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  • 11
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 143-161 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystallization of highly oriented homopolymer melts (or glasses) is modeled. It is shown that in such cases heat flow controls the kinetics and microstructure of the transforming material. The situation is modeled similarly to the growth of a thermal dendrite, with the inclusion of large and variable concentrations of defects in the fibrillar crystals. Expressions relating the undercooling, growth velocity, filament tip radius, and defect concentration to a normalized tensile force are derived. Example predictions for the case of isotactic polystyrene are given.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 12
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The microstructure of polypropylene, annealed after cold drawing to an oriented state, was examined using density measurements and small- and wide-angle x-ray scattering (SAXS and WAXS) techniques. SAXS patterns were obtained after annealing (in an oil bath), and during annealing (of samples annealed in a furnace placed directly in the x-ray beam). Data, for isothermal annealing, showed an increase in SAXS intensity, in crystal perfection, and in density over the observed time range, but no change in long spacing during the same period. Long spacing, SAXS intensity, and density were all strongly dependent upon annealing temperature, increasing at higher temperatures. Upon annealing the elastic modulus and yield strength dropped below the as-drawn values in an immeasurably short time, and did not appear to change thereafter during the time range examined. The decrease was more marked for higher-temperature annealing. The kinetics of the micro-structural changes are compared qualitatively to the predictions of nucleation and growth theory and of spinodal decomposition. The defects in the microstructure are considered as the “solute molecules” of the spinodal model. The experimental results do not agree neatly with either model. However, a nonequilibrium thermodynamic approach appears to be the more promising. It is suggested that the kinetics of mechanical property change may be due to different rates of migration for different defect species.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 13
    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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  • 14
    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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  • 15
    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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  • 16
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 781-792 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Melt-spun nylon 66 fibers were drawn and subsequently heat treated isothermally and quenched. The heat-treated fibers were then examined by wide-and small-angle x-ray scattering (WAXS and SAXS), by differential scanning calorimetry (DSC), and by static mechanical testing. These measurements allow one to follow microstructural changes taking place during the course of the heat treatment. WAXS results show that as the treatment progresses, the crystallites become both more perfect and more disoriented with respect to the fiber axis. SAXS results show crystallite thickening. DSC results show that the melting point increases, goes through a maximum, and then decreases as the heat treatment progresses. The tensile modulus decreases with time to an asymptotic level. The changes in crystallite perfection and thickness occur more rapidly than do the changes in crystallite orientation, modulus, and melting point. A model is proposed whereby the two time frames are related to intracrystalline and intercrystalline processes, respectively.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 17
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Linear polyethylene was crystallized isothermally from the melt. Specimens were removed at different crystallization times and quenched to room temperature. The density, static mechanical properties, and small-angle x-ray scattering (SAXS) behavior of these specimens were measured at room temperature. The density and Young's modulus increased with crystallization time, whereas the upper yield point decreased with crystallization time. SAXS data showed that a zero-angle peak gradually disappeared as crystallization time increased. Concurrently, the breadth of the SAXS peaks, the Bragg angle, and the integrated intensity decreased. Changes in the ratio of second- and first-order peak intensities were also noted. On the basis of the SAXS and density data, it was concluded that a competition exists between the thickening of existing crystals and the creation of new crystallites between the older ones. At relatively low crystallization times, numerous new crystals can form during quenching to room temperature, whereas quenching after prolonged crystallization primarily results in the additional thickening of existing crystals. No change in the density of the amorphous material is found. A model is given whereby the upper yield stress is coupled to these morphological changes through a stress concentration effect caused by a decreased population of chains connecting adjacent crystallites. The tie-chain population change occurs by their elimination as crystallites disappear.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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  • 18
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 819-821 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 19
    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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  • 20
    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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