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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 2 (1964), S. 43-49 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We report a simple method for measuring partial specific volumes, of polymers in dilute solutions with an accuracy of 3 parts per thousand. This method has been applied to 7 polypeptides in 4 organic solvents. The residue volumes deduced from these data are compared to those calculated by a differential method. The discrepancy is generally of the order of 1.5%.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 6 (1968), S. 299-306 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The predominant role of van der Waal interactions in determining the helical conformations of a simple synthetic linear polymer, as well as helical polypeptides, was pointed out in systematic studies by Liquori et al.1,2. In the case of homopolypeptides the conformational analysis carried out on the basis of a simple semiempirical function describing the van der Waal pairwise interactions between the non directly bonded atoms lead to the conclusion that only five helices are allowed (Rα, β, γ, δ, Lα).2,3In view of the close similarities with poly-L-alanine, we have investigated by x-ray and conformational analysis the molecular conformation of poly(S-lactic acid) which has recently been described by Kleine and Kleine4 and Schuls and Schwaab5 and studied in solution by Goodman and D'Alagni.6 In fact, this polymer may be related to the polypeptide by the interchange of a peptide bond with ester bond along the main chain. This operation is expected to involve only a relatively small change in the steric interaction within the possible helical conformation, but obviously rules out any possibility of hydrogen bonding.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 2 (1979), S. 81-86 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The characteristic fetures of isobaric volume and enthalpy recovery of glasses are briefly recalled and analysed in terms of a multiparameter model involving a distribution of retardation times, τi. The latter are assumed to depend both on temperature and on the instantaneous state (structure) of the glass, whereas the shape of the retardation spectrum is invariant and merely shifts, as τi, along the logarithmic time scale. Qualitative comparison of the theoretical predictions with various types of experiment reveals an excellent agreement. Some effects of structural recovery on the mechanical, or electrical properties of polymer glasses are also recalled and discussed in terms of the theoretical model The text which follows is merely an extended abstract of the work published elsewhere (see Refs 5 & 10)..
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 2467-2532 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A multiordering parameter model for glass-transition phenomena has been developed on the basis of nonequilibrium thermodynamics. In this treatment the state of the glass is determined by the values of N ordering parameters in addition to T and P; the departure from equilibrium is partitioned among the various ordering parameters, each of which is associated with a unique retardation time. These times are assumed to depend on T, P, and on the instantaneous state of the system characterized by its overall departure from equilibrium, giving rise to the well-known nonlinear effects observed in volume and enthalpy recovery. The contribution of each ordering parameter to the departure and the associated retardation times define the fundamental distribution function (the structural retardation spectrum) of the system or, equivalently, its fundamental material response function. These, together with a few experimentally measurable material constants, completely define the recovery behavior of the system when subjected to any thermal treatment. The behavior of the model is explored for various classes of thermal histories of increasing complexity, in order to simulate real experimental situations. The relevant calculations are based on a discrete retardation spectrum, extending over four time decades, and on reasonable values of the relevant material constants in order to imitate the behavior of polymer glasses. The model clearly separates the contribution of the retardation spectrum from the temperature-structure dependence of the retardation times which controls its shifts along the experimental time scale. This is achieved by using the natural time scale of the system which eliminates all the nonlinear effects, thus reducing the response function to the Boltzmann superposition equation, similar to that encountered in the linear viscoelasticity. As a consequence, the system obeys a rate (time) -temperature reduction rule which provides for generalization within each class of thermal treatment. Thus the model establishes a rational basis for comparing theory with experiment, and also various kinds of experiments between themselves. The analysis further predicts interesting features, some of which have often been overlooked. Among these are the impossibility of extraction of the spectrum (or response function) from experiments involving cooling from high temperatures at finite rate; and the appearance of two peaks in the expansion coefficient, or heat capacity, during the heating state of three-step thermal cycles starting at high temperatures. Finally, the theory also provides a rationale for interpreting the time dependence of mechanical or other structure-sensitive properties of glasses as well as for predicting their long-range behavior.
    Additional Material: 26 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 1138-1141 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Cylindrical specimens of poly(methyl methacrylate) (PMMA) were quenched from above the glass transition and subsequently tested in torsion. Torque and normal-force relaxation responses were recorded simultaneously. The experiments were performed at 40, 60, and 80°C, at increasing aging times and at deformations ranging from γ = 0.0027 to γ = 0.074. It was found at 40 and 60°C, that, contrary to the classical picture of aging, the small-deformation torque-relaxation curves could not be superposed by any combination of vertical and horizontal shifts. On the other hand, at 80°C, and in the nonlinear deformation range even at lower temperatures, the relaxation curves are superimposable simply by horizontal shifts, but as γ increases they involve decreasing values of the double-logarithmic shift rate. At the same deformation level, however, the shift rate for the normal force is significantly higher than is that for the torque over most of the γ range investigated.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 26 (1988), S. 501-513 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The KAHR model of structural relaxation has been extended to include the effects of pressure upon the retardation times of glass-forming materials. The previously used methodology is applied with a continuous distribution of retardation times of the fractional exponential form. Several forms of the pressure dependence are examined. The combined temperature and pressure changes on structural recovery of glasses are addressed in this paper.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 1087-1103 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The response of glass-forming systems to isobaric three-step thermal cycles involving cooling, isothermal annealing, and subsequent reheating has been investigated comprehensively using numerous combinations of the experimental and material parameters. The latter include the retardation spectrum or response function and the parameter x which determines the relative contributions of temperature and structure to the retardation times. The results show that, on heating, multiparameter systems can display three kinds of peak in the expansion coefficient α or the heat capacity Cp originating from the interactions of the elementary retardation processes with the thermal history of the glass. The conditions under which these peaks occur, their shifts with x, and the experimental variables have been investigated in detail. In particular, it has been shown that for a thoroughly stabilized glass reheated rapidly, the temperature at which the main peak occurs is strongly dependent on the experimental variables and on x, and that this dependence can lead to an estimate of the value of x. For poorly stabilized glasses reheated slowly, on the other hand, the main peak apparently vanishes and allows an upper peak to appear, which is small and insensitive to x and the experimental variables. Intermediate situations in which the main and the upper peaks occur separately give rise to a range of effects which may become quite complicated as the two peaks approach each other. The occurrence of such multiple peaks, which has usually been overlooked or misinterpreted in the past, is discussed and explained in detail and is compared with some experimental observations reported in the literature.
    Additional Material: 19 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 16 (1972), S. 301-313 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This report describes a series of recent experiments in which various thermal transitions including stress relaxations and glass transitions in high polymers were characterized by observing birefringence changes during heating and cooling. An automatic recording device employing a hot stage, polarizing microscope, photocell, and chart recorder was employed in these investigations. A general discussion of the utility and advantages of the technique of thermo-optical analysis (TOA) as well as its deficiencies is presented. Characteristic birefringence-temperature profiles of a number of amorphous and semicrystalline polymers are included.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 26 (1981), S. 2665-2677 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The formation of a polymer/polymer composite by solid-state polymerization of trioxane (TOX) crystals grown within binary trioxane/polycaprolactone or trioxane/poly(oxythylene) mixtures is reported. At present, such composites have been formed with trioxane-rich (hypoeutectic) mixtures. It is observed that in this composition range, much higher yields are obtained through thermal orientation of the TOX crystals which result in very highly ordered systems as revealed by optical and electron microscopy. These POM-rich composites were not, however, amenable to mechanical testing.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 26 (1981), S. 2485-2500 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The solid-state polymerization by γ-radiation and postpolymerization of bulk samples of trioxane has been investigated. Different thermal treatment results in radically different initial morphologies of the melt-crystallized trioxane which in turn have a profound influence on the yield and morphology of the resulting poly(oxymethylene) (POM). The polymerization yield increases in the following series: melt-crystallized trioxane with an “opaque” (small grains) morphology, as-grown needles, trioxane with a “quasi-transparent” morphology, and finally thermally oriented crystals. Furthermore, little additional POM is formed during repeated polymerization cycles. The observation of an extensive nodulation of the polymer fibrils when the yield is high is consistent with a multiple-stage growth model for the solid-state polymerization of trioxane.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
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