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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. 3065-3077 
    ISSN: 0887-6266
    Keywords: polyurethanes ; AFM ; atomic force microscopy ; phase separation ; crosslinking ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of polyurea urethanes was isothermally synthesized from toluene diisocyanate (TDI), water, and trifunctional poly(propylene oxide) in the temperature range of 50-150°C. Morphologies of the samples vary significantly as a function of reaction temperature. In this system, phase separation competes with polymerization and crosslinking. Both transmission electron microscopy and atomic force microscopy have shown a network type of structure for the 50°C samples, while the 150°C samples appear to be homogeneous. Infrared analysis shows that samples prepared at 150°C possess a morphology that is less strongly hydrogen bonded and has a broader distribution of hydrogen-bonded states compared to those prepared at lower temperatures. From this combination of techniques, it can be inferred that phase separation occurs faster than crosslinking at low temperatures; consequently, a phase-separated morphology forms. In contrast, crosslinking occurs faster than phase separation at higher reaction temperatures. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3065-3077, 1998
    Additional Material: 10 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1097-1113 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: After flowing in a dilatometer bulb for a small fraction of the duration of the transformation, a relaxed melt of poly(ethylene oxide) (M̄n = (5.9 ± 0.1) × 103) showed marked increases in isothermal crystallization rate. The extent of increase was greater when flow was imposed at modestly later stages rather than at the earliest stage of a crystallization. Kinetic parameters for the flow-induced crystallizations were obtained via modification of the conventional mathematical treatment of the kinetics of phase change, thereby allowing the analytical resolution of the overall process into flowinduced and quiescent components. Determination of the flow-induced crystallization parameters required independent determination of the kinetic parameters for quiescent crystallizations at that temperature. The Avrami exponents nf which characterized the flow-induced portions of the crystallizations were larger for those instances in which flow was imposed at the more advanced stages of the crystallizations, thus indicating a transition in crystallization mechanism. It is suggested that prior crystallinity present at the time of flow contributed to the crystallization by serving as a source of nucleation sites. However, in light of the experimental procedure employed, values of nf approximating 4 that were obtained are not susceptible to mechanistic interpretations now extant.
    Additional Material: 9 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 2679-2681 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Tab.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 633-634 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 497-513 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solutions of cellulose (degree of polymerization: 296 ± 16) in tris(ethylenediamine)cadmium(II)hydroxide-ethylenediamine-water (cadoxen), 1.015% (weight per volume) were diluted 1:1.5 with water. The ensuing isothermal precipitations were followed dilatometrically at temperatures ranging from 27.50 to 48.45°C. The precipitation data were characterized by a positive temperature coefficient. They generally conformed to a one-dimensional nucleation rate law; the Avrami exponents were close to unity. Alternatively, they fit a first-order reaction rate expression with respect to cellulose concentration. The low crystallinity of the precipitated cellulose leads to the interpretation of the kinetics in terms of the dissociation of a cellulose-cadoxen complex, rather than phase separation, as the rate-determining step. The nucleation rate law suggests a one-dimensional nonrandom cooperative chemical process, while the first-order rate law suggests a random process.
    Additional Material: 9 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 2651-2661 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A quasi-equilibrium model of a step-growth copolymer that crystallizes and interchanges structural units simultaneously is presented. Equilibrium values of counit-sequence-length distribution in the amorphous phase and degree of crystallinity are calculated in a system for which crystallite thickness is determined by nucleation. When applied to calculations, the model predicts that the counits of the amorphous phase will tend to be ordered in blocks. The crystalline content of the whole polymer and the extent of ordering counits along the chain decreases with increasing temperature. The model predicts temperature ranges for some whole copolymers in which one of two similarly stable, disparate combinations of crystallinity and sequence-length distribution may prevail.
    Additional Material: 9 Ill.
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