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The development of the poly(3‐hydroxybutyrate) (PHB) morphology in the presence of already existent poly(vinylidene fluoride) (PVDF) spherulites was studied by two‐stage solidification with two separate crystallization temperatures. PVDF formed irregular dendrites at lower temperatures and regular, banded spherulites at elevated temperatures. The transition temperature of the spherulitic morphology from dendrites to regular, banded spherulites increased with increasing PVDF content. A remarkable amount of PHB was included in the PVDF dendrites, whereas PHB was rejected into the remaining melt from the banded spherulites. When PVDF crystallized as banded spherulites, PHB could consequently crystallize only around them, if at all. In contrast, PHB crystallized with a common growth front, starting from a defined site in the interfibrillar regions of volume‐filling PVDF dendrites. It formed by itself dendritic spherulites that included a large number of PVDF spherulites. For blends with a PHB content of more than 80 wt %, for which the PVDF dendrites were not volume‐filling, PHB first formed regular spherulites. Their growth started from outside the PVDF dendrites but could later interpenetrate them, and this made their own morphology dendritic. These PHB spherulites melted stepwise because the lamellae inside the PVDF dendrites melted at a lower temperature than those from outside. This reflected the regularity of the two fractions of the lamellae because that of those inside the dendrites of PVDF was controlled by the intraspherulitic order of PVDF, whereas that from outside was only controlled by the temperature and the melt composition. The described morphologies developed without mutual nucleating efficiency of the components. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 873–882, 2003 相似文献
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Hans-Rudolf Buser Michael Oehme Walter Vetter Bernd Luckas 《Fresenius' Journal of Analytical Chemistry》1993,347(12):502-512
Summary Conventional electron ionization (EI) mass spectrometry (MS) and MS/MS techniques were applied to the analysis of two abundant octa and nonachlorobornanes isolated from seals of the Baltic sea and originating from technical toxaphene. The exact sterical structures of the two compounds were previously determined using nuclear magnetic resonance (NMR) spectroscopy by two independent research groups. The MS and MS/MS data generated in this study allowed partial structure elucidation of these polychlorobornanes, in particular revealing the distribution of the Cl substituents between the six-membered carbon ring, the bridge and the bridgehead in the parent bornane structure. Fragmentation of the six-membered carbon ring and the bridge by retro-Diels-Alder (RDA) and related mechanisms was discovered by studying specific parent/daughter ion transitions. The detailed fragmentation pathways formulated may be applicable to the structure elucidation of other toxaphene congeners and the monitoring of strategic transitions is highly selective for the detection of these compounds in technical toxaphene and in environmental samples. 相似文献
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We propose a new approach towards proving that the fixed point property for ordered sets is preserved by products. This approach uses a characterization of fixed points in products via isotone relations. First explorations of classes of isotone relations are presented. These first explorations give us hope that this approach could lead to advances on the Product Problem. 相似文献
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The change of the superstructure of different polyethylenes during uniaxial deformation is investigated. The method used is small-angle scattering with synchrotron radiation. For branched polyethylene (Lupolen 1840D) the whole deformation range is analyzed. Beginning with superstructure of the lamellar cluster type, the superstructure partly disappears on a time scale of a few minutes and the fibrillar structure is built up. The degree of destruction and rebuilding depends on the drawing temperature. For very high molecular weight polyethylene (GUR) a reversible change of the superstructure at higher deformation ratios and at different temperatures is observed. The superstructure of (ethylene—hexene) copolymers (TIPELIN) at high draw ratios depends on the drawing temperature and is almost independent of the side group content. Interfibrillar microcracks parallel to the draw direction are produced in samples with a low side group content for draw ratios λ ≥ 1.5. 相似文献
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The reactions of bis(trimethylstannyl)ethyne, Me3Sn–C?C–SnMe3 ( 4 ), with trimethylsilyl‐ or dimethylsilyl‐dialkylboryl‐substituted alkenes 1 – 3 afford organometallic‐substituted allenes 5 , 6 and 8 , 9 in high yield. In the case of (E)‐2‐trimethylsilyl‐3‐diethylboryl‐2‐pentene ( 1) , a butadiene derivative 7 could be detected as an intermediate prior to rearrangement into the allene. All reactions were monitored by 29Si and 119Sn NMR, and the products were characterized by an extensive NMR data set (1H, 11B, 13C, 29Si, 119Sn NMR). Copyright © 2003 John Wiley & Sons, Ltd. 相似文献