Title page for ETD etd-06062008-164002

Type of Document Dissertation
Author Arnold, Lisa
URN etd-06062008-164002
Title Crystallization and melting behavior of (e-caprolactone)-based homopolymer and triblock copolymer
Degree PhD
Department Chemistry
Advisory Committee
Advisor Name Title
Marand, Herv L. Committee Chair
Gibson, Harry W. Committee Member
Ward, Thomas C. Committee Member
Wightman, James P. Committee Member
Wilkes, Garth L. Committee Member
  • poly(propylene oxide)
  • block copolymer
  • poly(e-caprolactone)
Date of Defense 1995-08-04
Availability restricted

The goal of this work is to examine the applicability of the Lauritzen-Hoflinan (LH) surface nucleation theory to the crystallization kinetics of poly(ε-caprolactone), PCL. This theory has successfully predicted a number of experimental observations such as the temperature dependence of spherulitic growth rates and the inverse relation between undercooling and the lamellar thickness. Claims have appeared in the literature that analysis of growth rate data using the LH theory does not yield physically meaningful parameters. This work will show that the lateral and fold interfacial free energy parameters, σ and σe, found by analysis with the LH theory are related to the chemical structure of the polymer chain in the case ofPCL. The fold interfacial free energy is related to the chain stiffness, and a recent proposal relates σ to the characteristic ratio, C∞. This work will examine the validity of the proposed relationship for the case of PCL. The effect of polymer chain architecture on the crystallization behavior was also investigated. The crystallization behavior of poly(ε-caprolactone) was compared and contrasted to that of a triblock copolymer containing (ε-caprolactone) blocks.

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