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.     

Detection of failure sites by focused ion beam and nano-probing in the interconnect of three-dimensional stacked circuit structures

Focused ion beam (FIB) and nano-probing were applied for failure analysis of three-dimensional stacked circuits with copper through-silicon-vias between the stacked chips. The failure analysis was done after high temperature storage and thermal cycling tests. Passive voltage contrast in FIB allowed to pinpoint the open sites. FIB cross-sections showed the presence of opens at the bottom of the copper vias. The failure cause was suspected to be an interlayer particle, which was confirmed by optical profilometry. Nano-probing was used on another sample to pinpoint the failure location through the measurement of the local resistance within the daisy chains. The failure was traced out to be related with surface contamination.     

KATRIN NEG pumping concept investigation

The Karlsruhe Tritium Neutrino experiment (KATRIN) is going to use a very large electro-static tandem spectrometer to measure the electron spectrum from the tritium beta decay, where several kilometers of non-evaporable getter (NEG) strips (type ST707) are to be used to achieve the UHV requirements. Different geometrical configurations of the NEG strips have been studied by Monte Carlo simulations. It is shown that the resulting pumping speed of the getter pumps will allow to get a pressure below 10⁻¹¹ mbar in the huge vessel with a volume of 1400 m³. By systematic assessment of the statistics of the pumping surfaces, it could be demonstrated that the design is sound.     

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.     

Effects of age and schooling on the acquisition of elementary quantitative skills.

The influence of school- and age-related variables was examined separately on 2 tasks involving elementary quantitative skills: conservation of number and mental addition. Performance on these tasks was compared by using a cutoff design with 3 groups of kindergarten and Grade 1 children who differed in age but not amount of schooling (grade), in schooling but not age, or in both age and schooling. The effects of age and schooling were distinct. On conservation of number, performance improved as a function of age but not schooling. On mental arithmetic, accuracy improved with schooling rather than age but children's use of various solution procedures (e.g., retrieval, counting) was not influenced by schooling. Thus, in the domain of elementary mathematical skills, the influence of schooling can be very specific, and age-related variables other than schooling play an important role in the development of elementary mathematical skills. Results illustrate the utility of the cutoff design for investigating instructional and developmental influences on cognitive development. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Energy efficiency, carbon emissions and economic development in Venezuela

Venezuela's vast natural resource base has largely shaped the nation's economic and energy-use patterns. Major opportunities exist for improving the efficiency of energy use in Venezuela and, consequently, restraining the growth of energy-related carbon emissions. This paper presents a detailed report of one potential development path for Venezuela and estimates the ensuing levels of energy demand and CO₂ emissions associated with pursuing this path through the year 2025. The results indicate that by adopting a development strategy that incorporates structural changes in the economy, fuel-switching measures and improved end-use efficiencies, Venezuela can introduce energy efficiency and carbon restraints as part of its economic development process.     

The ontogeny and significance of infants' facial expressions in the first 9 months of life.

Four studies examined aspects of the differential emotions theory (DET) hypothesis of expressive behavior development. In Study 1, facial-expressive movements of 108 2.5–9-mo-old infants were video recorded in positive and negative mother–infant interactions (conditions). As expected, Max-specified full-face and partial expressions of interest, joy, sadness, and anger were morphologically stable between the 2 ages. Studies 1 and 2 confirmed predicted differential responding to mother sadness and anger expressions and to composite positive and negative conditions. Discrete negative expressions exceeded negative blends, and the amount of both expression types remained stable across ages. Studies 3 and 4 provided varying degrees of support for the social validity of Max-specified infant negative affect expressions. Conclusions include revisions and clarifications of DET. (PsycINFO Database Record (c) 2010 APA, all rights reserved)