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1.
E.‐A. McGonigle J. J. Liggat R. A. Pethrick S. D. Jenkins J. H. Daly D. Hayward 《Journal of Polymer Science.Polymer Physics》2004,42(15):2916-2929
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 相似文献
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Ryan B. Hayward 《Discrete and Computational Geometry》1987,2(1):327-343
Consider a drawing in the plane ofK
n
, the complete graph onn vertices. If all edges are restricted to be straight line segments, the drawing is called rectilinear. Consider a Hamiltonian cycle in a drawing ofK
n
. If no pair of the edges of the cycle cross, it is called a crossing-free Hamiltonian cycle (cfhc). Let (n) represent the maximum number of cfhc's of any drawing ofK
n
, and
(n) the maximum number of cfhc's of any rectilinear drawing ofK
n
. The problem of determining (n) and
(n), and determining which drawings have this many cfhc's, is known as the optimal cfhc problem. We present a brief survey of recent work on this problem, and then, employing a recursive counting argument based on computer enumeration, we establish a substantially improved lower bound for (n) and
(n). In particular, it is shown that
(n) is at leastk × 3.2684
n
. We conjecture that both (n) and
(n) are at mostc × 4.5
n
.This research, part of which was conducted at Queen's University, was supported by an N.S.E.R.C. postgraduate scholarship. 相似文献
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The percolation transition of geometric clusters in the three-dimensional, simple cubic, nearest neighbor Ising lattice gas model is investigated in the temperature and concentration region inside the coexistence curve. We consider quenching experiments, where the system starts from an initially completely random configuration (corresponding to equilibrium at infinite temperature), letting the system evolve at the considered temperature according to the Kawasaki spinexchange dynamics. Analyzing the distributionn
l(t) of clusters of sizel at timet, we find that after a time of the order of about 100 Monte Carlo steps per site a percolation transition occurs at a concentration distinctly lower than the percolation concentration of the initial random state. This dynamic percolation transition is analyzed with finite-size scaling methods. While at zero temperature, where the system settles down at a frozen-in cluster distribution and further phase separation stops, the critical exponents associated with this percolation transition are consistent with the universality class of random percolation, the critical behavior of the transient time-dependent percolation occurring at nonzero temperature possibly belongs to a different, new universality class. 相似文献
6.
Dr. Lun Jin Prof. Michael A. Hayward 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(5):2092-2095
Hole or electron doping of phases prepared by topochemical reactions (e.g. anion deintercalation or anion-exchange) is extremely challenging as these low-temperature conversion reactions are typically very sensitive to the electron counts of precursor phases. Herein we report the successful hole and electron doping of the transition-metal oxyhydride LaSr3NiRuO4H4 by first preparing precursors in the range LaxSr4−xNiRuO8 0.5<x<1.4 and then converting into the corresponding LaxSr4−xNiRuO4H4 phases. This is particularly noteworthy as the (Ni/Ru)H2 sheets in the LaxSr4−xNiRuO4H4 phases are structurally analogous to the CuO2 sheets in cuprate superconductors and hole doping (Ni1+/2+, Ru2+) or electron doping (Ni2+, Ru1+/2+) yields materials with partial occupancy in Ni/Ru –H 1s bands which are analogous to the partially occupied Cu –O 2p bands present in the CuO2 sheets of doped superconducting cuprates. 相似文献
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The problem of defining N(E), the density of states, for molecular systems is discussed. It is shown that a numeric evaluation of N(E) is often only approximate, even for continuous data, and is not well defined for quantized systems. The application of the concept of density of states is discussed, particularly with regard to the RRKM theory of unimolecular reactions. The sum of states, W(E), and density of states curves are evaluated for several harmonic and anharmonic model systems and the results discussed in order to illustrate the foregoing considerations. 相似文献
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Hayward JD 《Physical review D: Particles and fields》1995,52(2):1019-1025
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