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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 261 (1983), S. 721-735 
    ISSN: 1435-1536
    Keywords: Polyethylene ; shish-kebabs ; overgrowth-spacing ; morphology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The platelet component of shish-kebabs crystallizes after the core, during cooling or storage below the formation temperature of the core. Three basic platelet morphologies were previously identified which were mutually interconvertible, a process we have termed “hairdressing”. In this paper we show that these three categories are special cases of a continuous range of overgrowth spacings. Crystallization at high temperatures gives widely spaced overgrowths and, as the crystallization temperature is reduced, so the overgrowth spacing decreases gradually. In the extreme case (only obtainable by quenching) the overgrowths become so close as to overlap and appear continuous. We also report a variety of further effects which were caused by exposing the shish-kebabs, while in solvent, to temperatures above their initial formation temperature. A new theoretical approach is described which considers the depletion of material available to form new overgrowths during crystallization. Two versions of this theory are presented (one a computer simulation and one analytic); interpreting our results on the basis of this theory we show that shish-kebabs crystallize at high temperatures even when quenched (90°C and above except in a few exceptional circumstances) and we are able to explain all the features of shish-kebab crystallization that we have observed.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 262 (1984), S. 22-45 
    ISSN: 1435-1536
    Keywords: Isotactic polystyrene ; gels ; structure ; morphology ; conformation ; X-ray diffraction ; electron microscopy ; DSC ; FTIR ; crystallization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The thermoreversible gelation phenomena exhibited by isotactic polystyrene (i-PS) was examined in depth, utilising a variety of experimental techniques. The primary aims were identification, relationship, description and visualisation of the morphologies corresponding to the two types of crystallization as diagnosed by the different crystal structures revealed by X-ray diffraction. While centred on electron microscopy the investigation used X-ray and electron diffraction, differential scanning calorimetry and Fourier transform infra-red spectroscopy in combination. A satisfactory correlation between all these techniques was established, including the important reassurance that the characteristics of the gel state are preserved on drying, a feature necessitated by most structure methods. Thei-PS gel system as a whole displays particularly clearly the distinction between gel forming and chain folded lamellar crystallization and the coexistence, morphological relationship and competition between the two crystallizable species. In addition, and most significantly, the gel crystals possess a crystal structure involving extended chains, close to an all-trans conformation, which are quite different to those obtained from conventionally crystallizedi-PS (31 helix). This former extended conformation in itself has become the starting point for new geometric and stereochemical considerations and in addition offers a convenient diffraction based fingerprint to delineate between the two modes of crystallization. Thus the conversion of the gel crystal structure to the conventional 31 helix structure on heating could be monitored. Further, that in the processes of heat annealing, remnants of these gel fibres initiate the development and dictate the orientation of a shish-kebab type platelet growth with the 31 helix crystal structure. This conversion process has been followed by electron microscopy and supplemented infra-red spectroscopy, low angle X-ray diffraction and differential scanning calorimetry. The different roles of fibres and platelets on stretching have been identified. Conditions for the existence of the gel crystals in their different variants are specified with relevance to ongoing arguments and discussions in the subject. Further, it was established that passing through the gel phase significantly enhanced the crystallization in the conventional crystal form making the normally slowly crystallizingi-PS into a fast crystallizable polyolefin.
    Type of Medium: Electronic Resource
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