Crystallization and Melting Studies of Poly(ε-caprolactone) and Poly(ethylene oxide) using Flash™ Differential Scanning Calorimetry and Preparation and Characterization of Poly(δ-valerolactone) Fractions

The isothermal crystallization and melting temperatures of poly(ε-caprolactone) were correlated using fast differential scanning calorimetry. The melting kinetics was found to be independent of isothermal crystallization temperature and time. The conventional Hoffman-Weeks method could not be used to determine the equilibrium melting temperature because the observed melting temperatures were greater than the crystallization temperatures by a constant, so the Gibbs-Thomson method was used instead, yielding an equilibrium melting temperature of 103.4 ± 2.3°C. A modification was proposed to the non-linear Hoffman-Weeks equation that included a non-linear undercooling dependence for the kinetic fold surface free energy upon crystallization and permitted accurate modeling of the observed melting behavior. The isothermal crystallization rates of four narrow molecular weight poly(ethylene oxide) fractions were characterized using fast differential scanning calorimetry for crystallization temperatures spanning 100°C range with the lower limit approaching the glass transition. A transition from homogeneous to heterogeneous primary nucleation was observed at −5°C. The kinetic analysis suggested that the crystal growth geometry depends strongly on temperature, where rod-like structures begin to appear near the glass transition temperature, highly branched solid sheaves grow throughout the homogeneous primary nucleation temperature range, and spherulites grow in the heterogenous primary nucleation range. Poly(δ-valerolactone) was synthesized using microwave-assisted techniques. Narrow molecular weight fractions were obtained using successive precipitation fractionation. Preliminary isothermal crystallization studies suggest that conventional thermal analysis methods are not adequate to measure the melting temperatures accurately due to reorganization during heating.

Name thesis:degree_name

Doctor of Philosophy

Level thesis:degree_level

doctoral

Discipline thesis:degree_discipline

Chemistry

Department dc:contributor.department

Chemistry

Grantor dc:publisher

Virginia Tech

Year dc:date.issued

2019

Author dc:creator

• Vincent, Matthew Ryan

Chair dc:contributor.committeechair

• Marand, Herve

Committee members dc:contributor.committeemember

• Madsen, Louis A.
• Esker, Alan R.
• Moore, Robert Bowen

• polymer
• crystallization
• melting
• kinetics
• fast differential scanning calorimetry
• poly(ε-caprolactone)
• poly(ethylene oxide)
• poly(δ-valerolactone)
• fold surface free energy
• Gibbs-Thomson
• Hoffman-Weeks
• equilibrium melting temperature

Statement dc:rights

• In Copyright

Licence dc:rights.uri

• http://rightsstatements.org/vocab/InC/1.0/

Dc Identifier Other

vt_gsexam:21551

OAI identifier oai:identifier

oai:vtechworks.lib.vt.edu:10919/101668