Thermodynamics of polymer -diluent systems at high pressure

2005 2005

Other formats: Order a copy

Abstract (summary)

Diblock copolymers have enormous potential use as templating materials for the fabrication of highly ordered materials on a nanometer scale. This derives from the complexity of phase behavior in microphase-separated block copolymer systems. In the ordered state block copolymers commonly self-organize into ordered lamellae, cylinders or spheres. Recently, high-pressure diluents have been used as a processing aid when using block copolymers as a templating material. In this study several aspects of polymer-diluent phase behavior have been investigated using high-pressure carbon dioxide as a diluent.

It is well established that dilation of a copolymer changes the characteristic interdomain spacing of a phase-separated system. The interdomain spacing decreases with dilation by non-selective diluents and increases with selective diluents. The characteristic spacing of poly(styrene-block-dimethyl siloxane) has been measured using small angle neutron scattering (SANS) in high-pressure CO2. A new power-law scaling for the change in interdomain spacing induced by dilation, which accounts for selectivity of the diluent, is presented.

The effect of high-pressure carbon dioxide on the order-to-disorder transition (ODT) of poly(styrene-block-2-vinyl pyridine) has been investigated using static birefringence. The results of these experiments indicate that in addition to the suppression of the ODT, dilation of a copolymer by carbon dioxide can induce the appearance of a second morphology. Further the appearance of this second morphology is strongly dependant on the sample history.

Methods for measuring the swelling of homopolymers in carbon dioxide have also been investigated. High-pressure spectroscopic ellipsometry and laser interferometry have been developed as methods to measure the swelling of homopolymer films. It is shown that spectroscopic ellipsometry and laser interferometry are both capable of measuring the swelling of homopolymer films at high pressure.

Indexing (details)

Materials science;
Chemical engineering
0794: Materials science
0542: Chemical engineering
Identifier / keyword
Applied sciences; Block copolymers; Interparticle spacing; Polymer-diluent; Thermodynamics
Thermodynamics of polymer -diluent systems at high pressure
Francis, Timothy John
Number of pages
Publication year
Degree date
School code
DAI-B 66/11, Dissertation Abstracts International
Place of publication
Ann Arbor
Country of publication
United States
9780542382734, 0542382733
Watkins, James J.
University of Massachusetts Amherst
University location
United States -- Massachusetts
Source type
Dissertations & Theses
Document type
Dissertation/thesis number
ProQuest document ID
Database copyright ProQuest LLC; ProQuest does not claim copyright in the individual underlying works.
Document URL
Access the complete full text

You can get the full text of this document if it is part of your institution's ProQuest subscription.

Try one of the following:

  • Connect to ProQuest through your library network and search for the document from there.
  • Request the document from your library.
  • Go to the ProQuest login page and enter a ProQuest or My Research username / password.