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Polarization‐optical investigation of polymers in fluid and high‐elastic states under oscillatory deformation

机译:Polarization‐optical investigation of polymers in fluid and high‐elastic states under oscillatory deformation

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AbstractThe relationship was investigated between birefringence and oscillatory shear deformation of linear high molecular mass polymers exemplified by narrow‐ and broad‐distribution polybutadienes and polyisoprenes. Polymer deformation at different frequencies and amplitudes was carried out in an annular gap. The stress field uniformity was not below 95. It was shown that in oscillatory deformation of polymers in the fluid and high‐elastic states, birefringence contains a time‐independent steady component and an oscillatory component with a frequency equal to that of the assigned oscillation. A linear interrelation was found to exist between the amplitude of the oscillatory component of birefringence and that of the shear stresses, with a proportionality factor equal to the stress‐optical coefficient of the polymers. The phase of the oscillatory component of birefringence coincides with that of the shear stresses. Measurements of the steady component of the birefringence make it possible to find the steady component of the first normal stress difference resulting from the assignment of shear oscillations to the polymer. On the basis of the experimental data obtained for polybutadienes and polyisoprenes, and the literature data for polystyrene solutions, a master curve was constructed that generalizes the dependence of the steady component of the first normal stress difference in the linear and nonlinear deformation regimes on the product of the square of the deformation amplitude and the storage modulus measured at low amplitudes. This dependence is valid in the linear and nonlinear deformation regimes. It is invariant with frequency, amplitude deformation, molecular mass, and molecular mass distribution of the polymers. It is shown by visual observation of deformation that the abrupt drop in resistance of polymer to shear in large‐amplitude deformation is due to polymer rupture near the surface of the inner cylinder and is accompanied by a slip‐stick process. This is the phenomenon of spurt early observed in capillary viscometers at high shear stresses and recently investigated in coaxial cylinder devices at large amplitud

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