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Constitutive modelling of the stress-strain response of rubbery polymers isdescribed, with an emphasis on the limits to linearity for both neat and filledrubber (the latter due to the Payne effect). Deviations from the Boltzmannsuperposition principle (time-strain invariance) under reversing strainhistories are reviewed, including a discussion of the Mullins effect. Thechapter also reviews the application of the stress optic law and the conditionscausing its breakdown: internal stress, the glass transition, orientationalcoupling, and creep recovery. Different empirical rules for nonlinear flow areconsidered, including the Cox-Merz rule and the relations of Laun and Gleissle.

Constitutive modeling, non-linear behavior, and the stress-optic law