Differential scanning calorimetry and thermogravimetric analysis investigation of the thermal properties and degradation of some radiation‐grafted films and membranes

The influence of irradiation and grafting on the crystallinity of three base polymers has been investigated with differential scanning calorimetry. Grafting has the largest effect on the base polymer crystallinity and results in a reduction of the crystallinity. The thermal degradation of the base polymers and grafted films has been investigated with thermogravimetric analysis. The extent of the fluorination of the base polymer, the irradiation method, and the graft level all influence the thermal degradation and its activation energy. It is proposed that the variation of the chain lengths of the grafted polystyrene chains is actually a primary underlying factor responsible for the influence of these various parameters on the degradation process. The first results of a comparative thermal analysis of some fuel‐cell membranes are also presented, and the promise and shortcomings of this method are discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2612–2624, 2004     

New efficient catalysts for the aerobic oxidation of ethers

Some nickel, copper, and silver salts or complexes are efficient catalysts for the oxidation of benzylic ethers with oxygen in 1,2-dimethoxyethane. Salts of the weakly coordinating anion trifluoroacetate are particularly efficient, approaching (and, in some cases, improving) the yields obtained with cobalt(II) chloride, the best catalyst so far reported.     

Giant shot-like voltage noise in high current density Nb–AlOx–Nb superconducting tunnel junctions

The flat voltage noise component of current biased, high-transparency Nb/AlO_x/Nb superconducting tunnel junctions has been investigated at frequencies up to 70 kHz. Several aspects of the analyzed phenomena suggest the presence of current noise effects induced by the discreteness of the charge carriers. At subgap voltages, where excess currents occur, a behavior coherent with a multiple Andreev reflection-assisted transport through the tunnel barrier has been found. However, the measured charge values exceed any theoretical prediction.     

A short synthesis of (±)-tecomanine via a Pauson-Khand-based route

The N-carboethoxy precursor to (±)-tecomanine has been prepared in 11 steps from 2-methyl-1-buten-3-yne. The key step, Pauson-Khand cyclization of a methylated 5-aza-6-nonen-1-yne succeeds, but only in low yield, a consequence of the dialkyl substitution about the azaenyne framework. Nevertheless, the overall sequence to that point is one of the more efficient to be described.     

A model for the interaction of near-infrared laser pulses with metal powders in selective laser sintering

A thermal model of the interaction of pulsed near-infrared laser radiation from a Nd:YAG laser was made, taking the measured powder properties such as reflectance, optical penetration depth and thermal conductivity into account. It allows an estimation of the evolution of two different temperatures: the average temperature of the powder (taken over the grains in a volume given by the laser beam diameter and the optical penetration depth) and the temperature distinction within a single grain. It showed that in pulsed mode consolidation can be achieved at much lower average power as the surface of the powder particles are molten but their cores remain at nearly room temperature. This leads to a much lower average temperature and therefore a dramatic decrease in residual thermal stresses in the finished piece. The results of the model were experimentally tested and confirmed. Received: 26 July 2001 / Accepted: 23 November 2001 / Published online: 23 January 2002     

Synchronization Analysis of Coupled Noncoherent Oscillators

We present two different approaches to detect and quantify phase synchronization in the case of coupled non-phase coherent oscillators. The first one is based on the general idea of curvature of an arbitrary curve. The second one is based on recurrences of the trajectory in phase space. We illustrate both methods in the paradigmatic example of the R?ssler system in the funnel regime. We show that the second method is applicable even in the case of noisy data. Furthermore, we extend the second approach to the application of chains of coupled systems, which allows us to detect easily clusters of synchronized oscillators. In order to illustrate the applicability of this approach, we show the results of the algorithm applied to experimental data from a population of 64 electrochemical oscillators.     

Phospha-palladacycles and N-heterocyclic carbene palladium complexes: efficient catalysts for CC-coupling reactions

Due to the great importance of palladium-catalyzed Heck-type reactions in scientific and industrial chemistry, a lot of publications and reviews have been published during the last years describing this matter under different aspects. This article presents a summary of catalytic applications of palladium complexes with phosphorus ligands containing a metallated sp³-carbon centre (“palladacycles”) or with N-heterocyclic carbene ligands in C-C and C-N coupling reactions of aryl halides including recent results of mechanistic discussions about their role in the catalytic cycle.     

Time-Resolved Femtosecond Degenerate Four-Wave Mixing in LiNbO3：Fe,Mg Crystal

Forward degenerate four-wave mixing （DFWM） processes are investigated with a femtosecond pulsed laser in lithium niobate crystal doubly-doped with magnesium and iron （LiNbO3：Fe, Mg）. The pulse energy dependence reveals a pure third-order nonlinear response, and the third-order nonlinear susceptibility x^（3） in the material is evaluated to be 4.96 × 10^-13 esu. The time-resolved DFWM process shows a response time of x^（3） shorter than 100fs, which is due to the nonresonant electronic nonlinearities. Our results indicate that LiNbO3 crystals have potentials for ultrafast real-time optical processing systems, which require a large and fast x^（3） optical nonlinearity.     

A Borsuk–Ulam Theorem for Maps from a Sphere to a Generalized Manifold

H. J. Munkholm obtained a generalization for topological manifolds of the famous Borsuk–Ulam type theorem proved by Conner and Floyd. The purpose of this paper is to prove a version of Conner and Floyd's theorem for generalized manifolds.