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The Spatial Distribution of Local Gl...

Christie, Dane.

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The Spatial Distribution of Local Glass Transition Temperatures in Nanostructured Block Copolymers.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	The Spatial Distribution of Local Glass Transition Temperatures in Nanostructured Block Copolymers./
作者:	Christie, Dane.
出版者:	Ann Arbor : ProQuest Dissertations & Theses, : 2019,
面頁冊數:	192 p.
附註:	Source: Dissertations Abstracts International, Volume: 80-08, Section: B.
Contained By:	Dissertations Abstracts International80-08B.
標題:	Polymer chemistry. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=10978634
ISBN:	9780438866584

The Spatial Distribution of Local Glass Transition Temperatures in Nanostructured Block Copolymers.
Christie, Dane.

The Spatial Distribution of Local Glass Transition Temperatures in Nanostructured Block Copolymers. - Ann Arbor : ProQuest Dissertations & Theses, 2019 - 192 p.

Source: Dissertations Abstracts International, Volume: 80-08, Section: B.

Thesis (Ph.D.)--Princeton University, 2019.

This item must not be sold to any third party vendors.

This dissertation demonstrates the use of fluorescence labeling and spectroscopy as a characterization tool which provides component- and location-specific measurements of the glass transition temperature (Tg), a fundamental polymer property, in a model nanostructured diblock copolymer-a polymer chain comprised of two chemically dissimilar homopolymers bound by a single covalent bond. Nanostructured diblock copolymers are self-assembled periodic materials with domains rich in either block, confined by the domain interface. The parameters governing the domain Tg-namely, the bulk T g of the homopolymers, the domain period, and the degree of segmental mixing between the blocks-can be systematically varied by choosing the block chemistries and total chain length. This combination of features offers a wide parameter space for property optimization. Until now, no characterization tool has demonstrated the capability of providing spatially-resolved Tg measurements across the domain structure, information that is crucial for optimizing the end-use properties. The length scales associated with the domain period, O(10-100 nm), pose a significant barrier towards performing such measurements. Here, this barrier was overcome by selectively incorporating a fluorescent monomer into the diblock copolymer chain during synthesis, thereby controlling the location where Tg was measured in the self-assembled structure. In diblock copolymers of poly(n-butyl methacrylate- b-methyl methacrylate), PBMA-PMMA, which self-assemble into a lamellar morphology, a strong gradient in Tg of the higher-Tg PMMA block-42 K over 4 nm-was mapped with nanometer resolution. These measurements also revealed a strongly asymmetric influence of the domain interface on Tg, with a much smaller dynamic gradient being observed for the lower-Tg PBMA block. Tg was characterized for a series of fluorescently-labeled homopolymers dilutely blended into an unlabeled diblock copolymer matrix. Unlike in the neat diblock copolymer, the labeled PMMA chains were not attached to the domain interface. A comparison of the Tg depression of the homopolymers in the blends to equivalent labeled diblock copolymers reveal ~ 5 K and 10 K contributions due to nanoscale confinement and block attachment to the interface, respectively.

ISBN: 9780438866584Subjects--Topical Terms:

3173488
Polymer chemistry.

The Spatial Distribution of Local Glass Transition Temperatures in Nanostructured Block Copolymers.
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520 $a This dissertation demonstrates the use of fluorescence labeling and spectroscopy as a characterization tool which provides component- and location-specific measurements of the glass transition temperature (Tg), a fundamental polymer property, in a model nanostructured diblock copolymer-a polymer chain comprised of two chemically dissimilar homopolymers bound by a single covalent bond. Nanostructured diblock copolymers are self-assembled periodic materials with domains rich in either block, confined by the domain interface. The parameters governing the domain Tg-namely, the bulk T g of the homopolymers, the domain period, and the degree of segmental mixing between the blocks-can be systematically varied by choosing the block chemistries and total chain length. This combination of features offers a wide parameter space for property optimization. Until now, no characterization tool has demonstrated the capability of providing spatially-resolved Tg measurements across the domain structure, information that is crucial for optimizing the end-use properties. The length scales associated with the domain period, O(10-100 nm), pose a significant barrier towards performing such measurements. Here, this barrier was overcome by selectively incorporating a fluorescent monomer into the diblock copolymer chain during synthesis, thereby controlling the location where Tg was measured in the self-assembled structure. In diblock copolymers of poly(n-butyl methacrylate- b-methyl methacrylate), PBMA-PMMA, which self-assemble into a lamellar morphology, a strong gradient in Tg of the higher-Tg PMMA block-42 K over 4 nm-was mapped with nanometer resolution. These measurements also revealed a strongly asymmetric influence of the domain interface on Tg, with a much smaller dynamic gradient being observed for the lower-Tg PBMA block. Tg was characterized for a series of fluorescently-labeled homopolymers dilutely blended into an unlabeled diblock copolymer matrix. Unlike in the neat diblock copolymer, the labeled PMMA chains were not attached to the domain interface. A comparison of the Tg depression of the homopolymers in the blends to equivalent labeled diblock copolymers reveal ~ 5 K and 10 K contributions due to nanoscale confinement and block attachment to the interface, respectively.
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