Trends in Hydrological Parameters of a Southern Brazilian Watershed and its Relation to Human Induced Changes

The Piracicaba river basin is a subtropical watershed located in the southeastern region of Brazil. With an area of 12 400 km², the basin is a typical example of new landscape resulting from development in tropical and sub-tropical regions: establishment of intensive industrial and agricultural processes were followed by significant population growth and water management. This scenario has led to significant increase in water demand and decrease in water quality. The main objective of this study is the detection of changes in the patterns of flow and precipitation in the basin, and its possible relation to man-induced changes. Statistical analyses were performed on records of precipitation, evapotranspiration and streamflow, from 1947 to 1991. Precipitation and evapotranspiration totals showed significant increasing trends for the entire basin. From eight streamflow gauge stations, half showed significant decreasing trend. The most probable cause of such trends is the export of water from the basin to the metropolitan region of São Paulo city.     

Hydrodechlorination of 3-chloropyridine and chlorobenzene in methanol solution over alkali-modified zirconia-supported palladium catalysts

The liquid-phase hydrodechlorination of 3-chloropyridine and chlorobenzene has been studied over alkali-modified zirconia-supported palladium catalysts. The modification of the ZrO₂ with alkali metal carbonates improves the catalytic activity of the final palladium catalyst. Therefore, the larger the ionic radii (Li⁺ < Na⁺ < K⁺), the greater the catalytic activity (TOF) of the palladium catalyst. For 3-chloropyridine, hydrodechlorination proceeds without catalyst deactivation. This is explained as the result of the interaction of reaction products (pyridine and HCl) forming pyridinium chloride, thus avoiding the detrimental effect of HCl on the palladium particles. Catalytic hydrodechlorination of chlorobenzene over Pd catalysts exhibits an initial catalytic activity (TOF) much lower than that of 3-chloropyridine and the Pd catalysts deactivate as the reaction proceeds. Finally, chlorobenzene hydrodehalogenation has also been carried out in the presence of an equimolecular amount of pyridine resulting in a decrease in the initial reaction rate on the one hand, but also in an increase in final conversion on the other.     

Infrared and ultraviolet–visible spectroscopic studies of silica, [(Cp)2ZrCl2] and trimethylaluminum interactions

Infrared and UV–vis studies of metallocene immobilization on silica are reported here. The results have indicated changes in the Zr coordination sphere of metallocene depending on the immobilization route used. The reaction of [(Cp)₂ZrCl₂] with silica formed [(Cp)₂ZrCl]⁺[SiO]⁻ species. The same metallocene, reacting with TMA modified silica, formed monomethylated and dimethylated species by the substitution of chloro for methyl ligands, stabilized on the surface by interaction with “MAO-like” species (methylaluminoxane, MAO). These monomethylated and dimethylated cationic zirconium species are the active centers for the polymerization reaction. Different order of TMA addition in the silica modification step generated surface species of a similar nature, differing in their relative quantities. The highest amount of these active species was obtained when the support was added to the TMA solution rather than adding the TMA solution to the silica support. This was the most significant parameter affecting catalytic activity in ethylene polymerization.     

Evaluation and enhancement of COBRA-TF efficiency for LWR calculations

Detailed representations of the reactor core generate computational meshes with a high number of cells where the fluid dynamics equations must be solved. An exhaustive analysis of the CPU times needed by the thermal-hydraulic subchannel code COBRA-TF for different stages in the solution process has revealed that the solution of the linear system of pressure equations is the most time consuming process. To improve code efficiency two optimized matrix solvers, Super LU library and Krylov non-stationary iterative methods have been implemented in the code and their performance has been tested using a suite of five test cases. The results of performed comparative analyses have demonstrated that for large cases, the implementation of the Bi-Conjugate Gradient Stabilized (Bi-CGSTAB) Krylov method combined with the incomplete LU factorization with dual truncation strategy (ILUT) pre-conditioner reduced the time used by the code for the solution of the pressure matrix by a factor of 20. Both new solvers converge smoothly regardless of the nature of simulated cases and the mesh structures and improve the stability and accuracy of results compared to the classic Gauss–Seidel iterative method. The obtained results indicate that the direct inversion method is the best option for small cases.     

Optical and electrical characterization of fluorine doped cadmium oxide thin films prepared by the sol-gel method

Highly transparent and conducting fluorine (F) doped cadmium oxide (CdO) thin films were deposited on glass slides by the sol-gel method. The films were doped by the addition of ammonium fluoride to the precursor solution whose optimum concentration was determined. The films were fired in an open atmosphere at 350 °C and after that, exposed to annealing treatments in different atmospheres (N₂, N₂/H₂ mixture and Ar) at the same temperature. The films were characterized by ultraviolet-visible spectroscopy, X‐ray diffraction and scanning electron microscopy. The resistivity was determined by the four probes method and current-voltage measurements in accordance with the standard Van der Pauw configuration. The CdO:F thin films obtained, showed high polycrystalline quality and high transmission in the visible region (≥ 90%), shifting towards the blue region of the absorption edge as the fluorine concentration in the precursor solution was increased from 0 to 30 at.%. The lowest resistivity values were reached for the samples with F content higher or equal to 5% and annealed in either N₂ or a 96/4 N₂/H₂ gas mixture. Our resistivity value reached in the CdO:F layers was 4.5 × 10^{− 4} Ω cm (20 Ω/square).     

An educational resource for information literacy in higher education: Functional and users analyses of the e-COMS academic portal

As in today’s knowledge society the Internet is playing an important role in the information literacy of university students the goal of this paper is to analyse, after its first year on the Web, the informational impact of an e-learning resource developed by Granada’s University lecturers (the e-COMS educational portal), a pioneer in Spain for training in information literacy. From the objective and subjective data provided by the own portal and by it users, two different and complementary kinds of analysis (functional and users’) are performed. Assessment of various capabilities, among which visibility and usability stand out, is provided. The highly positive but improvable results offer a detailed analysis of the functional aspects of the portal itself and of the users’ relations with this information resource. From these analyses strengths and weaknesses are extracted and some proposals for improvement are derived.     

XPS studies of directly fluorinated HDPE: problems and solutions

X-ray photoelectron spectroscopy (XPS) applied to the study of fluorinated polymer surfaces presents several problems related both to peak assignment and to degradation. In this work, we analyse extensively the question of XPS peak assignments in this kind of surfaces. We conclude that in this kind of surfaces using binding energy differences between fluorine and carbon is better than using absolute binding energies. Also a useful relation between fluorine photoelectron energy vs. polymer composition expressed through the atomic ratio fluorine/carbon (F/C) was found. A protocol for data treatment is proposed and applied to a XPS study of the degradation induced by X-ray on high-density polyethylene surfaces modified by direct fluorination. Results obtained for the degradation, namely the atomic ratio F/C obtained by two different methods, combined with angle resolved X-ray photoelectron spectroscopy (ARXPS) were used to study the fluorine concentration profile in depth, producing self-consistent results.