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Additive Manufacturing of 3D Functional Materials: From Surface Chemistry to Combustion-Derived Materials


Yee, Daryl Wei Liang (2020) Additive Manufacturing of 3D Functional Materials: From Surface Chemistry to Combustion-Derived Materials. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/ya58-cn88.


Over the past decade, additive manufacturing has emerged as one of the most powerful manufacturing tools available today. Vat photopolymerization techniques, in particular, are especially promising as they are capable of achieving high resolutions and throughputs. However, the vast majority of materials that are compatible with them only have structural functionality. The fabrication of functional materials still remains a challenge in the field: functional polymers often require a complex multi-step synthesis. Ceramics-based photoresins are limited in composition and are challenging to use or synthesize. Metals have also been hardly explored with vat photopolymerization techniques.

This thesis explores methods of fabricating functional materials with vat photopolymerization. We develop accessible techniques for the fabrication of functional polymers, ceramics, metals, and multimaterials at a variety of length scales, from sub-micron to centimeter scales. On the polymer front, we first explore how surface coatings can be an accessible method of introducing chemical functionality to a material. In particular, we demonstrate the surface coating of genomic DNA on an architected polymeric structure and show how it can be used as a drug capture device to reduce off-target toxicity in chemotherapy. We also explore the use of click chemistry, the thiol-Michael reaction in particular, in the facile synthesis of acrylate monomers with a variety of functional groups. We demonstrate the compatibility of these functionalized monomers with two-photon lithography and highlight some potential applications of these functional polymers structures.

In the fabrication of ceramics and metals, we present a novel technique called photopolymer complex synthesis that combines solution combustion synthesis with vat photopolymerization to enable their fabrication. We illustrate the use of this technique by first fabricating piezoelectric zinc oxide architected structures with sub-micron features using two-photon lithography. Following that, we fabricate lithium cobalt oxide structures using digital light processing printing and highlight their use as architected lithium-ion battery cathodes. Lastly, we show how photopolymer complex synthesis can be expanded to fabricate metal and multimaterial architected structures. Our work highlights the use of polymer chemistry and materials science in expanding the range of materials that are compatible with vat photopolymerization, with the vision of democratizing the fabrication of advanced functional materials and enabling the production of previously impossible 3D devices.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Additive Manufacturing; Metal Oxides; Metals; Surface Chemistry; Combustion Synthesis; Vat Photopolymerization; Chemotherapy; Architected Materials; Zinc Oxide; Genomic DNA; Lithium Cobalt Oxide; Hydrogels; Photopolymer Complex Synthesis; Thiol-Michael Addition
Degree Grantor:California Institute of Technology
Division:Engineering and Applied Science
Major Option:Materials Science
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Greer, Julia R.
Thesis Committee:
  • Faber, Katherine T. (chair)
  • Grubbs, Robert H.
  • Johnson, William Lewis
  • Greer, Julia R.
Defense Date:29 May 2020
Non-Caltech Author Email:yee.daryl (AT)
Funding AgencyGrant Number
National Institutes of Health (NIH)1R01 CA194533-01
Department of Energy (DOE)DE-SC0006599
Department of Energy (DOE)DE-SC0019166
National Security Science and Engineering Faculty FellowshipN00014-16-1-2827
Record Number:CaltechTHESIS:06042020-112316408
Persistent URL:
Related URLs:
URLURL TypeDescription adapted for ch. 3: Describes the thiol-Michael click chemistry synthesis adapted for ch. 4: Describes the zinc oxide fabrication DocumentPatent US10646505B2, discussed in ch. 2 . Describes some of the ChemoFilter concepts
Yee, Daryl Wei Liang0000-0002-4114-6167
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:13777
Deposited By: Daryl Yee
Deposited On:08 Jun 2020 18:01
Last Modified:08 Nov 2023 00:27

Thesis Files

PDF (Full Thesis) - Final Version
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[img] Video (AVI) (Confocal fluorescence z-image stacks from PETTA/N-BOC (Chapter 3)) - Supplemental Material
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[img] Video (AVI) (Confocal fluorescence z-image stacks from PETTA/N-BOC(Cys) (Chapter 3)) - Supplemental Material
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