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  • 1
    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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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1153-1165 
    ISSN: 0887-6266
    Keywords: even-odd nylons ; lamellar crystals ; structure ; hydrogen-bonding schemes ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Nylon 6 9 has been shown to have structures with interchain hydrogen bonds in both two and in three directions. Chain-folded lamellar crystals were studied using transmission electron microscopy and sedimented crystal mats and uniaxially oriented fibers studied by X-ray diffraction. The principal room-temperature structure shows the two characteristic (interchain) diffraction signals at spacings of 0.43 and 0.38 nm, typical of α-phase nylons; however, nylon 6 9 is unable to form the α-phase hydrogen-bonded sheets without serious distortion of the all-trans polymeric backbone. Our structure has c and c* noncoincident and two directions of hydrogen bonding. Optimum hydrogen bonding can only occur if consecutive pairs of amide units alternate between two crystallographic planes. The salient features of our model offer a possible universal solution for the crystalline state of all odd-even nylons. The nylon 6 9 room-temperature structure has a C-centered monoclinic unit cell (β = 108°) with the hydrogen bonds along the C-face diagonals; this structure bears a similarity to that recently proposed for nylons 6 5 and X3. On heating nylon 6 9 lamellar crystals and fibers, the two characteristic diffraction signals converge and meet at 0.42 nm at the Brill temperature, TB · TB for nylon 6 9 lamellar crystals is slightly below the melting point (Tm), whereas TB for nylon 6 9 fibers is ≅ 100°C below Tm. Above TB, nylon 6 9 has a hexagonal unit cell; the alkane segments exist in a mobile phase and equivalent hydrogen bonds populate the three principal (hexagonal) directions. A structure with perturbed hexagonal symmetry, which bears a resemblance to the reported γ-phase for nylons, can be obtained by quenching from the crystalline growth phase (above TB) to room temperature. We propose that this structure is a “quenched-in” perturbed form of the nylon 6 9 high-temperature hexagonal phase and has interchain hydrogen bonds in all three principal crystallographic directions. In this respect it differs importantly from the γ-phase models. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1153-1165, 1998
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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