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  • 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.
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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.
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  • 3
    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.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 869-882 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystallization kinetics of a high molecular weight fraction of linear polyethylene was studied in dilute solutions of p-xylene, n-hexadecane, and decalin by dilatometric methods. For all solvents and temperatures, the experimental isotherms could be quantitatively described by the Avrami formulation for the complete transformation. This result is unique in the realm of polymer crystallization, since marked deviations from this theory are usually observed in more concentrated systems. The Avrami exponent is found to be n = 4 in all cases. The temperature coefficients of the rate constants are indicative of a nucleation controlled process. The data fit either a two-dimensional or three-dimensional nucleation mode, and a discrimination can not be made between these two cases. The interfacial free energies are found to be independent of the solvent medium. It is also shown that, irrespective of the type of nucleation control governing the kinetics, the same type governs the crystallite thickness of the lamella-like crystals that are formed.
    Additional Material: 8 Ill.
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  • 5
    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
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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.
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  • 7
    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.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 225-242 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Calorimetric and dilatometric studies have been made of the fusion process of linear polyethylene crystals precipitated by high speed stirring from solution. It is shown that long-time annealing at elevated temperatures alleviates the superheating observed when rapid heating rates are employed. By the annealing procedures that have been adopted, a small but demonstrable fraction of high melting material can be produced whose melting temperature depends on the crystallization temperature. For crystallization at 105°C, followed by annealing at 142°C, a melting temperature of 146.0 ± 0.5°C is observed. The dissolution temperature in xylene, determined for the same sample, is consistent with the high melting temperature observed for the pure polymer. It is recognized that a state of high axial orientation need not necessarily be identified with extended chain crystals. Consequently, the increased melting temperature can result from either an increase in the crystallite size or a reduced interfacial free energy relative to crystallites produced by the more conventional mode of crystallization.
    Additional Material: 11 Ill.
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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. 957-967 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melting temperatures of homopolymers of poly(ethylene sebacate) possessing a most probable molecular weight distribution and ordered copolymers of ethylene sebacate/propylene adipate were studied by slow heating processes and by the analysis of the dependence of the melting temperature on the crystallization temperature utilizing rapid heating rates. For the ordered copolyesters, where the composition of the crystallizing co-units ranged from 0.8 to 0.2 mole fraction the latter method gave results which were similar to those that have been obtained for the other polymer systems that have been studied. Extrapolated equilibrium melting temperatures could be obtained in a straightforward manner and were found to be independent of the copolymer composition in accord with theoretical expectations. On the other hand, a unique set of results were obtained for the homopolymers. A plot of the relationship between the melting temperature and the crystallization temperature for all the molecular weights studied gave a slope close to unity. This made it operationally impossible to extrapolate to the equilibrium melting temperature for this system.
    Additional Material: 6 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 2079-2087 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The unit-cell dimensions and density, at room temperature, of bulk- and solution-crystallized linear polyethylene have been determined. The macroscopic measured densities for the bulk-crystallized samples ranged from 0.917 to 0.993 g/cc, and the lattice parameters were found to be independent of the sample density. In contrast, for solution-formed crystals, despite the limited range in macroscopic densities that can be attained, there is a systematic variation in the a and b dimensions with the measured density and the crystallite thickness. The implication of these results for the calculation of the degree of crystallinity and the interpretation of certain infrared bands are discussed.
    Additional Material: 2 Ill.
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