Local chain‐configuration dependence of the mechanisms of the chemical reaction of poly(vinyl chloride). IX. Novel results on stereoselectivity of chlorination reaction

A poly(vinyl chloride) (PVC) sample was chlorinated in solution in the presence of 2,2′‐azobisisobutyronitrile and by the fluid‐bed method. The aim was to evaluate the scope of the stereoselectivity of the chlorination reaction. The quantitative microstructural analysis of the residual PVC with a degree of chlorination was followed by ¹³C NMR spectroscopy. From the evolution of the content of isotactic (mm), heterotactic (mr), and syndiotactic (rr) triads and of mmmm, mmmr, and rmmr isotactic pentads in the unchlorinated parts of the polymer, it was unambiguously inferred that the chlorination reaction proceeds by a stereoselective mechanism in that the mr heterotactic triads are the most reactive structures followed by the isotactic triad at mmmr and rmmr pentads. This conclusion was confirmed on the basis of the Fourier transform infrared results. The results provide valuable information regarding the effect of tacticity and related local conformations in the chemical reactions of PVC. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 508–519, 2003     

Determination of the rheological behavior of epoxy–amine thermosets by dynamic mechanical analysis: Isothermal methods versus nonisothermal methods

The reticulation process of an epoxy resin using an amine as a cure agent was studied at different temperatures and concentrations of the cure agent with dynamic mechanical thermal analysis. The study was performed under both isothermal and nonisothermal conditions, and a temperature–time–transformation diagram was obtained. The measurements from the two modes gave similar results, although the nonisothermal mode required fewer experiments. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1965–1977, 2003     

Analysis and finite element simulations of a second‐order fluid model in a bounded domain

This article is concerned with the equations governing the steady motion of a viscoelastic incompressible second‐order fluid in a bounded domain. A new proof of existence and uniqueness of strong solutions is given. In addition, using appropriate finite element methods to approximate a coupled equivalent problem, sharp error estimates are obtained using a fixed point argument. The method is applied to the two‐dimensional lid‐driven cavity problem, at low Reynolds number and in a certain range of values of the viscoelastic parameters, to analyze the combined effects of inertia and viscoelasticity on the flow. © 2007 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2007     

Near-infrared laser photoacoustic detection of methane: the impact of molecular relaxation

A photoacoustic sensor has been developed for trace-gas monitoring using a near-infrared semiconductor laser emitting in the 2ν₃ band of methane at 1.65 μm. The apparatus was designed for on-line process control in the manufacturing of the novel low-water-peak fibres developed for optical telecommunications. The importance of collisional relaxation processes in the generation of the photoacoustic signal is reported in the particular case of CH₄ detection in dry O₂ and O₂–N₂ mixtures. The negative influence of these effects results in a strongly reduced and phase-shifted photoacoustic signal, induced by a fast resonant coupling between the vibrational states of methane and oxygen, associated with the slow relaxation of the excited oxygen molecules. An unusual parabolic response of the sensor with respect to the methane concentration has been observed and is discussed. Finally, the beneficial effect of several species, including water vapour and helium, acting as a catalyst to hasten the relaxation of the CH₄–O₂ system, is demonstrated. PACS 42.62.Fi; 33.20.Ea; 34.50.Ez     

Selective spatial localization of the atom displacements in one-dimensional hybrid quasi-regular (Thue-Morse and Rudin-Shapiro)/periodic structures

We have studied the vibrational frequencies and atom displacements of one-dimensional systems formed by combinations of Thue-Morse and Rudin-Shapiro quasi-regular stackings with periodic ones. The materials are described by nearest-neighbor force constants and the corresponding atom masses. These systems exhibit differences in the frequency spectrum as compared to the original simple quasi-regular generations and periodic structures. The most important feature is the presence of separate confinement of the atom displacements in one of the parts forming the total composite structure for different frequency ranges, thus acting as a kind of phononic cavity.     

Towards an universal classification of scale invariant processes

We consider fields which take random values over several decades. Starting from physical examples, we postulate that scale is not an absolute quantity. We then establish the equivalence between two existing approaches based on scale symmetry arguments as general as possible. This yields a classification of log-infinitely divisible laws, possibly universal. The physical significance of the parameters entering in the classification is discussed. Received: 7 November 1997 / Received in final form: 26 March 1998 / Accepted: 30 March 1998     

Collisions for the quantum Coulomb Hamiltonian

We study the propagation of phase space singularities for the time dependent Schrödinger equation with potential having Coulomb-type singularities in space dimension equal tothree. We prove that the singularities (frequency set) of the solution are reflected by a Coulomb center exactly as in the classical problem, i.e. the frequency set follows theregularized trajectories of Classical Mechanics after a collision.