Rhodium complexes modified by simple trialkylphosphines can be used to carry out homogeneous hydroformylation in supercritical carbon dioxide (scCO(2)). The catalyst derived from PEt3 is more active and slightly more selective for the linear products in scCO2 than in toluene, and under the same reaction conditions [100degreesC, 40 bar of CO/H-2 (1:1)] P(OPri)(3) is also an effective ligand giving good catalyst solubility and activity. Other ligands such as PPh3, POct(3), PCy3, and P(4-C6H4But)(3) are less effective because of the low solubility of their rhodium complexes in scCO(2). P(4-C6H4SiMe3)(n) Ph3-n (n = 3 or 1) and P(OPh)(3) impart activity despite their complexes only being poorly soluble in scCO(2). Under subcritical conditions, using PEt3 as the ligand, C7-alcohols from hydrogenation of the first formed aldehydes are the main products whilst above a total pressure of 200 bar, where the solution remains supercritical (monophasic) throughout the reaction, aldehydes are obtained with 97% selectivity. High pressure IR studies in scCO(2) using PEt3 as the ligand are reported.

In this paper we present an improved version of large area (5 mm × 80 mm) flexible position sensitive detectors deposited on polyimide (Kapton® VN) substrates with 75 μm thickness, produced by plasma enhanced chemical vapor deposition (PECVD). The structures presented by the sensors are Kapton/ZnO:Al/(pin)a-Si:H/Al and the heterostructure Kapton/Cr/(in)a-Si:H/ZnO:Al. These sensors were characterized by spectral response, photocurrent dependence as a function of light intensity and position detectability measurements. The set of data obtained on one-dimensional position sensitive detectors based on the heterostructure show excellent performances with a maximum spectral response of 0.12 A/W at 500 nm and a non-linearity of ±10%. © 2002 Elsevier Science B.V. All rights reserved.

In practice one has often to deal with the problem of inconsistency between constraints, as the result, among others, of the comple\-xi\-ty of real models. To overcome these conflicts we can outline two major \mbox{actions}: removal of constraints or changes in the coefficients of the model. This last approach, that can be generically described as ``model corre\-ction" is the problem we address in this paper. The correction of the right hand side alone was one of the first approaches. The correction of both the matrix of coefficients and the right hand side introduces non linearity in the constraints. The degree of difficulty in solving the problem of the optimal correction depends on the objective function, whose purpose is to measure the closeness between the original and corrected model. Contrary to other norms, the optimization of the important Frobenius was still an open problem. We have analyzed the problem using the KKT conditions and derived necessary and sufficient conditions which enabled us to unequivocally characterize local optima, in terms of the solution of the Total Least Squares and the set of active constraints. These conditions justify a set of pruning rules, which proved, in preliminary experimental results, quite successful in a tree search procedure for determining the global minimizer.

The room temperature ozone sensing properties of polycrystalline undoped zinc oxide (ZnO) thin films have been investigated. ZnO thin films have been produced by the d.c. and r.f. magnetron sputtering technique as well as with spray pyrolysis with a variety of parameters. The as-grown films were brought to a high conducting state through a reversible photoreduction process by UV light exposure and were subsequently exposed to ozone resulting in a strong resistivity increase caused by re-oxidation. The magnitude of the effect was largest for the sputtered films, which exhibited resistivity changes of more than 8 orders of magnitude, whereas films deposited by spray pyrolysis showed changes of less than 3 orders of magnitude. XRD and AFM analysis of the films revealed that all films were microcrystalline. The film texture, however, was strongly related to the growth technique and the parameters used. Best results were achieved with r.f.-sputtered films, which have been deposited at high total pressures. These films exhibited a sensor response of 1.2 × 108. © 2002 Elsevier Science B.V. All rights reserved.

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.

For the study of astrophysically relevant capture reactions in the underground laboratory LUNA a new setup of high sensitivity has been implemented. The setup includes a windowless gas target, a 4$π$ BGO summing crystal, and beam calorimeters. The setup has been recently used to measure the d(p,$\gamma$)3He cross-section for the first time within its solar Gamow peak, i.e. down to 2.5keV c.m. energy. The features of the optimized setup are described. © 2002 Elsevier Science B.V. All rights reserved.