Rheological and physical properties of aliphatic hyperbranched polyesters

The effects of the size (pseudo‐generation number) and nature of end groups on physical and rheological properties were investigated for a series of hyperbranched polyesters based on an ethoxylated pentaerythritol core and 2,2‐bis‐(hydroxymethyl)propionic acid repeat units. The observed linear dependence of the melt viscosity on the molar mass in the high pseudo‐generation‐number limit indicated that entanglement effects were substantially absent. Moreover, the marked influence of end capping of the end groups on the physical and rheological properties suggested that intermolecular interactions were dominated by contacts between the outer shells of the molecules, in which the end groups were assumed to be concentrated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1218–1225, 2004     

Permeability of N2, Ar,He, O2, and CO2 through as‐extruded amorphous and biaxially oriented polyester films: Dependence on chain mobility

For as‐extruded amorphous and biaxially orientated polyester films based on poly(ethylene terephthalate), poly(ethylene naphthalate), and copolymers containing poly(ethylene terephthalate) and poly(ethylene naphthalate) moieties, permeability, diffusion, and solubility coefficients are interpreted in terms of chain mobility. The influence of polymer morphology is determined by comparison of the data for as‐extruded amorphous sheets and materials produced with different biaxial draw ratios. The crystallinities of the samples were assessed using differential scanning calorimetry and density measurements. Changes in mobility at a molecular level were investigated using dielectric spectroscopy and dynamic mechanical thermal analysis. The study, in conjunction with our earlier work, leads to the conclusion that the key to understanding differences in gas transport is the difference in local chain motions rather than in free volume. This was illustrated by the permeability results for He, Ar, N₂, and O₂ in the range of polyesters. However, the permeability of CO₂ was found to require alternative explanations because of polymer–penetrant interactions. For biaxially oriented samples, the differences in diffusivity are not only due to differences in local chain motions, but also additional constraints resulting from the increased crystallinity and chain rigidity—which also act to hinder segmental mobility. The effectiveness of the reduction in permeability in the biaxially oriented films is consequently determined by the ability of the polymer chains to effectively align and form crystalline structures. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2916–2929, 2004     

Dynamic surface tension measurements of surfactant solutions using the maximum bubble pressure method – limits of applicability

One of the essential differences in the design of bubble pressure tensiometers consists in the geometry of the measuring capillaries. To reach extremely short adsorption times of milliseconds and below, the so-called deadtime of the capillaries must be of the order of some 10 ms. In particular, for concentrated surfactant solutions, such as micellar solutions, short deadtimes are needed to minimize the initial surfactant load of the generated bubbles. A theoretical model is derived and confirmed by experiments performed for a wide range of experimental conditions, mainly in respect to variations in deadtime and bubble volume.     

Three-dimensional structure of Saccharomyces cerevisiae inorganic pyrophosphatase complexed with cobalt and phosphate ions

Crystals of Saccharomyces cerevisiae inorganic pyrophosphatase suitable for X-ray diffraction study were grown by cocrystallization of the enzyme with cobalt chloride and imidodiphosphate. Saccharomyces cerevisiae is a metal-dependent enzyme which catalyzes hydrolysis of inorganic pyrophosphate to orthophosphate. The three-dimensional structure of this enzyme was solved by the molecular-replacement method and refined at 1.8 Å resolution to an R factor of 19.5%. Cobalt and phosphate ions were revealed in the active centers of both identical subunits (A and B) of the pyrophosphatase molecule. In subunit B, a water molecule was found between two cobalt ions. It is believed that this water molecule acts as an attacking nucleophile in the enzymatic cleavage of the pyrophosphate bond. It was demonstrated that cobalt ions and a phosphate group occupy only part of the potential binding sites (two chemically identical and crystallographically independent subunits have different binding sites). The arrangement of ligands and the structure of the nucleophile-binding site are discussed in relation to the mechanism of action of the enzyme and the nature of the metal activator.     

A grid‐free upwind relaxation scheme for inviscid compressible flows

A new grid‐free upwind relaxation scheme for simulating inviscid compressible flows is presented in this paper. The non‐linear conservation equations are converted to linear convection equations with non‐linear source terms by using a relaxation system and its interpretation as a discrete Boltzmann equation. A splitting method is used to separate the convection and relaxation parts. Least squares upwinding is used for discretizing the convection equations, thus developing a grid‐free scheme which can operate on any arbitrary distribution of points. The scheme is grid free in the sense that it works on any arbitrary distribution of points and it does not require any topological information like elements, faces, edges, etc. This method is tested on some standard test cases. To explore the power of the grid‐free scheme, solution‐based adaptation of points is done and the results are presented, which demonstrate the efficiency of the new grid‐free scheme. Copyright © 2005 John Wiley & Sons, Ltd.     

Energetics of an adiabatically-loaded excited anharmonic oscillator

The dependence of the energy characteristics on an adiabatically slowly increasing external force is determined analytically for an anharmonic oscillator. The analytical results are confirmed by a numerical calculation. The nature of the force dependences of the energy characteristics are determined and discussed. Fiz. Tverd. Tela (St. Petersburg) 39, 153–157 (January 1997)     

Shell effects in the symmetric-modal fission of pre-actinide nuclei

Mass distributions of fragments in the low-energy fission of nuclei from ¹⁸⁷Ir to ²¹³At have been analysed. This analysis has shown that shell effects in symmetric-mode fragment mass yields from the fission of pre-actinide nuclei could be described if one assumes the existence of two strongly deformed neutron shells in the arising fragments with neutron numbers N₁ ≈ 52 and N₂ ≈ 68. A new method has been proposed for quantitatively describing the mass distributions of the symmetric fission mode for pre-actinides with A ≈ 180–220.     

On nonspecular “total internal reflection” of powerful electromagnetic waves

It is shown that the nonstable character of nonlinear interaction of a system of waves similar to that resulting from double stimulated Brillouin scattering is retained upon the oblique incidence of a powerful electromagnetic wave on a layer of supercritical plasma. In this case we have nonlinear back reflection from a layer of supercritical plasma. The threshold intensity of the pump wave is greater than that in the case of subcritical plasma for TE polarization waves but can markedly decrease for waves polarized in the incidence plane. Instability is possible only for a layer of finite thickness.Radiophysical Research Institute, Nizhny Novgorod. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 38, Nos. 3–4, pp. 298–303, March–April, 1995.