Alexandria Digital Research Library

Self-Consistent Field Theory for the Design of Thermoplastic Elastomers from Miktoarm Block Copolymer - Homopolymer Blends

Author:
Hamilton, Andrew Lawrence
Degree Grantor:
University of California, Santa Barbara. Materials
Degree Supervisor:
Glenn H. Fredrickson
Place of Publication:
[Santa Barbara, Calif.]
Publisher:
University of California, Santa Barbara
Creation Date:
2014
Issued Date:
2014
Topics:
Engineering, Materials Science, Chemistry, Polymer, and Engineering, Chemical
Genres:
Online resources and Dissertations, Academic
Dissertation:
M.S.--University of California, Santa Barbara, 2014
Description:

We have used self-consistent field theory to study the morphological characteristics of blends of miktoarm block copolymers and homopolymers. More specifically, we have studied the effects of segregation strength, miktoarm block copolymer composition, and homopolymer size and volume fraction on the phase diagrams of these systems. A15 domains with discrete A-monomer spherical domains were found to be stable with A-monomer loading fractions of at least as high as 52%. Hexagonally-packed cylindrical domains were found to be stable at A-monomer loadings of at least as high as 72%. These findings represent a significant improvement from the loading fractions of 43% and 60% reported by Lynd et al. for spherical and cylindrical domains in neat miktoarm block copolymers, respectively. It is also quite possible that even greater loading fractions are achievable in systems too large for our simulations. These results predict exciting new materials for next-generation thermoplastic elastomers, since the ideal TPE has a large loading of A monomers in discrete, crystalline or glassy domains, surrounded by a continuous matrix of elastomeric B domains.

Additionally, we have performed SCFT simulations modelled after experimental blends of polystyrene and polyisoprene-based miktoarm block copolymers and homopolymers. Certain experimental samples showed fascinating new "bricks and mortar" phases and swollen asymmetric lamellar phases. In both cases, the A domains are highly swollen with homopolymer, forcing the miktoarm block copolymer to segregate near the interface and adopt the role of a surfactant. The resulting structures maintain separate A and B domains, but lack long-range order. While it is not possible to study these mesophases using SCFT, since they lack long-range order and therefore well-defined symmetry, our SCFT results show the onset of macrophase separation at similar homopolymer loadings, for both the bricks and mortar phases and the highly swollen lamellae. This supports the theory that both phases are fluctuation-induced mesophases, similar to microemulsions in character, that lie in between the typical ordered structures and full macrophase separation.

Physical Description:
1 online resource (52 pages)
Format:
Text
Collection(s):
UCSB electronic theses and dissertations
ARK:
ark:/48907/f3xg9p9q
ISBN:
9781321567861
Catalog System Number:
990045118320203776
Rights:
Inc.icon only.dark In Copyright
Copyright Holder:
Andrew Hamilton
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