Thermal stability of shear-induced precursor structures in isotactic polypropylene by rheo-X-ray techniques with couette flow geometry

Combined in situ rheo-SAXS (small-angle X-ray scattering) and -WAXD (wide-angle X-ray diffraction) studies using couette flow geometry were carried out to probe thermal stabilty of shear-induced oriented precursor structure in isotactic polypropylene (iPP) at around its normal melting point (162 °C). Although SAXS results corroborated the emerging consensus about the formation of “long-living” metastable mesomorphic precursor structures in sheared iPP melts, these are the first quantitative measures of the limiting temperature at which no oriented structures survive. At the applied shear, rate = 60 s⁻¹ and duration t_s = 5 s, the oriented iPP structures survived a temperature of 185 °C for 1 h after shear, while no stable structures were detected at and above 195 °C. Following Keller's concepts of chain orientation in flow, it is proposed that the chains with highly oriented high molecular weight fraction are primarily responsible for their stability at high temperatures. Furthermore, the effects of flow condition, specifically the shear temperature, on the distributions of oriented and unoriented crystals were determined from rheo-WAXD results. As expected, at a constant flow intensity (i.e., rate = 30 s⁻¹ and duration, t_s = 5 s), the oriented crystal fraction decreased with the increase in temperature above 155 °C, below which the oriented fraction decreased with the decrease in temperature. As a result, a crystallinty “phase” diagram, i.e., temperature versus crystal fraction ratio, exhibited a peculiar “hourglass” shape, similar to that found in many two-phase polymer–polymer blends. This can be explained by the competition between the oriented and unoriented crystals in the available crystallizable species. Below the shear temperature (155 °C), the unoriented crystals crystallized so rapidly that they overwhelmed the crystallization of the oriented crystals, thus depleting a major portion of the crystallizable species and increasing their contribution in the final total crystalline phase. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3553–3570, 2006     

Moisture sorption, transport, and hydrolytic degradation in polylactide

Management of moisture penetration and hydrolytic degradation of polylactide (PLA) is extremely important during the manufacturing, shipping, storage, and end-use of PLA products. Moisture transport, crystallization, and degradation, in PLA have been measured through a variety of experimental techniques including size-exclusion chromatography, differential scanning calorimetry, and X-ray diffraction. Quartz crystal microbalance and dynamic vapor sorption experiments have also been used to measure moisture sorption isotherms in PLA films with varying crystallinity. A surprising result is that, within the accuracy of the experiments, crystalline and amorphous PLA films exhibit identical sorption isotherms.     

CONFLICT AND COOPERATION IN UTILIZING A COMMON PROPERTY RESOURCE

Noncooperative games are used to demonstrate that, while free riding is always an option, the “tragedy of the commons” is not inevitable. When the decision to cooperate or free ride is considered in a dynamic setting, there is no intermediate case where some cooperate and others free ride. The game is only stabilized in either full cooperation or full defection. The important factor in obtaining a cooperative outcome is the critical number of players that decide to cooperate. The concept of commitment is used to demonstrate the necessary and sufficient conditions for full cooperation. Although the analysis is based on a shared water resource, it can be extended to other natural resources with common costs and private benefits, especially in the cases where there are no international authorities or treaties that internalize the externalities involved in privatizing the resource.     

Inclusive\bar K^{0*} (892) andK 0*(892) production on silicon by 200 GeVK − andπ −

The production of the neutralK ^? (892) resonances by 200 GeVK ^? andπ ^? has been studied over the kinematic range 0.0<x _f<1.0 andp _t ² <5.0 GeV². Longitudinal and transverse momentum distributions are presented. In addition the decay angular distributions inK ^? fragmentation to \(\bar K^{0*} \) have been investigated.     

Inner multipliers of de Branges's spaces

For a given functionb in the unit ball ofH and an arbitraryH functionm, the question of whenm is a multiplier of the de Branges space (that is, when is invariant under multiplication bym) is examined. Some necessary and sufficient conditions thatm be a multiplier of are found and it is shown that there are no nonconstant inner multipliers of whenb is a nonconstant extreme point of the unit ball ofH . A new proof is given of the known fact that is invariant under multiplication byz whenb is not an extreme point of the unit ball ofH . Finally, we give a new proof of the known fact that an inner functionm is a multiplier of forb(z)=(1+z)/2 if and only ifm belongs to the range of .Some of the work in this paper originally appeared in the author's doctoral disseratation written at the University of California at Berkeley under the supervision of Donald Sarason.     

Coherent motion of a hole in a two-dimensional quantum antiferromagnet

The dispersion relation for the coherent propagation of a hole moving in a two-dimensional quantum antiferromagnet is discussed. The system is described by two model Hamiltonians, thet-J model and thet-t-J model, which have been used frequently to discuss strong electron-correlation effects present in high-T _c superconductors. The calculations are based on the introduction of a new wave function which is constructed by use of equations derived by Shraiman and Siggia. The different mechanisms for the coherent propagation, which are due to the spin fluctuation and the hopping terms of the Hamiltonian, are treated on the same footing. As a result of the inclusion of an effective hopping mechanism along spiral paths-first discussed by Trugman-the minimum of the band is somewhat changed compared to results recently obtained in the literature. For large values of the ratiot/J an inversion of the whole dispersion relation occurs. The overall shapes of the dispersion within both models are found to agree quite well, though for small values oft/J the bandwidth within thet-J model becomes significantly smaller than that of thet-t-J model.     

Two-dimensional visualization of the flame front in an internal combustion engine by laser-induced fluorescence of OH radicals

Two-dimensional laser-induced fluorescence (2D-LIF) imaging of OH radicals, excited at 308 nm, has been employed to visualize the flame front in an internal combustion engine burning air/propane mixtures. Light sheet thicknesses down to 70 m have been attained for excitation. Hydroxyl radicals were detected up to pressures of 7.5 bar at engine speeds of 500 rpm. An upper limit of 300 m for the flame front thickness was obtained from line intensity profiles.