Thermodynamics and Dynamics of Branched Polystyrenes and Their Mixtures

Bibliographic Details
Main Author: Yang, Sewoo
Language:English
Published: University of Akron / OhioLINK 2008
Subjects:
PS
Online Access:http://rave.ohiolink.edu/etdc/view?acc_num=akron1212601903
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spelling ndltd-OhioLink-oai-etd.ohiolink.edu-akron12126019032021-08-03T05:25:36Z Thermodynamics and Dynamics of Branched Polystyrenes and Their Mixtures Yang, Sewoo Polymers blends BRANCHED hydrogenous polymer PS ¿¿¿¿¿ eff The effect of long-chain branching on the bulk and surface thermodynamics of polymer blends, as well as its effect on dynamics of pure melts, has been studied using well-defined polystyrene chains synthesized using anionic polymerization. Three specific aspects of branching were addressed: i.) the effect of changing chain end chemistry, ii.) the effect of changing branch point chemistry, and iii.) the effect of altering the distance between junction points in a molecule that is otherwise identical. Variations in values of the interaction parameter for isotopic linear blends, measured using small angle neutron scattering, were found, but their magnitudes were small. For chains of 30,000 molecular weight any differences in surface segregation arising from changes in chain end and branch point chemistry were not larger than the isotopic labeling effect. Shortening the central linear portion of a pom-pom chain while keeping overall molecular weight constant reduced the hydrodynamic radius of the chain. The contribution due to architecture to the interaction parameter for isotopic binary blends of linear and branched chains increased with a growing disparity in hydrodynamic volumes. A Gaussian field theory captures this effect. The strength of segregation to the surface of a blend film is seen with neutron reflectivity to increase with a reduced length of the central linear portion of the pom-pom, rather than depending on only the number and type of chain ends and junction points as approximated by the existing linear response theory. While in most cases the contribution to the interaction parameter due to architecture alone was estimated by subtracting an estimate of the isotopic effect from the overall interaction parameter, measurements were also done that allowed us to extrapolate data measured in blends of branched PS and linear PS-r-deuterated PS random copolymers to zero deuterium labeling. Relaxation times for the surface fluctuations of films of highly branched PS were measured using X-ray photon correlation spectroscopy. These revealed trends different from those for bulk viscosity measurements when film viscosities were calculated assuming a continuum model for surface capillary waves applied. 2008-08-26 English text University of Akron / OhioLINK http://rave.ohiolink.edu/etdc/view?acc_num=akron1212601903 http://rave.ohiolink.edu/etdc/view?acc_num=akron1212601903 unrestricted This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws.
collection NDLTD
language English
sources NDLTD
topic Polymers
blends
BRANCHED
hydrogenous
polymer
PS
¿¿¿¿¿ eff
spellingShingle Polymers
blends
BRANCHED
hydrogenous
polymer
PS
¿¿¿¿¿ eff
Yang, Sewoo
Thermodynamics and Dynamics of Branched Polystyrenes and Their Mixtures
author Yang, Sewoo
author_facet Yang, Sewoo
author_sort Yang, Sewoo
title Thermodynamics and Dynamics of Branched Polystyrenes and Their Mixtures
title_short Thermodynamics and Dynamics of Branched Polystyrenes and Their Mixtures
title_full Thermodynamics and Dynamics of Branched Polystyrenes and Their Mixtures
title_fullStr Thermodynamics and Dynamics of Branched Polystyrenes and Their Mixtures
title_full_unstemmed Thermodynamics and Dynamics of Branched Polystyrenes and Their Mixtures
title_sort thermodynamics and dynamics of branched polystyrenes and their mixtures
publisher University of Akron / OhioLINK
publishDate 2008
url http://rave.ohiolink.edu/etdc/view?acc_num=akron1212601903
work_keys_str_mv AT yangsewoo thermodynamicsanddynamicsofbranchedpolystyrenesandtheirmixtures
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