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3D in Situ Chemical Synthesis : = Additive Manufacturing of Functional Polymeric Materials Via Vat Photo-Polymerization.

Record Type:	Language materials, manuscript : Monograph/item
Title/Author:	3D in Situ Chemical Synthesis :/
Reminder of title:	Additive Manufacturing of Functional Polymeric Materials Via Vat Photo-Polymerization.
Author:	Chen, Amylynn C.
Description:	1 online resource (117 pages)
Notes:	Source: Dissertations Abstracts International, Volume: 85-03, Section: B.
Contained By:	Dissertations Abstracts International85-03B.
Subject:	Mechanical properties. -
Online resource:	click for full text (PQDT)
ISBN:	9798380267465

3D in Situ Chemical Synthesis : = Additive Manufacturing of Functional Polymeric Materials Via Vat Photo-Polymerization.
Chen, Amylynn C.

3D in Situ Chemical Synthesis :Additive Manufacturing of Functional Polymeric Materials Via Vat Photo-Polymerization. - 1 online resource (117 pages)

Source: Dissertations Abstracts International, Volume: 85-03, Section: B.

Thesis (Ph.D.)--California Institute of Technology, 2023.

Includes bibliographical references

As additive manufacturing gains popularity in rapid-prototyping, manufacturing, and customized production, there is a continuous demand in seeking new materials with advanced functionalities to satisfy the wide range of applications in aerospace, construction, optics, actuation, dentistry, biomedical practices, and even food industry. Vat photopolymerization (VP), a light-enabled AM technique, is particularly promising due to its ability to achieve good surface quality, high resolution, and large volumetric throughput. The vast majority of materials obtained by VP are covalently-crosslinked thermosets with nondegradable carbon backbones. This highly crosslinked polymer structure gives rise to stiff and brittle materials, limiting the structural functionality in desired applications.This thesis explores a variety of polymer network structures for new VP photopolymers: a) dynamically-crosslinked compliant polymer, b) interpenetrating network (IPN) hydrogel, and c) covalently-crosslinked polymer with labile group (ex. ester) insertion to polymer backbone. With the dynamic crosslinking system, we demonstrate tunable mechanical behaviors of the metal-coordinated supramolecular polymers. These materials display a range of failure strain of 450%-940% and ultimate tensile strength (UTS) of 12.4-2.2 MPa with varying resin compositions. To incorporate multifunctionality, we design thermoresponsive IPN hydrogels by fabricating a hydrophilic host polymer network via VP and a subsequent formation a thermoresponsive 2nd network (poly(N-Isopropylacrylamide)). The architected IPNs consistently display strong polymer-liquid phase separation behavior and a tunable water release behavior with volumetric shrinkage between 30% and 70% upon heating at 50\uD835\uDC5CC. Finally, to promote the degradability of the acylate-based photoresin, we demonstrated successful incorporation for ester functional groups into the polymer backbone via radical ring opening polymerization of cyclic ketene acetals. The obtained polymer undergoes 84% mass loss within 7 hours under hydrolytic degradation condition. Overall, we demonstrated VP as a powerful technique to achieve one-pot synthesis and fabrication of functional materials. Our explorations on the development of degradable photopolymers, thermoresponsive double-network hydrogels, and metal-coordinated supramolecular polymers provide valuable insights into the impact of resin formulation on mechanical properties. From analyzing the molecular weight of 3DP materials to finetuning of phase separation behavior and degradability, we demonstrate that VP provides a new platform to inspire advanced photoresin design strategies for desirable mechanical performance.

Electronic reproduction.
Ann Arbor, Mich. :
ProQuest,
2024

Mode of access: World Wide Web

ISBN: 9798380267465Subjects--Topical Terms:

1004682
Mechanical properties.
Index Terms--Genre/Form:

554714
Electronic books.

3D in Situ Chemical Synthesis : = Additive Manufacturing of Functional Polymeric Materials Via Vat Photo-Polymerization.
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500 $a Source: Dissertations Abstracts International, Volume: 85-03, Section: B.
500 $a Advisor: Greer, Julia R.
502 $a Thesis (Ph.D.)--California Institute of Technology, 2023.
504 $a Includes bibliographical references
520 $a As additive manufacturing gains popularity in rapid-prototyping, manufacturing, and customized production, there is a continuous demand in seeking new materials with advanced functionalities to satisfy the wide range of applications in aerospace, construction, optics, actuation, dentistry, biomedical practices, and even food industry. Vat photopolymerization (VP), a light-enabled AM technique, is particularly promising due to its ability to achieve good surface quality, high resolution, and large volumetric throughput. The vast majority of materials obtained by VP are covalently-crosslinked thermosets with nondegradable carbon backbones. This highly crosslinked polymer structure gives rise to stiff and brittle materials, limiting the structural functionality in desired applications.This thesis explores a variety of polymer network structures for new VP photopolymers: a) dynamically-crosslinked compliant polymer, b) interpenetrating network (IPN) hydrogel, and c) covalently-crosslinked polymer with labile group (ex. ester) insertion to polymer backbone. With the dynamic crosslinking system, we demonstrate tunable mechanical behaviors of the metal-coordinated supramolecular polymers. These materials display a range of failure strain of 450%-940% and ultimate tensile strength (UTS) of 12.4-2.2 MPa with varying resin compositions. To incorporate multifunctionality, we design thermoresponsive IPN hydrogels by fabricating a hydrophilic host polymer network via VP and a subsequent formation a thermoresponsive 2nd network (poly(N-Isopropylacrylamide)). The architected IPNs consistently display strong polymer-liquid phase separation behavior and a tunable water release behavior with volumetric shrinkage between 30% and 70% upon heating at 50\uD835\uDC5CC. Finally, to promote the degradability of the acylate-based photoresin, we demonstrated successful incorporation for ester functional groups into the polymer backbone via radical ring opening polymerization of cyclic ketene acetals. The obtained polymer undergoes 84% mass loss within 7 hours under hydrolytic degradation condition. Overall, we demonstrated VP as a powerful technique to achieve one-pot synthesis and fabrication of functional materials. Our explorations on the development of degradable photopolymers, thermoresponsive double-network hydrogels, and metal-coordinated supramolecular polymers provide valuable insights into the impact of resin formulation on mechanical properties. From analyzing the molecular weight of 3DP materials to finetuning of phase separation behavior and degradability, we demonstrate that VP provides a new platform to inspire advanced photoresin design strategies for desirable mechanical performance.
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