Title page for ETD etd-09072011-132950

Type of Document Dissertation
Author Heinzer , Michael J
Author's Email Address heinzerm@vt.edu
URN etd-09072011-132950
Title Phase behavior and ordering kinetics of block copolymers in solution during solvent removal
Degree PhD
Department Chemical Engineering
Advisory Committee
Advisor Name Title
Baird, Donald G. Committee Chair
Davis, Richey M. Committee Member
Martin, Stephen M. Committee Member
McGrath, James E. Committee Member
  • solution-cast films
  • ordering kinetics
  • SAXS
  • rheology
  • copolymer
Date of Defense 2011-08-25
Availability restricted
This dissertation is part of an effort to understand and to facilitate the modeling of the ordering kinetics of block copolymers in solution during the extraction of solvent from a solution-cast film. Central to this work was determining a suitable method for measuring the ordering kinetics during solvent removal and being able to interpret the measurements in terms of structure development. It was also necessary to assess a model for quantifying the ordering kinetics to use in conjunction with a mass transfer model to predict structure formation during solvent extraction.

Changes in the dynamic mechanical response (DMR) over time of block copolymer solutions at fixed concentrations following solvent removal were explored as a means to track the growth of ordered domains. It was found that DMR measurements performed following solvent extraction were sensitive to the nucleation and growth process of the phase separation process over a wide range of concentrations, beginning near the order-disorder transition concentration. Based on complimentary small angle X-ray measurements, it was determined that the changes in the DMR are caused by the development of individual microstructures, The SAXS experiments also indicated that the DMR is insensitive to late stages of the growth process. Ultimately, DMR measurements under-predicted the ordering times at several concentrations and did not detect ordering at concentrations above which SAXS data indicated ordering was still occurring.

The ability to use the parallel and series rules of mixtures for determining (t) in conjunction with the Avrami equation to quantitatively model the ordering kinetics was also determined. These models allowed the ordering kinetics during solvent removal to be qualitatively analyzed. However, using the two different rules of mixtures resulted in a wide range of possible ordering times for a given copolymer concentration, making these approximations unsuitable for modeling a real solvent extraction process. Further, the parameters of the model were insensitive to the type of microstructures developing.

As a continuation of this work, a new apparatus to track block copolymer ordering in situ during solvent extraction was designed. Experiments using the apparatus allowed the ordering kinetics and domain dimensions as a function of concentration to be monitored in real-time under several solvent removal conditions. These experiments study the ordering kinetics is a manner more akin to real processing conditions and will allow future assessment of the ability of iso-concentration ordering kinetics to predict phase separation during film processing.

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