Abstract
AbstractThe discrete relaxation spectrum of an ABS (acrylonitrile–butadiene–styrene) polymer at 190°C. was calculated by using results from tensile relaxation moduli and the principle of reduced variables. The shift factor was found to conform well to the WLF equation, and the free volume fraction at Tg was calculated to be 0.026 in good agreement with the universal value. The values of the thermal expansion coefficient of free volume were calculated to be 9.8 X 10‐4 deg.−1 and 7.0 × 10−4 deg.−1, respectively, from the WLF coefficients and from dilatometric results. The width of the entanglement plateau of the relaxation spectrum was observed to be a factor of approximately 2 larger than that calculated from molecular weights between entanglement couplings determined either from rubber elasticity theory or from an assumed molecular model which discounts the presence of the butadiene in the ABS system. By using Pao's theory, flow curves at 190°C. were calculated both from the discrete relaxation spectrum and from the dynamic modulus. These curves were essentially identical. However, the stress values of these curves were found to be about a decade higher than those experimentally determined from capillary flow measurements. Nevertheless, the shapes of the curves are in good agreement, and an explanation is suggested for existing discrepancies. Flow instability, processing variables, and residual strains are discussed in light of the flow curves and the calculated recoverable shear strains.
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