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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
2.
R. K. Jenkins 《Journal of Polymer Science.Polymer Physics》1966,4(1):41-52
The dynamic moduli, E′ dyn, and loss tangents, tan δ, of polydimethylsiloxane and polydimethyldiphenylsiloxane polymers have been investigated by an in situ technique during γ-irradiation. These viscoelastic properties were calculated and plotted as a function of irradiation exposure time by measuring the free end displacements and resonance frequencies of polymeric cantilever reeds. The reeds were swept through a small frequency range from about 20 to 100 cycles/sec. The moles of effectively elastic chains per unit volume (v) of the two unfilled polysiloxahes were calculated from in situ modulus data and compared to values obtained utilizing the swelling technique. The approximate molecular weights between entanglements, Me, of these unfilled polymers were determined by extrapolation of moduli data to zero radiation exposure. The addition of a large silica filler, SiO2, into the polymers did not alter the crosslinking rates, and the filler did not enter into polymer—filler bonding. 相似文献
3.
The analytical gas chromatography of a range of fluorinated and unfluorinated beta-diketonates of aluminium, chromium and iron has been studied m detail and conditions have been established for their complete separation; the complexes of trifluoroacetylpivaloylmethane show the best characteristics for this purpose. A range of liquid phases and column conditions have been considered and Apiezon substrates have been shown to give optimal resolution. The technique has been extended to a preparative scale with up to 0.1-g chelate samples, and the efficiency of the process demonstrated by the removal of 2% proportions of two metal complexes from a sample of the third. Implications of the technique for the purification of metals are discussed. 相似文献
4.
A helium glow discharge is employed as a gas Chromatographie detector which is selective for silicon. Operated with spectral background compensation at 251.6 nm or 288.2 nm, the detector shows a lower limit of detection of 5 ng of silicon per injection. The detector is applied to the rapid screening of trimethylsilylated fractions of shale-derived liquids being prepared for biossay. 相似文献
5.
1- and 2-Methoxy-heptafluorophenazine and 1- and 2-bromoheptafluorophenazine have been obtained by anodic oxidation of appropriately substituted 2-amino-octafluorodiphenylamines, the synthesis of which is described. By reaction of octofluorophenazine with suitable nucleophiles, 2-methoxy-, 2-hydroxy and 2-N,N1-dimethylamino-heptafluorophenazine were formed; some of their reactions are described. 相似文献
6.
Paul Richard Jenkins Rudolf Gut Hansjürg Wetter Albert Eschenmoser 《Helvetica chimica acta》1979,62(6):1922-1931
Note on a preparation of β, γ-unsaturated carboxylic acid derivatives using the amide acetal Claisen rearrangement 3-(Trimethylsilyl)allyl alcohols smoothly undergo the amide acetal Claisen rearrangement furnishing allyl silanes. Subsequent protolysis with HF at ?20° provides a convenient, stereoselective method for the preparation of β, γ-unsaturated carboxylic acid derivatives. Three model examples illustrate the procedure. 相似文献
7.
The structures of non-crystalline vapour-quenched GdAg alloy films containing between 0 and 16 at% silver have been examined by X-ray diffraction techniques. Radial distribution functions calculated from the experimental data, are in general appearance similar to those generated from a binary hard-sphere model derived from random layers of unequal-sized spheres for all compositions except those near 13 at% Ag. A hard-sphere model proposed by Sadoc et al. [13] generated from a seed cluster gives better agreement in the region of 13 at% Ag. Magnetic measurements show a Curie-Weiss behaviour for the magnetic susceptibility with peff = 7.6 ± 1.9 μB for these alloys. 相似文献
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10.
Seweryniak D Woods PJ Carpenter MP Davinson T Janssens RV Jenkins DG Lauritsen T Lister CJ Ruiz C Shergur J Sinha S Woehr A 《Physical review letters》2005,94(3):032501
The level structure of (22)Mg has been studied with high-sensitivity gamma-ray spectroscopy techniques. A complete level scheme is derived incorporating all subthreshold states and all levels in the energy region relevant for novae burning. The excitation energy of the most important astrophysical resonance is measured with improved accuracy and found to differ from previous values. Combining the present result with a recent resonance energy measurement of this state leads to a derived (22)Mg mass excess of -400.5(13) keV. 相似文献