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  • 1955-1959  (3)
  • 1
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 20 (1956), S. 515-536 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The viscoelastic properties of four kinds of nylon-6 and viscoses rayon having various degrees of crystallinity and of drawing are studied. The crystallinity is estimated from the density measurement for nylon-6, while for viscose rayon it is determined by the acid hydrolysis method of Nickerson. The various kinds of measuring instruments are described by which the complex Young's modulus of fiber monofilament is measured over a wide range of frequency. The dynamical measurements for both materials are made over the frequency range from 0.047 c./sec. to 100 kc./sec. at 20°C. and 66% RH, and then the spectra of relaxation times and the distribution function of retardation times for each sample are obtained. From the experimental results, it is concluded that the mechanical dispersion found in the audio-frequency range for partially crystallized nylon-6 is due to the motion of segments in strained amorphous parts. The distribution function of retardation times for the heat conditioned nylon-6 is well represented by a Cole-Cole's distribution function with β = 0.29. On the other hand, the shock-cooled nylon-6 shows distinctively a non-linear property at the strain of order of 10-3. Besides, it is found that the increase of the degree of crystallinity and drawing results in shifting the dispersion regions, as a whole, to longer time regions, and that the shapes of spectra of relaxation times are almost independent of the degree of crystallinity, while the shapes of spectra corresponding to wedge-type spectra become less steep with increase of the degree of mechanical drawing. These facts are attributed to the sterile hindrance against the segmental motion. As regards viscose rayon, the mechanical dispersion represents itself at about 65°C. in 65% RH, and the activation energy for the segmental motion in amorphous parts is about 190 Kcal/mole. The water molecules adsorbed in fibrous structure are supposed to be playing the role of a plasticizer. The degree of crystallinity (70-75%) does not affect the mechanical behaviours of viscose rayon so much.
    Additional Material: 23 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 27 (1958), S. 255-267 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Taking, as the samples for investigation, filaments of viscose rayon (60% crystallinity) and acetate rayon (54% acetyl) both crosslinked to various extents by tetramethylenebisethylene urea and tetramethylenediisocyanate urea as the crosslinking agents, the dynamic and transient moduli, E′, G1, G2, the internal friction, Q-1, and the apparent activation energy for relaxation of segment, ΔU, were measured and the results were considered in their relation to the degree of crosslinking. From the results, the following conclusions were made: (1) When crosslinking is caused by long molecular chains of the crosslinking agents between the nearest neighboring molecules, the intermolecular spaces are widened to some extent and the restraint of segmental motion due to the dipole interaction of the strong polar hydroxyl groups is partly relieved so that the decreases in ΔU, E′, G1, and G2 are rather caused by a small amount of the crosslinking agents; for example, while the values of ΔU and E′, for the original viscose rayon not crosslinked are 230 kcal./mole and 2.0 × 1011 dynes/cm.2, respectively, they both decrease with an increase in degree of crosslinking and each shows a minimum (ΔU = 95 kcal./mole, E′ = 0.9 × 1011 dynes/cm.2) at the amount of bound nitrogen N = 0.73%. When the crosslinking proceeds further, the primary crosslinking effect makes its appearance so that ΔU, E′, G1, and G2 begin to rise with an increase in degree of crosslinking. (2) Due to the strong solvating or plasticizing effects, the water molecules absorbed bring about a strong decrease in the apparent activation energy; ΔU = 90 kcal./mole at 80% RH, 200 kcal./mole at 66% RH, and 210 kcal./mole at 55% RH for viscose rayon.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 31 (1958), S. 359-382 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Viscose fibers preswollen by treatment with very dilute sulfuric acid solutions of various concentrations (pH 2.4-5.1) were heat treated at various temperatures (60-200°C.). The effects of the heat treatment were considered from the measurements of: (1) The transition modulus of elasticity and other constants of a three-parameter model for viscoelasticity, as well as the dynamic modulus of elasticity. (2) The breaking strength as well as elongation. (3) The percentage crystallinity. (4) The amount of water absorbed. Thus it was concluded that the effects of heat treatments of stabilizing viscose rayon, as exhibited by the above-mentioned properties of the fibers, make their most prominent appearance in the range of pH optimal for the maximal hydration of regenerated cellulose, that is, pH = 3.0-5.0 of the acid bath, in which the fibers are soaked and swollen, and in the range of the temperature for the heat treatment near, or just above, the glass transition temperature of cellulose hydrate, i.e., at 60-70°C. where the acid-bath-treated fibers are heat treated. From the results of these measurements and also from the characteristic features of x-ray diagrams qualitatively observed, it was considered that the heat treatment affects mainly the more disordered (amorphous) regions so that the more ordered regions are newly developed at the expense of the former.
    Additional Material: 18 Ill.
    Type of Medium: Electronic Resource
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