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  • 1990-1994  (2)
  • 1990  (2)
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  • 1990-1994  (2)
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  • 1
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The sub-Tg relaxations of bisphenol-A-based thermosets cured with diaminodiphenyl methane and diaminodiphenyl sulfone have been studied by dielectric measurements over the frequency range 12 Hz to 200 kHz from their ungelled or “least” cured states to their fully cured states. Both thermosets show two relaxation processes, γ and β, as the temperature is increased toward their Tgs. In the ungelled states, the γ process is more prominent than the β process. As curing proceeds, the strength of the γ process decreases and reaches a limiting value, while that of the β process initially increases, reaches a maximum value, and then decreases. An increase in the chain iength and the number of crosslinks increases the number of -OH dipoles and/or degree of their motions in local regions of the network matrix. This is partly caused by the decreasing efficiency of segmental packing as the curing proceeds. The sub-Tg relaxations become increasingly more, separated from the α relaxation during curing. Physical aging causes a decrease in the strength of the β relaxation of the thermosets as a result of the collapse of loosely packed regions of low cross-linking density, and this decrease competes against an increase caused by further crosslinking during the “post-cure” process.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 28 (1990), S. 1621-1639 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dielectric permittivity ∊′ and loss ∊″ during the crosslinking or curing of diglycidyl ether of bisphenol-A with diaminodiphenyl methane and diaminodiphenyl sulfone have been measured from the sol to gel to glass-formation regions. The ∊′ monotonically decreases with time and the ∊″ initially decreases, then increases to a peak value and finally reaches extremely low values characteristic of the glassy state. These features shift to shorter times with an increase in the temperature of curing. Complex-plane plots of ∊′ and ∊″ have the shape of an are skewed at both the short-time and the long-time intercepts and resemble Cole-Cole plots of ∊*. Thus the dielectric consequences of the chemical changes with time during the cross-linking of a thermoset are analogous to the frequency dependence of ∊* in an amorphous solid. The time dependence of ∊* follows a stretched exponential decay, φ(t) = exp [- (t/τ)γ] where 0 〈 γ 〈 1. The parameter γ is in the range 0.2 to 0.4, and increases with a decrease in the curing temperature. Additional curing at longer times produces polymer segments in the network with a high reorientation rate. This is observed as deviations from the shape of a skewed arc at the limiting long-time intercept and appears as a secondary relaxation during the curing process, but at very long times. The ∊′ and ∊″ have been analyzed and the roles of dc conductivity, Δ∊, and γ in determining the shape of the curing isotherms have been estimated. A representation of the data in the complex electrical modulus, M*, formalism shows the occurrence of two relaxation processes during the period of a typical isothermal cure. The feature observed at the shortest time is due to conductivity relaxation and the subsequent feature is due to the dipolar relaxation processes during the curing. The time of cure at which the relaxation rate reaches a fixed value follows an exponential relation with the reciprocal curing temperature with parameters which are characteristic of a thermoset. The decrease in dc conductivity during sol → gel conversion follows the scaling law used in the description of a critical phenomenon.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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