Saturation of Shear-Induced Isothermal Crystallization of Polymers at the Steady State and the Entanglement−Disentanglement Transition

• Published in: Macromolecules Vol. 39; no. 22; pp. 7626 - 7634
• Main Authors: Martins, José A, Zhang, Weidong, Brito, António M
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 31.10.2006
• Subjects: Applied sciences; Crystallization; Exact sciences and technology; Organic polymers; Physicochemistry of polymers; Properties and characterization; Melt crystallization; Liquid state structure; Shear flow; Isotactic polymer; Propylene polymer; Temperature effect; Kinetics; Experimental study; Isothermal crystallization
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/ma061143u

To provide insight into the formation of shear-induced precursor structures, three apparently unrelated subjects are analyzed and discussed:  the saturation of crystallization from sheared polymer melts, evaluated with a new shear DTA instrument, the steady state in steady shear, and the entanglement−disentanglement transition. It is shown that the same large strains that saturate crystallization also lead to a reversible steady state in steady shear, where the viscosity of the sheared melt is constant in time, and their magnitude is only determined by the temperature of the sheared melt. Features of the melt morphology at this state are discussed, and their importance is highlighted to understand the possible mechanisms behind the formation of shear-induced precursors. Measurements of the reptation time for unsheared samples, and samples sheared up to the steady state, allowed the quantification of the entanglements loss during the transition between these two states (around 2/3), which is interpreted as an entanglement−disentanglement transition. The relevance of this result on assumptions of flow models, particularly the constant number of topological constraints, convective constraint release process, and chain stretch, is discussed.