Miscibility in poly(L-lactide)- b -poly( $ \upvarepsilon$ -caprolactone) double crystalline diblock copolymers

Thermally stimulated depolarization currents, TSDC, wide-angle X-ray scattering, WAXS, differential scanning calorimetry, DSC, and polarized light optical microscopy, PLOM, have been used to examine poly(L-lactide)-b -poly( -caprolactone) diblock copolymers in a wide composition range. Both components are crystallizable and the miscibility in the amorphous phase has been determined from the behavior of the primary relaxations which are the dielectric manifestation of the glass transition, and also from the superstructural morphology revealed by PLOM and the compositional dependence of the melting points as determined by DSC. Distinct segmental mobilities in the amorphous phase which can be well resolved by TSDC are present; the mode of the slower component shifts to lower temperatures as the PCL content increases while the glass transition of neat PCL is present for all compositions. A relaxation times bimodal distribution is apparent for PCL-rich copolymers. The composition dependence of the multiple glass transitions detected in these weakly segregated copolymers are predicted by the self-concentration model for a miscible blend made of components with a large T_g contrast.     

The phases of isospin-asymmetric matter in the two-flavor NJL model

We investigate the phase diagram of isospin-asymmetric matter at T=0$T=0$ in the two-flavor Nambu–Jona-Lasinio model. Our approach describes the single nucleon as a confined quark–diquark state, the saturation properties of nuclear matter at normal densities, and the phase transition to normal or color superconducting quark matter at higher densities. The resulting equation of state of charge-neutral matter and the structure of compact stars are discussed.     

Influence of radial electric field on trajectories of plug potential bounce ion in the tandem mirror

Bouncing ions between the plug potentials play an important role in improvement of the axial confinement in the tandem mirror. We examined the influence of the radial electric field on the trajectories of the ions passed through the anchor cell with nonaxisymmetric magnetic configuration on the assumption that the shape of the magnetic flux tube was shifted from the shape of the equipotential surface of the plasma at the mirror throats of the anchor cells. The discrepancy between the shapes enhanced the radial drift of the bounce ion. Radial potential profile of the core plasma was controlled by adjustment of the radially separated endplate potentials, and it was found that the flattened radial potential profile was effective for the decrease of the radial drift. Presented at 5th Workshop “Role of Electric Fields in Plasma Confinement and Exhaust”, Montreux, Switzerland, June 23–24, 2002.     

Probing alkali coordination environments in alkali borate glasses by multinuclear magnetic resonance

Five series of binary alkali borate glasses were prepared to compare the alkali dependence of network and modifier short-range order. ¹¹B magic-angle spinning (MAS) NMR reveals that the fraction of four-coordinate boron depends strongly upon alkali type at high-alkali concentrations: heavier alkalis favour the formation of non-bridging oxygens, whereas lithium borates contain a much higher concentration of tetrahedral boron units. The alkali modifiers were observed directly by MAS NMR to measure the change in chemical shift with composition. All alkali peaks shift to higher frequency with increasing loading, indicative of decreasing average coordination numbers. Relative to their known chemical shift ranges, the heavier alkalis exhibit the greatest shifts, whereas the lithium shifts are subtle. This is interpreted in terms of the availability of charged and partially charged coordinating oxygens in the network. Moreover, the ¹³³Cs chemical shifts plateau at 40 mol%, implying that the Cs⁺ coordination number reaches a lower limit at this composition. This work demonstrates that NMR instrumentation and methodology have reached a level where even challenging nuclei like ³⁹K and ⁸⁷Rb can be probed to yield structural information in glasses.     

Steady drainage in emulsions: corrections for surface Plateau borders and a model for high aqueous volume fraction

We compare extensive experimental results for the gravity-driven steady drainage of oil-in-water emulsions with two theoretical predictions, both based on the assumption of Poiseuille flow. The first is from standard foam drainage theory, applicable at low aqueous volume fractions, for which a correction is derived to account for the effects of the confinement of the emulsion. The second arises from considering the permeability of a model porous medium consisting of solid sphere packings, applicable at higher aqueous volume fractions. We find quantitative agreement between experiment and the foam drainage theory at low aqueous volume fractions. At higher aqueous volume fractions, the reduced flow rate calculated from the permeability theory approaches the master curve of the experimental data. Our experimental data demonstrates the analogy between the problem of electrical flow and liquid flow through foams and emulsions.     

The evolution of poly(lactic acid) degradability by dielectric spectroscopy measurements

Dielectric spectroscopy is a powerful method that allows the study of the dynamics of polymers in a wide frequency range. The different regimes of the dielectric spectra can be observed and the dynamics of the primary and secondary relaxations can be found.In this work, the systems investigated included industrial and purified poly(lactic acid), PLA. This is an aliphatic polyester, one of the most important biocompatible and biodegradable material that has received increasing attention in the last 10 years.Thermal analyses indicated that the glass transition temperature of the polymer was about 320 K.The β relaxation was observed between −150 °C and −30 °C, depending on the measurement frequency (1 Hz-100 kHz), and was assigned to the secondary relaxation in the glassy state. We studied the changes that are connected with the water penetration in the polymer, and directly affect that relaxation process. Water molecules confined by polymer chains and in the polymer networks play an important role in the degradation of the matrix, and then we can observe the evolution of that degradation during some weeks, in a controlled humidity environment. It is accepted that water preferentially enters in the amorphous zones, but also affects the crystalline regions. It is observed a clear evolution of the relaxation activation energy during the degradation of the polymer.The dielectric relaxation results are complemented with molar mass measurements during the degradation process with time.     

An experimental study of the regimes of motion of spheres falling or ascending freely in a Newtonian fluid

This paper presents the results of an experimental investigation aimed at verifying some of the interesting conclusions of the numerical study by Jenny et al. concerning the instability and the transition of the motion of solid spheres falling or ascending freely in a Newtonian fluid. The phenomenon is governed by two dimensionsless parameters: the Galileo number G, and the ratio of the density of the spheres to that of the surrounding fluid ρ_s/ρ. Jenny et al. showed that the (G, ρ_s/ρ) parameter space may be divided into regions with distinct features of the trajectories followed eventually by the spheres after their release from rest. The characteristics of these ‘regimes of motion’ as described by Jenny et al., agree well with what was observed in our experiments. However, flow visualizations of the wakes of the spheres using a Schlieren optics technique raise doubts about another conclusion of Jenny et al., namely the absence of a bifid wake structure.     

Laser induced thermal profiles in thermally and optically thin films

The temperature field generated by the weak absorption of a gaussian laser beam in an optically and thermally thin film bounded by two transparent plates is discussed. An analytical solution of the problem is presented together with an algorithm for the numerical integration. The influence of the finite thermal conductivity of the plates is shown in an example.