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  • Physics  (7)
  • 1965-1969  (7)
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Year
  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 695-706 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Data already existing in the literature for the overall crystallization kinetics of a variety of polymers have been analyzed according to different possible nucleation mechanisms. The conclusions reached are similar to those previously deduced from an examination of ata for spherulite growth rates. It is demonstrated that, if allowed a reasonable choice for the equilibrium melting temperature, no unbiased selection of a unique nucleation process can be made. Moreover, a set of universal parameters exists for each of the nucleation and growth processes considered which allows the data for all polymers to be represented by a single straight line. The only quantities that are unique to a given polymer are the equilibriun melting temperature and the activation energy for transport.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 239-262 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The infrared absorption spectra of selected crystalline and noncrystalline bands were studied in bulk-crystallized specimens of linear polyethylene which encompassed the extremely wide density range of 0.92-0.99 g./cm.3. The analysis of the data obtained at room temperature yield degrees of crystallinity by infrared methods which are in very good accord with the values deduced from the density measurements. Studies of the infrared spectra as a function of temperature give fusion curves which are in agreement with those obtained by thermodynamic methods. However, in order to obtain these latter results cognizance must be taken of the large negative temperature coefficient of the specific extinction coefficients of the crystalline bands from room temperature to the melting point. The necessary data to account for this phenomena were obtained from studies of the spectra of the n-paraffin, C94H190, where molecular crystals are formed. Analysis of the two gauche bands, at 1352 and 1303 cm.-1, which are assigned to the noncrystalline regions demonstrate that for bulk-crystallized samples of lowest densities the intensity ratio at room temperature is identical to that expected from the pure melt at this temperature. The conclusion is thus reached that the noncrystalline regions in these cases and the pure melt are structurally very similar. For samples of higher density, where the crystallite size is comparable to the extended chain length, the intensity ratio of the two gauche bands is altered. This change could reflect a change in the sequential distribution of gauche bonds. This intensity ratio for crystals formed from dilute solution is very similar to that for the high-density bulk-crystallized material and indicates a similarity in structure of the noncrystalline regions in the two cases.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 181-196 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Studies of the crystallization kinetics of natural rubber networks held in simple extension are reported. In these experiments the length of the specimen was held constant, and the crystallization process was followed by the decay in stress that occurred. A wide range of extension ratios and crystallization temperatures was encompassed by these experiments. From an analysis of the shapes of the crystallization isotherms, it can be concluded that major changes take place in the nucleation and growth processes as the extension ratio is increased. This conclusion is in accord with reports in the literature of changes in the crystallite morphology with extension ratio. Analysis of the temperature coefficient of crystallization, by means of nucleation theory, indicates a substantial increase in apparent interfacial free energies with increased deformation. This latter observation is interpreted to indicate a departure from a correlated crystallization process to one where isolated crystallites are formed.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 165-180 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The spherulitic growth data that exist in the literature for a wide diversity of polymers have been analyzed according to various possible nucleation mechanisms. It is demonstrated that, if allowed a reasonable choice for the equilibrium melting temperature, no unbiased selection of a unique nucleation process can be made. Moreover, a set of universal parameters exists for each of the allowable nucleation processes which enables the data to be represented by a single straight line which encompasses all the polymers. The only quantities specific to a given polymer are the equilibrium melting temperature and the activation energy for transport. The magnitude of the latter quantity is shown to be dependent on the glass temperature of the polymer.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1883-1894 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Data existing in the literature for the spherulitic growth rate of molecular weight fractions of linear polyethylene, poly-(tetramethyl-p-silphenylene)siloxane, and trans-1,4-polyisoprene have been analyzed according to nucleation theory on taking into account the influence of chain length on the free energy of fusion. All three polymers display very similar behavior in that the interfacial free energy reaches an asymptotic value at high molecular weights, decreases as the molecular weight is lowered, and appears to also reach an asymptotic value at low molecular weights. Although the changes in the interfacial energy with molecular weight are quite distinct, the relative change is much less than has been previously reported when a molecular crystal analysis is used. The same general behavior observed points out the dominating influence of the chain-like character of the molecules in governing the growth rate.
    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 Part A-2: Polymer Physics 4 (1966), S. 385-400 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Replicas of fracture surfaces of fractions of linear polyethylene, which were crystallized at elevated temperatures for extended time periods, were examined by electron microscopy. Striated. lamella-type crystallites were observed for all molecular weights over the range 3.2 × 103-5.7 × 105. In agreement with Anderson's previous report, for molecular weights of 12,000 or less, the crystallite thicknesses were comparable to the extended chain length. As the molecular weight increased above this level, however, the crystallite sizes increased only slightly and hence at high molecular weights were very much smaller than the extended chain length. From the measured melting temperatures, crystallite interfacial free energies were calculated from the theory for the melting of finite size crystals comprised of chains of finite length. The crystallite interfacial free energy was found to increase with molecular weight. Based on these results, a crystallization process is outlined which allows for the formation of either extended chain crystallites, or crystallites whose size is much smaller than the extended chain length without any change in nucleation mechanism or arbitrary adjustment in growth mechanism with molecular weight.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 1029-1029 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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