Shear-Enhanced Crystallization in Isotactic Polypropylene. 1. Correspondence between in Situ Rheo-Optics and ex Situ Structure Determination

Abstract

The effects of “short term shearing” on the subsequent crystallization of a polydisperse Ziegler−Natta isotactic polypropylene are observed using in situ optical measurements and ex situ microscopy. Imposition of brief intervals of shear (0.25−20 s, less than a thousandth of the quiescent crystallization time) can reduce the crystallization time by 2 orders of magnitude (e.g., at 141 °C with a wall shear stress of 0.06 MPa). With increasing shearing time, the crystallization time saturates and highly anisotropic growth ensues. This transition to oriented growth correlates with changes in the transient behavior during flow and the semicrystalline morphology observed ex situ. During flow, we observe the generation of long-lived, highly oriented structures (evident in the transient birefringence) under all conditions that induce subsequent growth of highly oriented crystallites. In turn, the development of oriented crystallites observed in situ after cessation of flow correlates with development of a “skin-core” morphology (highly oriented skin on a spherulitic core) observed ex situ. Interestingly, the long-lived structures generated during flow appear at shorter times with increasing temperature (at fixed shear stress), the opposite of the trend one would expect on the basis of the temperature dependence of quiescent crystallization.