This paper deals with the growth process of nanostructured silicon films produced by chemical vapour deposition technique, at or close to the γ-regime where powders are formed. There, besides the set of chemical reactions undertaken by the species decomposed on the growth surface, the importance of the physics of the plasma in managing the powders and on the final film performances will be shown. To identify the plasma region where Si nanoaggregates are formed, we propose the use of a new parameter that translates the energy coupling of the rf power to the species of the gas flow, per pressure range of the process. By doing so we could establish an excellent correlation between this ratio and the plasma parameters such as peak to peak rf voltage and plasma impedance, or with the films defect density and their transport properties. Apart from that, we also show that high compact Si nanoclusters could be grown under moderate ion bombardment. Finally, to allow the growth at high rates of controlled silicon nanostructures, a three cycling process based on hot wire chemical vapour deposition and plasma assisting the hot wire technique will be discussed. © 2002 Elsevier Science Ltd. All rights reserved.

The catalytic step that initiates formation of the ferric oxy-hydroxide mineral core in the central cavity of H-type ferritin involves rapid oxidation of ferrous ion by molecular oxygen (ferroxidase reaction) at a binuclear site (ferroxidase site) found in each of the 24 subunits. Previous investigators have shown that the first detectable reaction intermediate of the ferroxidase reaction is a diferric-peroxo intermediate, F-peroxo, formed within 25 ms, which then leads to the release of H2O2 and formation of ferric mineral precursors. The stoichiometric relationship between F-peroxo, H2O2, and ferric mineral precursors, crucial to defining the reaction pathway and mechanism, has now been determined. To this end, a horseradish peroxidase-catalyzed spectrophotometric method was used as an assay for H2O2. By rapidly mixing apo M ferritin from frog, Fe2+, and O-2 and allowing the reaction to proceed for 70 ms when F-peroxo has reached its maximum accumulation, followed by spraying the reaction mixture into the H2O2 assay solution, we were able to quantitatively determine the amount of H2O2 produced during the decay of F-peroxo. The correlation between the amount of H2O2 released with the amount of F-peroxo accumulated at 70 ms determined by Mossbauer spectroscopy showed that F-peroxo decays into H2O2 with a stoichiometry of 1 F-peroxo:H2O2. When the decay of F-peroxo was monitored by rapid freeze-quench Mossbauer spectroscopy, multiple diferric mu-oxo/mu-hydroxo complexes and small polynuclear ferric clusters were found to form at rate constants identical to the decay rate of F-peroxo. This observed parallel formation of multiple products (H2O2, diferric complexes, and small polynuclear clusters) from the decay of a single precursor (F-peroxo) provides useful mechanistic insights into ferritin mineralization and demonstrates a flexible ferroxidase site.

Currently, microactuators are being developed using shape memory alloys (SMAs), which allow simple design geometries and provide large work outputs in restricted space. Several techniques have been used to produce NiTi shape memory alloy thin films, but from the practical point of view, only the sputter deposition method has succeeded so far. Vacuum evaporation of NiTi binary alloy entails the potential problem of the evaporation rates of each component not being the same due to differences in vapour pressure. Aiming to study the possible applications of SMAs to microfabrication, NiTi thin films were produced at CENIMAT by sputter and vacuum evaporation using raw materials from different sources. The films were analysed by differential scanning calorimetry (DSC) and X-ray diffraction (XRD) at room temperature, as well as in situ high temperature, in order to characterise the temperature ranges at which the different structural transformations occur. © 2002 Elsevier Science B.V. All rights reserved.

In this work, we present a study of the effect of temperature, type and concentration of the dopant on the structural characteristics of ZnO thin films produced by spray pyrolysis; the crystallite size has been determined from profile peak shape analysis. These results are compared to the electrical characterisation performed on these materials. The effect of the dopant on the properties of ZnO thin films depends on its characteristics, mainly its ionic radius. Al, Ga and In have been studied as dopants, the best one being In, since it leads to the lowest resistivity.

Space charge in electrically aged LDPE was studied using a recently developed technique combining isothermal charging and discharging with non-isothermal measurements. Samples were aged in a NaCl aqueous solution at 40degreesC for 1500h under an AC field of 6MV/m (50Hz). The samples were then isothermally DC charged and discharged (both currents recorded). Next a non-isothermal experiment with constant heating rate was performed. Finally the sample was kept at the highest temperature and the final isothermal discharge current registered. The last step has to be carried on for long time to ensure an almost complete discharge of the remnant charge so that results become reproducible and possible to analyze. Selective charging (careful choice of the field, temperature and the ratio of charging/discharging times) revealed the presence of different trapping sites. From the analysis of the isothermal and non-isothermal data the relaxation times and activation energies could be obtained.

Space charge in electrically aged LDPE was studied using a recently developed technique combining isothermal charging and discharging with non-isothermal measurements. Samples were aged in a NaCl aqueous solution at 40degreesC for 1500h under an AC field of 6MV/m (50Hz). The samples were then isothermally DC charged and discharged (both currents recorded). Next a non-isothermal experiment with constant heating rate was performed. Finally the sample was kept at the highest temperature and the final isothermal discharge current registered. The last step has to be carried on for long time to ensure an almost complete discharge of the remnant charge so that results become reproducible and possible to analyze. Selective charging (careful choice of the field, temperature and the ratio of charging/discharging times) revealed the presence of different trapping sites. From the analysis of the isothermal and non-isothermal data the relaxation times and activation energies could be obtained.

The crystallization of a commercial borosilicate glass powder has been studied in the temperature range 750-900°C. Crystal growth was investigated by high temperature XRD and cristobalite precipitation was identified. Glass devitrification exhibited a characteristic incubation period that decreased with increasing temperature: 25-30 min at 750°C, 9-12 min at 775°C, 5-10 min at 810°C, and 0-5 min at 840°C. Cristobalite is an unfavorable transformation product in terms of thermal expansion behavior. The precipitation of cristobalite in sintered glass compacts was confirmed by dilatometric analysis, where the increase in thermal expansion coefficient due to the presence of cristobalite and its transition from the tetragonal to the cubic phase were verified. Correlation between the XRD results and the dilatometric data from sintered glass compacts showed the partial dissolution of cristobalite when the glass was heated at the highest temperatures.

Hall effect measurements are one of the most powerful techniques for obtaining information about the conduction mechanism in polycrystalline semiconductor materials, which is the basis for understanding semiconductor gas sensors. In order to investigate the correlation between the microscopic characteristics and the macroscopic performances exhibited by undoped tin oxide gas sensors deposited by spray pyrolysis, Hall effect measurements were performed at different temperatures, from room temperature up to 500 K, and in the presence of two different atmospheres, air and methane. From these measurements, it was possible to infer the potential barrier and its dependence with the used atmosphere. The obtained results were analysed in terms of the oxygen mechanism at grain boundaries on the basis of the grain boundary-trapping model. In the presence of methane gas, the electrical resistivity decreases due to the lowering of the inter-grain boundary barrier height.

Hall effect measurements are one of the most powerful techniques for obtaining information about the conduction mechanism in polycrystalline semiconductor materials, which is the basis for understanding semiconductor gas sensors. In order to investigate the correlation between the microscopic characteristics and the macroscopic performances exhibited by undoped tin oxide gas sensors deposited by spray pyrolysis, Hall effect measurements were performed at different temperatures, from room temperature up to 500 K, and in the presence of two different atmospheres, air and methane. From these measurements, it was possible to infer the potential barrier and its dependence with the used atmosphere. The obtained results were analysed in terms of the oxygen mechanism at grain boundaries on the basis of the grain boundary-trapping model. In the presence of methane gas, the electrical resistivity decreases due to the lowering of the inter-grain boundary barrier height.

The surfaces of cordierite and glass particles were modified by coating them with an alumina precursor using a precipitation process in the presence of urea. Scanning electron microscopy (SEM), high-resolution transmission electron microscopy, X-ray diffraction, electrophoresis, and rheological measurements were used to characterize the coated powders. SEM and transmission electron microscopy morphologies of the coated powders revealed that amorphous and homogeneous coatings have been formed around the particles. The morphology of the coated powders showed a coiled wormlike surface. The coating Al2O3 layer dominated the surface properties of the coated glass and cordierite powders. The influence of the coating layer on the processing ability of cordierite-based glass-ceramics substrates by tape casting was studied in aqueous media. It could be concluded that the coating of the powders facilitates the processing and yields green and sintered tapes with denser, more homogeneous microstructures compared with the uncoated powders.

The surfaces of cordierite and glass particles were modified by coating them with an alumina precursor using a precipitation process in the presence of urea. Scanning electron microscopy (SEM), high-resolution transmission electron microscopy, X-ray diffraction, electrophoresis, and rheological measurements were used to characterize the coated powders. SEM and transmission electron microscopy morphologies of the coated powders revealed that amorphous and homogeneous coatings have been formed around the particles. The morphology of the coated powders showed a coiled wormlike surface. The coating Al2O3 layer dominated the surface properties of the coated glass and cordierite powders. The influence of the coating layer on the processing ability of cordierite-based glass-ceramics substrates by tape casting was studied in aqueous media. It could be concluded that the coating of the powders facilitates the processing and yields green and sintered tapes with denser, more homogeneous microstructures compared with the uncoated powders.

The new compound [Co(eta(5)-C5H5)(dppf-P,P')I]I, 1, was synthesised by the stoichiometric reaction of the Co(III) complex [Co(eta(5)-C5H5)(CO)I-2], 2, with 1,1'-bis(diphenylphosphino)ferrocene (dppf) in CH2Cl2, and was characterised by multinuclear NMR spectroscopy. Exposure to air of THF or CH2Cl2 solutions of compound 1 gave, in an unexpected way, a polymeric chain comprising bridging 1,1'-bis(oxodiphenylphosphoranyl) ferrocene (dppfO(2)) joining tetrahedral Co(II) units [CoI2(mu-dppfO(2))](n), 3. Attempts to obtain the polymeric chain 3 by the direct reaction of dppfO(2) with CoI2, in CH2Cl2, gave instead the monomeric compound [CoI2(dppfO(2))], 4, in which dppfO2 is coordinated in a chelating mode. The structural characterisation of compounds 2, 3, and 4 was carried out by single crystal X-ray diffraction studies. The magnetic behaviour of [CoI2(dppfO(2))] and [CoI2(mu-dppfO(2))](n) was studied, and the results are consistent with tetrahedral S = 3/2 Co-II, possessing a (4)A(2) ground state, and S = 0 Fe-II. In these compounds, Co-II negative zero field splittings were determined from an analysis of the magnetic susceptibility temperature dependence, with D/k = -13 and -14 K for CoI2(dppfO(2)) and [CoI2(mu-dppfO(2))](n), respectively. DFT calculations were performed in order to understand the electronic structure of [Co(eta(5)-C5H5)(dppf-P,P')I]I, 1, as well as that of the paramagnetic specie [CoI2(dppfO(2))], 4. The [CoI2(mu-dppfO(2))](n) chain was also analysed and found to behave very similarly to the monomeric iodine derivative 4. The calculations showed the unpaired electrons to be localized on the Co(II) centre in all these species. The rather complicated electrochemical behaviour exhibited by the dppf complex [Co-III(eta(5)-C5H5)(dppf-P,P')I]I and by [Co(dppfO(2))I-2] is discussed.