Title page for ETD etd-09232004-105021

Type of Document Master's Thesis
Author Li, Bingbing
URN etd-09232004-105021
Title Surface Characterization of Poly (epsilon-caprolactone) at the Air/Water Interface
Degree Master of Science
Department Chemistry
Advisory Committee
Advisor Name Title
Esker, Alan R. Committee Chair
Marand, Hervé L. Committee Member
Riffle, Judy S. Committee Member
  • Dendritic Crystals
  • Crystallization
  • Poly (epsilon-caprolactone)
  • Langmuir monolayer
  • Brewster Angle Microscopy
Date of Defense 2004-09-09
Availability unrestricted
Surface behavior of poly (epsilon-caprolactone) (PCL) have been studied at the air/water interface (A/W). PCL is a hydrophobic and crystalline polyester with a glass transition temperature around -60 degrees centigrade, a melting point around 55 degrees centigrade, excellent biocompatibility, and low toxicity. In the past decade, PCL based systems have attracted considerable interest for controlled-release drug delivery and as scaffolds for tissue engineering, that require a fundamental understanding of PCL's degradation mechanisms and crystallization properties. PCL spherulites were commonly observed in previous bulk studies. This thesis focuses on PCL crystallization in Langmuir monolayers. Brewster angle microscopy (BAM) studies show that square, distorted rectangular, and dendritic crystals form at the A/W interface. While dendritic structures have been observed in poly (ethylene oxide) (PEO) thin film on solid substrates, this study of PCL is the first time that dendritic morphologies have been observed at the A/W interface for a linear flexible-coil polymer. As far as we know, the crystallization of flexible-coil polymers at the A/W interface is a brand new area of research. These findings may provide an interesting model system for studying crystallization in confined geometries and the effect of crystallinity on enzyme catalyzed hydrolysis of this important biodegradable polymer at the A/W interface.

The main objectives of this thesis were to investigate the phase behavior of PCL at the A/W interface, gain a deeper understanding of the nucleation and growth mechanism of PCL crystallization at the A/W interface through surface pressure-area isotherms and isobaric area relaxation analyses, and interpret the effects of molecular weight on the nucleation and growth mechanism, and morphologies of semicrystalline PCL crystallized in Langmuir monolayers at the A/W interface.

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