Polyethylene waxes by metallocenes

The syntheses of low‐molecular‐weight polyethylene (PE), in the presence of catalysts based on five different metallocene frameworks, have been compared. High yields and low molecular masses, typical of industrially relevant PE waxes, can be easily achieved by using overpressure of hydrogen. Particularly suitable for the production of PE waxes are catalytic systems based on the C₂ symmetric rac‐dimethyl‐silyl‐bis‐(2‐methyl‐4‐phenyl‐1‐indenyl)‐zirconium dichloride ( 1 ) and the C_2v symmetric bis‐cyclopentadienyl‐zirconium dichloride ( 5 ). The wax yields can be substantially increased by increasing the MAO/Zr molar ratio. The control of the PE molecular weight allows an easy control of physical properties. In fact, as M_n increases in the range 10³–10⁴ g/mol, the degree of crystallinity decreases from nearly 85 to 60% while the melting temperature increases from 125°C up to 135°C. Copyright © 2010 John Wiley & Sons, Ltd.     

Metal Coordination Properties of a Chromophoric Desferrioxamine (DFO) Derivative: Insight on the Coordination Stoichiometry and Thermodynamic Stability of Zr4+ Complexes

Desferrioxamine (DFO) is the current “gold standard” chelator for ⁸⁹Zr⁴⁺, which is used to label monoclonal antibodies for applications in immunopositron emission tomography. Recently, controversial data have been reported regarding the speciation and the stability of the complexes formed by DFO with Zr⁴⁺ in solution. To shed some light on this point, we studied the coordination properties in solution ofa chromophoric DFO derivative bearing a substituted pyrimidine residue (DFO–Pm) toward several metal ions (Zr⁴⁺, Cu²⁺, Zn²⁺, Mg²⁺, Ca²⁺, Na⁺, K⁺). Potentiometric titrations showed that DFO–Pm and pristine DFO form complexes with very similar stoichiometry and stability. DFO–Pm, which can consequently be taken as a model system for DFO, provides a photochemical response to metal coordination that can be used to further define the complexes formed. In the critical case of Zr⁴⁺, spectrophotometric measurements allowed the verification of the formation of 1:1 and 2:3 complexes that, together with 2:2 complexes form the coordination model that was obtained through the use of our potentiometric measurements. Additionally, mass spectrometry measurements verified the formation of 1:1 and 2:3 complexes and showed that 1:2 species can be easily generated through the fragmentation of the 2:3 species. In conclusion, the results obtained with DFO–Pm validate the complexation model of Zr⁴⁺/DFO composed of 1:1, 2:2, and 2:3 metal-to-ligand complexes. Convergences and conflicts with other works are addressed.     

Sono-photocatalytic degradation of 2-chlorophenol in water: kinetic and energetic comparison with other techniques.

The degradation of 2-chlorophenol in water was kinetically investigated using the following different techniques, employed either separately or simultaneously, always with the same experimental set-up: light irradiation (315-400 nm), sonication, photocatalysis with different types of TiO2, photocatalysis with sonication. The influence of the reaction volume and of different gas mixtures, containing Ar and O2, as well as O2/O3, was also investigated. Finally, an energetic comparison among these different techniques was performed, focused on an industrial application of some of them.     

Chromium doped γ-Al2O3 powders. Features of the electrical double layer and state of the surface species

γ-Al₂O₃ samples, both pure and Cr doped, were prepared by heating at 470°C sol–gel precursors obtained by using aluminum tri-sec-butoxide [Al(OC₄H₉)₃] as the starting compound. The samples were characterised for phase composition (X-ray diffraction) and surface area (BET). Electrochemical determinations of the double layer reactivity of the pure and doped oxides were performed both by surface charge and by electrokinetic sonic amplitude (ESA) determinations. The interfacial electrostatic response is discussed and analysed also with reference to the sample surface state obtained by X-ray photoelectron spectroscopy (XPS).     

A Note on Equilibrium Problems with Properly Quasimonotone Bifunctions

In this paper, we consider some well-known equilibrium problems and their duals in a topological Hausdorff vector space X for a bifunction F defined on K x K,where K is a convex subset of X. Some necessary conditions are investigated, proving different results depending on the behaviour of F on the diagonal set. The concept of proper quasimonotonicity for bifunctions is defined, and the relationship with generalized monotonicity is investigated. The main result proves that the condition of proper quasimonotonicity is sharp in order to solve the dual equilibrium problem on every convex set.     

Resource assignment with preference conditions

This paper deals with a modification of the standard assignment problem, where subsets of resources express preferences in being, or not being, assigned together to the same activity. The problem arises in several real settings, among which the job assignment of the crew personnel of an airline company. We provide an integer programming formulation for both the Split Preference Problem, where couples of assignees do not want to work together, and for the Join Preference Problem, where, oppositely, couples of assignees want to work together. The mathematical nature of the two problems is indeed different, as for the first one it is possible to determine a minimum cost flow formulation on a suitable graph, and thus a polynomial time algorithm, while for the second one we face a NP-hard problem and device some heuristic solution approaches. Experimental tests conducted on instances of variable size confirm the effectiveness of the models and of the algorithms proposed.     

The conductivity of dilute electrolyte solutions: Expanded lee and wheaton equation for symmetrical,unsymmetrical and mixed electrolytes

The conductivity equation of Lee and Wheaton is expanded in a power series in the ionic strength I. Different levels of approximation are analyzed and it is shown that for unsymmetrical electrolytes it is necessary to keep the terms I^3/2lnI and I² to maintain the performance of the full equation.     

The worldwide NORM production and a fully automated gamma-ray spectrometer for their characterization

Materials containing radionuclides of natural origin and being subject to regulation because of their radioactivity are known as Naturally Occurring Radioactive Material (NORM). By following International Atomic Energy Agency, we include in NORM those materials with an activity concentration, which is modified by human made processes. We present a brief review of the main categories of non-nuclear industries together with the levels of activity concentration in feed raw materials, products and waste, including mechanisms of radioisotope enrichments. The global management of NORM shows a high level of complexity, mainly due to different degrees of radioactivity enhancement and the huge amount of worldwide waste production. The future tendency of guidelines concerning environmental protection will require both a systematic monitoring based on the ever-increasing sampling and high performance of gamma-ray spectroscopy. On the ground of these requirements a new low-background fully automated high-resolution gamma-ray spectrometer MCA_Rad has been developed. The design of lead and cooper shielding allowed to reach a background reduction of two order of magnitude with respect to laboratory radioactivity. A severe lowering of manpower cost is obtained through a fully automation system, which enables up to 24 samples to be measured without any human attendance. Two coupled HPGe detectors increase the detection efficiency, performing accurate measurements on small sample volume (180 cm³) with a reduction of sample transport cost of material. Details of the instrument calibration method are presented. MCA_Rad system can measure in less than one hour a typical NORM sample enriched in U and Th with some hundreds of Bq kg^?1, with an overall uncertainty less than 5 %. Quality control of this method has been tested. Measurements of three certified reference materials RGK-1, RGU-2 and RGTh-1 containing concentrations of potassium, uranium and thorium comparable to NORM have been performed. As a result, this test achieved an overall relative discrepancy of 5 % among central values within the reported uncertainty.