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  • 1
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2311-2325 
    ISSN: 0887-6266
    Keywords: poly(ethylene oxide) ; crystallization ; AFM ; spherulites ; crystal growth ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The atomic force microscope (AFM) has been used to investigate morphological development during the crystallization of poly(ethylene oxide) (PEO) from the melt. PEOs with molecular weights of 1 × 105 and 7 × 106 were used. Height and amplitude images were recorded, using the tapping mode. For both polymers, the mode of spherulite development varied with the velocity of the growth front. For slow growth velocities, the growth of the crystallites was linear, with growth initially occurring by single lamellae, later developing into growth arms by screw dislocation spawning of crystallites. At intermediate growth velocities, stacks of lamellae develop rapidly. The splaying apart of adjacent crystals and growth arms is abundant. The operation of growth spirals was observed directly in this growth velocity range. The crystals formed by the giant screw dislocations diverge immediately from the original growth direction, providing a source of interlamellar splaying. At low and intermediate velocities, the front propagates by the advance of primary growth arms, with the regions between the arms filled in by arms growing behind the primary front. At the highest velocity observed here, the formation of lamellar bundles and immediate splaying results in recognizable spherulites developing at the earliest stages of crystallization. The change from linear growth to splaying and nonlinear growth are qualitatively explained in terms of driving force, elastic resistance and the presence of compositional and/or elastic fields in the melt. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2311-2325, 1998
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2291-2311 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Small-angle and wide-angle x-ray scattering measurements, using a position-sensitive detector, were made during melt-crystallization of linear polyethylenes and PEO-PS-PEO triblock copolymer. The scattering measurements indicated that the triblock copolymer grew by the enlargement of regions in which lamellae are regularly stacked. During primary crystallization at higher temperatures similar behavior is observed in two linear polyethylenes. At lower temperatures, changes in the shape of small-angle scattering curves during the primary stage of crystallization indicate that amorphous gaps within the lamellar stacking become filled in. During secondary crystallization at higher temperatures new crystallites appear to grow between those formed in the primary stage. Concurrent decrease of the overall scattered intensity leads to the conclusion that secondary crystallization has two components: crystallization of new lamellae behind the spherulite growth front and the thickening of existing lamellae.
    Additional Material: 18 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 2151-2183 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyethylene was spun into a heated chamber, with the spin-line temperature controlled in the range of 90-120°C. Within narrow limits, the stretch rate of the fiber was also controlled. Spin-line and crystallization onset conditions were characterized. Characteristics of fibers as-spun were measured via wide-angle x-ray scattering (WAXS), density, scanning electron microscopy, and differential scanning calorimetry. Spin-line data indicate that elongational flow enhances crystallization rate and that time under spin-line conditions is an important parameter. Analysis of WAXS data shows a typical “b-axis radial” orientation, the details of which change with spin-line parameters. This orientation is consistent with growth of lamellar crystals on extended-chain fibrils (shishkebab model). Other physical data are also consistent with this microstructure. Microcamera x-ray patterns show a similarity of microstructure generation in spinning and drawing.
    Additional Material: 25 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 239-245 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The course of melting of melt-crystallized polyethylene fractions and of a poly(ethylene oxide)-polystyrene-poly(ethylene oxide) triblock copolymer has been followed by small-angle x-ray scattering (SAXS). Changes in the intensity and shape of the SAXS curves indicated that both surface melting and melting over the full crystallite thickness (full-strand melting) take place. Full strand melting is the final, irreversible process. Comparison with an analytical model indicates that in the earlier stages of the irreversible, full-strand process the crystallites melt out randomly throughout the bulk. Later stages may occur by the simultaneous melting of a larger stack of crystallites.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polypropylene films were produced by solidification during high-rate (〉104s-1) melt drawing. Small-angle x-ray scattering (SAXS) data were collected during interruptions of the annealing of these films. Fibrillar crystallization took place during the melt-drawing process. The fibrils exhibit an axial density modulation as determined by SAXS and transmission electron microscopy. Annealing increases the amplitude of the density modulation. Detailed examination of the SAXS curves shows that the modulation is approximately sinusoidal and that the amplification of the density modulation occurs with no change in periodicity. Comparison of SAXS curves taken at different times during annealing suggests a process similar to spinodal decomposition. It is proposed that the microstructural change within a fibril takes place by the axial motion and clustering of chain defects.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1927-1953 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Melt-spun poly(ethylene terephthalate) fibers were isothermally heat-treated at constant length. Microstructural changes occurring during the heat-treatment were monitored using specific gravity, wide-angle x-ray scattering (WAXS), small-angle x-ray scattering (SAXS), optical birefringence, and static mechanical testing. Major changes in the density of the most highly oriented fiber examined occurred in times below 100 ms. For less oriented fibers, the time scale for significant density change increases to the 1-10 s range. The course of birefringence increase approximates that of the density. WAXS measurements show that crystallinity develops at essentially constant crystal perfection, but that the orientation of the crystallites first decreases and then increases with time. SAXS results show development of a four-point pattern, the azimuthal angle of the lobes decreasing with initial orientation, with temperature, and with time. A streak transverse to the fiber axis develops more rapidly than do the lobes. A two-stage transformation process is envisaged, the first stage being the formation of defective crystal fibrils and the second being internal rearrangement of the fibrils to form more perfect crystallites, separated by more amorphous zones. Changes in the crystallite orientation are related to constraints of the noncrystalline material on the crystallites.
    Additional Material: 24 Ill.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thin films of isotactic polypropylene were drawn from the melt at a very high rate of extension. Transmission electron micrographs of this material reveal fibrous crystals lying along the draw direction. The chain axis and fiber axis are identical. Dark field micrographs show a dark/light modulation along the fiber axis. Annealing at temperatures below 110°C produces no qualitative change in the electron microscope observations. Annealing between 110 and 150°C produces gradual dominance of lamellar crystals, oriented normal to the draw direction. Small-angle x-ray scattering (SAXS) data exhibit a strong streaking normal to the fiber axis, in broad agreement with the observed fibrosity. A Bragg peak along the draw directions shows that the modulation observed microscopically is a density modulation. The absence of second-order maxima and the dependence of the SAXS peak on treatment temperature strongly suggest that the axial modulation is a spinodal decomposition of the material into crystalline and amorphous regions.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 821-827 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A specimen of linear polyethylene was subjected to isothermal secondary crystallization at a series of temperatures below the primary isothermal crystallization temperature, the melting and primary crystallization stages being held constant throughout the investigation. Dilatometric measurements exhibit an S-character at low values of undercooling Tp - Ts, where Tp and Ts are, respectively, the primary and secondary crystallization temperatures, whereas at larger undercooling, an initial very rapid crystallization is followed by a very slow stage. When corrected for thermal contraction of the polymer, the net degree of secondary transformation is seen to peak at a temperature about 5°C below Tp. The S-character of the isotherms and the peaked temperature variation of degree of transformation lead to the conclusion that a large portion of the secondary crystallization consists of the nucleation and growth of the new crystallites. Johnson-Mehl-Avrami analysis leads to a model of heterogeneous nucleation within the remaining amorphous zones, followed by one-dimensional, diffusion-controlled growth.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 243-276 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An x-ray diffraction method for the simultaneous determination of crystallinity (including intracrystalline defects), effective Debye-Waller factors, and atomic positions has been developed and applied to semicrystalline polyethylene. It was found that this material unambiguously constitutes a two-phase system. Measurements of intracrystalline lattice disorder in the chain direction and perpendicular to the chain direction show these to be in the ratio 1:2.5. Lattice disorder was principally of the first kind. Paracrystalline disorder in the [110] direction was less than 2.4% at all experimental conditions. Results include measurements of degree of crystallinity, particle size, space group, and unit cell parameters and variation of these quantities with crystallization temperature, ambient temperature, and time.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 511-533 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The temperature dependence of x-ray small-angle scattering from fractionated linear polyethylene crystallized from the melt was determined experimentally over a range of temperatures from room temperature to the melting point. It was found in general that only the most intense of the several small-angle peaks exhibited a thermally dependent behavior. Below the crystallization temperature this peak increased in intensity with temperature, at constant peak position. Recrystallization was manifest in a discontinuous shift of the peak. During isothermal crystallization, the peak intensity first increased, then decreased, with time. It is concluded from supplementary electron microscopy and from the behavior of the peak that its position reflects the period of stacking of lamellae and that its intensity is controlled primarily by the thickness of the layer separating lamellae. The reversible peak intensity effect is attributed to an entropydriven growth of the interlamellar layer at the expense of the crystalline lamellae. The intensity effects observed during crystallization are associated with the primary and secondary phases of crystallization. Lamellar surface free energies were computed from melting point observations and were found to increase with molecular weight.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
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