Spinodal-Assisted Crystallization in Polymer Melts

P. D. Olmsted; W. C. K. Poon; T. C. B. McLeish; N. J. Terrill; A. J. Ryan

doi:10.1103/PhysRevLett.81.373

Spinodal-Assisted Crystallization in Polymer Melts

P. D. Olmsted, W. C. K. Poon, T. C. B. McLeish, N. J. Terrill, and A. J. Ryan

Phys. Rev. Lett. 81, 373 – Published 13 July 1998

Abstract

Recent experiments in some polymer melts quenched below the melting temperature have reported spinodal kinetics in small-angle x-ray scattering before the emergence of a crystalline structure. To explain these observations we propose that the coupling between density and chain conformation induces a liquid-liquid binodal within the equilibrium liquid-crystalline solid coexistence region. A simple phenomenological theory is developed to illustrate this idea, and several experimentally testable consequences are discussed. Shear is shown to enhance the kinetic role of the hidden binodal.

Received 3 February 1998

DOI:https://doi.org/10.1103/PhysRevLett.81.373

Authors & Affiliations

P. D. Olmsted^1,*, W. C. K. Poon^2,†, T. C. B. McLeish¹, N. J. Terrill³, and A. J. Ryan³

¹Department of Physics & Astronomy and Polymer IRC, University of Leeds, Leeds LS2 9JT, England
²Department of Physics & Astronomy, The University of Edinburgh, Mayfield Road, Edinburgh EH9 3JZ, Scotland
³Department of Chemistry, University of Sheffield, Brookhill, Sheffield S3 7HF, England

^*Electronic address: p.d.olmsted@leeds.ac.uk
^†Electronic address: w.poon@ed.ac.uk