systems, based on the experimental evidence and the results of supporting molecular orbital calculations.

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The final thermally stimulated discharge current (FTSDC) technique can be used to analyze charge trapping and transport in insulating materials. The experimental conditions can be selected so that the FTSDC is mainly determined by the space charge detrapping. Measurements of the FTSDC in a wide temperature range including the local (secondary) beta relaxation and the non-local (primary) cc relaxation, for different polymers, demonstrate the existence of an apparent peak. The shift of peak temperature T-m with respect to the charging temperature T-p is analyzed. The interval T-m - T-p decreases from about 25 K to zero, as T-p approaches the glass transition T-g. T-m - T-p is lower for materials of lower conductivity. The peak width at the half maximum intensity decreases as Tp increases and the thermal apparent activation energy increases. The variations are not monotonous revealing the temperature range where the molecular motion is stronger and consequently the charge trapping and detrapping processes are affected by the strong thermal motion.

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Space charge in electrically aged cross-linked polyethylene (XLPE) was studied using a procedure combining isothermal and non-isothermal measurements of charge and discharge currents. Aging is carried out using an AC field while immersing the disk-shaped samples in an ionic aqueous solution at constant temperature. After aging the samples were isothermally DC charged and discharged. Next a non-isothermal experiment with constant heating rate was performed (FTSDC). Finally the sample was kept at the highest temperature in order to completely discharge the polymer. The space charge introduced in the XLPE during aging can be analyzed from the study of the FTSDC spectra. The thermogram (FTSDC) shows a very broad peak. The peak is attributed to trapped space charge in traps with long relaxation times. It is possible to decompose it into three or four individual peaks and obtain the corresponding activation energies. The results were compared with previous ones obtained for LDPE (low density polyethylene) aged under similar conditions.

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The experimental results obtained in a wide range of temperatures, for polyethylene terephthalate, demonstrate that the apparent activation energy changes when the charging (polarization) time or the isothermal discharging time, prior to the final thermally stimulated discharge current measurement, are used as variable parameters. Consequently, the charging and/or discharging time can be used as a variable parameter to investigate the landscape of the apparent thermal activation energies. A continuous distribution of the traps in the range from 0.4 to 3 eV was observed. The experimental results demonstrate that there is a range of experimental conditions for which the thermal activation energy is independent of the experimental parameter values. This is the activation energy value which should be used to characterize a certain mechanism.

The experimental results obtained in a wide range of temperatures, for polyethylene terephthalate, demonstrate that the apparent activation energy changes when the charging (polarization) time or the isothermal discharging time, prior to the final thermally stimulated discharge current measurement, are used as variable parameters. Consequently, the charging and/or discharging time can be used as a variable parameter to investigate the landscape of the apparent thermal activation energies. A continuous distribution of the traps in the range from 0.4 to 3 eV was observed. The experimental results demonstrate that there is a range of experimental conditions for which the thermal activation energy is independent of the experimental parameter values. This is the activation energy value which should be used to characterize a certain mechanism.

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A new silylated $\alpha$-diimine ligand, bis[N,N′-(4-tert-butyl- diphenylsilyl-2,6-diisopropylphenyl)imino]acenaphthene 3, and its corresponding Ni(II) complex, {\{}bis[N,N′-(4-tert-butyl-diphenylsilyl-2,6- diisopropylphenyl)imino]acenaphthene{\}}dibromonickel 4, have been synthesized and characterized. The crystal structures of 3 and 4 were determined by X-ray crystallography. In the solid state, complex 4 is a dimer with two bridging Br ligands linking the two nickel centers, which have square pyramidal geometries. Complex 4, activated either by diethylaluminum chloride (DEAC) or methylaluminoxane (MAO) produces very active catalyst systems for the polymerization of ethylene and moderately active for the polymerization of propylene. The activity values are in the order of magnitude of 107 g PE (mol Ni [E] h)-1 for the polymerization of ethylene and of 105 g PP (mol Ni [P] h)-1 for the polymerization of propylene. NMR analysis shows that branched polyethylenes (PE) are obtained at room or higher temperatures and almost linear PE is obtained at 0°C with 4/DEAC. © 2004 Elsevier B.V. All rights reserved.

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An orange-coloured protein (ORP) isolated from Desulfovibrio gigas, a sulphate reducer, has been previously shown by extended X-ray absorption fine structure (EXAFS) to contain a novel mixed-metal sulphide cluster of the type {[}S2MoS2CuS2MoS2] {[}J. Am. Chem. Soc. 122 (2000) 8321]. We report here the purification and the biochemical/spectroscopic characterisation of this novel protein. ORP is a soluble monomeric protein (11.8 kDa). The cluster is non-covalently bound to the polypeptide chain. The presence of a MoS42- moiety in the structure of the cofactor contributes with a quite characteristic UV-Vis spectra, exhibiting an orange colour, with intense absorption peaks at 480 and 338 nm. Pure ORP reveals an Abs(480)/Abs(338) ratio of 0.535. The gene sequence coding for ORP as well as the amino acid sequence was determined. The putative biological function of ORP is discussed. (C) 2003 Elsevier Inc. All rights reserved.

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The present work reports results obtained from a series of preliminary experiments
aiming at complementing the current knowledge about the wear behaviour of centrifugally-cast
FGM Al/SiCp composites, through concurrent corrosion processes. Precursor MMC’s were
prepared by rheocasting, using 118.8 μm SiC particles and an Al-10Si–2.2 Mg alloy. Those MMC’s
were then molten and centrifugally cast in order to produce cylindrical FGMMC’s. Discs machined
from the top surface of each sample were tested against nodular cast iron pins, using an inverted
configuration pin-on-disc tribometer. Sliding tests took place at room temperature, over a 50000 m
sliding distance, with a sliding speed of 0.3 m s-1, under a 5 N normal load; both dry-sliding and
water-lubricated tests were performed. In order to elucidate the mechanisms involved, the wear
coefficients were calculated for each condition, and the samples were subjected to morphological
characterization via SEM/EDS. Concurrently, in the case of the water-lubrication tests, the
corrosion potential of the tribological pair was monitored. The results obtained show an increase in
material loss for the water-lubricated cases, although variations are registered depending on
reinforcing particle volume fraction. At the same time, the open circuit potential response of the
tribological pair may be correlated with the events of formation/destruction of the tribolayers.

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The main aim of the Valomat project was the development of new materials for quarry back-filling and underground constructions, based on the reuse of bottom ashes from MSWI. Bottom ashes were collected in six incineration plants of Europe. Some of them were selected for the development of new materials.
One task of this project comprised the study of the long-term behavior of new materials, under simulated conditions of environmental exposure. Three different scenarios were studied. For each scenario, a pilot plant was constructed and the new materials were studied under laboratory conditions or natural weather. The long-term behavior of these materials was assessed through the characterization of chemical and ecotoxicological properties of the leachates.
The chemical contamination and the ecotoxicological levels of the leachates were relatively low, although different levels had been determined for the three different scenarios. The immersion in dechlorinated tap water (scenario S1) had shown the highest emission levels of chlorides, sulphates, DOC, and Al, especially for the materials B2/1 and B2/2. The lowest ecotoxicological and chemical levels were determined in the scenario in which the materials were buried in a sieved soil.