Atomistic packing models for experimentally investigated swelling states induced by CO2 in glassy polysulfone and poly(ether sulfone)

Atomistic packing models have been created, which help to better understand the experimentally observed swelling behavior of glassy polysulfone and poly (ether sulfone), under CO₂ gas pressures up to 50 bar at 308 K. The experimental characterization includes the measurement of the time‐dependent volume dilation of the polymer samples after a pressure step and the determination of the corresponding gas concentrations by gravimetric gas‐sorption measurements. The models obtained by force‐field‐based molecular mechanics and molecular dynamics methods allow a detailed atomistic analysis of representative swelling states of polymer/gas systems, with respect to the dilation of the matrix. Also, changes of free volume distribution and backbone mobility are accessible. The behavior of gas molecules in unswollen and swollen polymer matrices is characterized in terms of sorption, diffusion, and plasticization. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1874–1897, 2006     

Quantification of stable minor species in confined flames by cavity ring-down spectroscopy: application to NO

Cavity ring-down spectroscopy (CRDS) is used to measure the NO mole fraction formed in the burnt gases of low-pressure premixed flames. It is shown that the line-of-sight absorption is greatly increased by the contribution of the NO molecules surrounding the burner. This contribution has been quantified by developing a mathematical procedure taking into account the spatial and spectral features of the CRDS measurement. Calculations have been undertaken in the general case of a stable species not consumed in the flame. The most sensitive parameter is the temperature both in the flame and outside the flame. Simulations allow the selection of the best spectroscopic transitions for a given flame (i.e. a given temperature profile), ensuring the weakest influence of the inaccuracy affecting the temperature determination. High quantum states belonging to the A–X (0–1) band of NO have been found to be the most valuable and have led to a NO mole fraction determination with an accuracy of ±13%. NO absorption in the flame was completely masked using the A–X (0–0) band. Finally, the prompt-NO mole fraction formed in a methane/air flame stabilized at 33 Torr is obtained by combining CRDS and laser induced fluorescence techniques. Received: 12 October / Revised version: 1 February 2002 / Published online: 14 March 2002     

The Kosterlitz-Thouless model in Perovskite superconductors

Il Nuovo Cimento D - The applicability of the Kosterlitz-Thouless theory to HTSC is examined. The model initially presented in its general lines for bidimensional systems is then applied to...     

Effect of Finite Spectral Width on the Modulational Instability of Langmuir Waves described by a Nonlinear Schrödinger Equation

By using the two-point space correlation function an equation for the power spectral density for a random Langmuir field has been derived. The dispersion relation for a monochromatic wave is regained for a delta spectrum. For a Gaussian spectrum, the maximum growth rate is less than that for a monochromatic wave. For a “meander spectrum”, the growth rate is increased with the width of the spectrum in the first stage then decreased for further increase of the width.     

The combined effects of evaporation and quench steps on asymmetric membrane formation by phase inversion

An analysis of the effects of combined evaporation and quench periods on the formation of asymmetric membranes by the phase inversion technique is presented. The model for the evaporation period assumes binary diffusion and includes composition dependence in the mutual diffusion coefficient and free convection mass transfer in the gas phase. The quench period model includes the use of 4 composition-dependent diffusion coefficients and incorporates a modified from of the interface jump mass balance which enables efficient numerical analysis of composition gradients in the film at the beginning of the quench period. Results for the effects of evaporation-period variable, including: evaporation time, initial cast film thickness, casting surface dimension, and vapor-phase composition, clearly indicate that significant effects of the evaporation period on membrane structure formation and its reproducibility occur within 20 seconds.     

Inertia-preserving secant updates

Corrections to the last two equations of Ref. 1 are given.     

Intersegmental interaction and critical concentrations in PET–HFIP solutions

Spectroscopic determinations of the concentrations associated with the onset of intermolecular interaction in solutions of poly(ethylene terephthalate) (PET) are described. The intersegment forces perturb the electronic spectra and induce ground-state aggregation. These phenomena become observable at different chain densities, reflecting the influence of concentration on the coil dimensions, as well as the dynamical nature of the interactions. An estimate of the equilibrium constant for PET dimer formation in hexafluoroisopropanol is reported.     

Step-strain deformations for viscoelastic fluids: Formulation of a strain-coupling constitutive equation

An integral constitutive equation which includes strain-coupling effects is proposed. The constitutive equation is more general than the K-BKZ equation, and it is shown that this equation can explain various important aspects of double-step stress-relaxation data.     

A composite methodology for multistage degradation of polymers

Five different analytical schemes for examining isothermal and nonisothermal degradation of polymers were reviewed and found inadequate for describing multistage decomposition. The different schemes were experimentally tested using thermogravimetric analysis data for an ethylene-vinyl acetate (EVA) copolymer, which exhibited a well-behaved two-step decomposition process in a nitrogen environment. Based on these experimental and analytical findings, a generalized methodology was developed capable of describing the exhibited complex decomposition behavior of polymers by combining two or more kinetic mechanisms in a series or parallel arrangement. This composite of combinational methodology thus extends established analytical schemes for describing complex decomposition of polymers in a rational manner, incorporating both experimental and theoretical considerations.