The problem of flow-induced crystallization (FIC) of polymer melts is addressed via a microrheological approach. In particular, the Doi−Edwards model with the so-called independent alignment approximation (DE−IAA) is used to calculate the flow-induced change of free energy. Subsequently, the crystallization induction time, i.e., the nucleation characteristic time, is calculated in isothermal steady shear and uniaxial elongational flows. Asymptotic, analytical expressions for the induction time are also derived in the limit of low and high Deborah number (the product of the deformation rate and the polymer relaxation time). The DE−IAA model is found to give more realistic predictions than those of simpler, dumbbell-like models already proposed in the literature. When compared to existing FIC experimental data in shear flow, good quantitative agreement is found with the polymer relaxation time as the only adjustable parameter of the model.

A new model is presented for describing the time‐dependent flow of entangled polymer liquids at high shear rates. The results were obtained by extending the Doi and Edwards theory to include the effect of chain stretching. This nonlinear phenomenon is predicted to occur when the product of the shear rate and longitudinal relaxation time of the polymer exceeds one. If a constant‐shear‐rate flow is started under these conditions, it is shown that the shear stress and the normal stress are considerably larger than that predicted by the original reptation model. We also find that both of these stresses can pass through maxima before reaching a steady state and that the times required to reach these maxima are constants independent of the shear rate. In general the new model requires the numerical solution of coupled partial differential equations. However, at the highest shear rates where reptative relaxation is no longer important, an analytical solution for the stresses is found. The results obtained here are shown to agree well with experimental data and to be an improvement over a simpler model recently proposed.

Using rheological techniques, we investigate the evolution of the microstructure evolution during the early stages of quiescent crystallization of poly(1-butene). In performing the measurements, use is made of an innovative experimental protocol, called “inverse quenching”, which allows stopping the crystallization process and producing a stable biphasic (crystalline/amorphous) system. In this way, very low frequency measurements at fixed degrees of crystallization are made possible. We find that crystallization, evidenced as a liquid-to-solid transition (LST) under isothermal conditions, with characteristics of critical gel behavior, takes place at surprisingly low degrees of crystallinity (below 1.5%). The critical gel properties, which are found to depend on both crystallization temperature and molecular weight, can be reduced to a single master curve when the gel strength is plotted as a function of the relaxation exponent. More importantly, the LST is preceded by the development of a long relaxation process. This latter process, although not fully understood, brings analogies to the slow dynamics observed in hybrid colloid−polymer systems (block copolymer micelles or multiarm star polymers) as well as the recently suggested presence of dormant nuclei. It is clear, however, that the connectivity among crystallites, apparently via the amorphous segments, plays a key role in this new process.

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