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Synthetic Methodologies to Tune Mixed Polymer Brush Morphology.
Record Type:
Language materials, manuscript : Monograph/item
Title/Author:
Synthetic Methodologies to Tune Mixed Polymer Brush Morphology./
Author:
Smith, Julia D.
Description:
1 online resource (165 pages)
Notes:
Source: Dissertations Abstracts International, Volume: 86-01, Section: B.
Contained By:
Dissertations Abstracts International86-01B.
Subject:
Polymer chemistry. -
Online resource:
click for full text (PQDT)
ISBN:
9798383200810
Synthetic Methodologies to Tune Mixed Polymer Brush Morphology.
Smith, Julia D.
Synthetic Methodologies to Tune Mixed Polymer Brush Morphology.
- 1 online resource (165 pages)
Source: Dissertations Abstracts International, Volume: 86-01, Section: B.
Thesis (Ph.D.)--The University of Wisconsin - Madison, 2024.
Includes bibliographical references
Polymer brushes are used for surface modification to tune interfacial properties. Mixed A/B polymer brushes, where two distinct types of polymers are tethered to the surface, are especially useful for creating nanoscale morphologies as well as switchable or responsive surfaces. Although simulations predict an array of unique phase-separated morphologies for mixed brushes, their phase behavior has not been extensively explored in experiments mainly due to challenges with synthesis. It is difficult to precisely tune molecular weight, grafting density, grafting ratio, and hence the conformation of the brushes, especially when A and B are highly incompatible with each other. This thesis addresses these synthetic challenges by a) development of a RAFT inimer for brush growth of previously difficult monomers along with efficient chain-end functionalization through click chemistry, b) design of a Y-shaped inimer with two orthogonal initiators attached at a common junction point for versatile growth of mixed A/B polymer brushes with a uniform 1:1 grafting ratio, and c) design of mixed inimer coating for non 1:1 stoichiometry of A:B. Using this chemistry, we perform the following morphological studies: a) probe the effect of a low-surface energy fluorinated chain end on the conformation of brushes grown from the RAFT inimer coating, b) demonstrate mixed PMMA/PS polymer brushes with 1:1 grafting ratio using the Y-inimer coating with a full range of microphase separated morphologies, and c) demonstrate a mixed PMAA/P2VP polyelectrolyte brushes with opposite charges that show a pH-dependent nanoscale porous morphology based on complex coacervation enabled by 1:1 grafting ratio. The main contribution of this thesis is in improving the synthesis methods for mixed polymer brushes to precisely control brush parameters and expand the monomer scope, hence paving the way for detailed experimental studies of morphological properties, especially in the high grafting density regime. .
Electronic reproduction.
Ann Arbor, Mich. :
ProQuest,
2024
Mode of access: World Wide Web
ISBN: 9798383200810Subjects--Topical Terms:
1182163
Polymer chemistry.
Subjects--Index Terms:
Polymer brushesIndex Terms--Genre/Form:
554714
Electronic books.
Synthetic Methodologies to Tune Mixed Polymer Brush Morphology.
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Smith, Julia D.
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Synthetic Methodologies to Tune Mixed Polymer Brush Morphology.
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Source: Dissertations Abstracts International, Volume: 86-01, Section: B.
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Advisor: Gopalan, Padma.
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Thesis (Ph.D.)--The University of Wisconsin - Madison, 2024.
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Includes bibliographical references
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Polymer brushes are used for surface modification to tune interfacial properties. Mixed A/B polymer brushes, where two distinct types of polymers are tethered to the surface, are especially useful for creating nanoscale morphologies as well as switchable or responsive surfaces. Although simulations predict an array of unique phase-separated morphologies for mixed brushes, their phase behavior has not been extensively explored in experiments mainly due to challenges with synthesis. It is difficult to precisely tune molecular weight, grafting density, grafting ratio, and hence the conformation of the brushes, especially when A and B are highly incompatible with each other. This thesis addresses these synthetic challenges by a) development of a RAFT inimer for brush growth of previously difficult monomers along with efficient chain-end functionalization through click chemistry, b) design of a Y-shaped inimer with two orthogonal initiators attached at a common junction point for versatile growth of mixed A/B polymer brushes with a uniform 1:1 grafting ratio, and c) design of mixed inimer coating for non 1:1 stoichiometry of A:B. Using this chemistry, we perform the following morphological studies: a) probe the effect of a low-surface energy fluorinated chain end on the conformation of brushes grown from the RAFT inimer coating, b) demonstrate mixed PMMA/PS polymer brushes with 1:1 grafting ratio using the Y-inimer coating with a full range of microphase separated morphologies, and c) demonstrate a mixed PMAA/P2VP polyelectrolyte brushes with opposite charges that show a pH-dependent nanoscale porous morphology based on complex coacervation enabled by 1:1 grafting ratio. The main contribution of this thesis is in improving the synthesis methods for mixed polymer brushes to precisely control brush parameters and expand the monomer scope, hence paving the way for detailed experimental studies of morphological properties, especially in the high grafting density regime. .
533
$a
Electronic reproduction.
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Ann Arbor, Mich. :
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ProQuest,
$d
2024
538
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Mode of access: World Wide Web
650
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Polymer chemistry.
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1182163
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Materials science.
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557839
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Molecular chemistry.
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Polymer brushes
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A/B polymer brushes
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RAFT inimer
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Grafting density
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ProQuest Information and Learning Co.
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The University of Wisconsin - Madison.
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Dissertations Abstracts International
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86-01B.
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http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=31335696
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click for full text (PQDT)
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