Highly Tunable Thiol-Ene Photoresins for Volumetric Additive Manufacturing

Cook, Caitlyn C.; Fong, Erika J.; Schwartz, Johanna J.; Porcincula, Dominique H.; Kaczmarek, Allison C.; Oakdale, James S.; Moran, Bryan D.; Champley, Kyle M.; Rackson, Charles M.; Muralidharan, Archish; McLeod, Robert R.; Shusteff, Maxim

doi:10.1002/adma.202003376

Highly Tunable Thiol-Ene Photoresins for Volumetric Additive Manufacturing

Journal Article · Thu Oct 01 00:00:00 EDT 2020 · Advanced Materials

DOI:https://doi.org/10.1002/adma.202003376· OSTI ID:1669190

^[1]; Fong, Erika J. ^[1]; ^[1]; Porcincula, Dominique H. ^[1]; Kaczmarek, Allison C. ^[1]; Oakdale, James S. ^[1]; Moran, Bryan D. ^[1]; Champley, Kyle M. ^[1]; Rackson, Charles M. ^[2]; Muralidharan, Archish ^[3]; McLeod, Robert R. ^[2]; ^[1]

Lawrence Livermore National Laboratory Livermore CA 94550 USA
Electrical, Computer, and Energy Engineering Department University of Colorado Boulder CO 80309 USA
Materials Science and Engineering Program University of Colorado Boulder CO 80303 USA

Volumetric additive manufacturing (VAM) forms complete 3D objects in a single photocuring operation without layering defects, enabling 3D printed polymer parts with mechanical properties similar to their bulk material counterparts. This study presents the first report of VAM-printed thiol-ene resins. With well-ordered molecular networks, thiol-ene chemistry accesses polymer materials with a wide range of mechanical properties, moving VAM beyond the limitations of commonly used acrylate formulations. Since free-radical thiol-ene polymerization is not inhibited by oxygen, the nonlinear threshold response required in VAM is introduced by incorporating 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) as a radical scavenger. Tuning of the reaction kinetics is accomplished by balancing inhibitor and initiator content. Coupling this with quantitative measurements of the absorbed volumetric optical dose allows control of polymer conversion and gelation during printing. Importantly, this work thereby establishes the first comprehensive framework for spatial–temporal control over volumetric energy distribution, demonstrating structures 3D printed in thiol-ene resin by means of tomographic volumetric VAM. Mechanical characterization of this thiol-ene system, with varied ratios of isocyanurate and triethylene glycol monomers, reveals highly tunable mechanical response far more versatile than identical acrylate-based resins. This broadens the range of materials and properties available for VAM, taking another step toward high-performance printed polymers.

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Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE; USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1669190

Alternate ID(s):: OSTI ID: 1773263
OSTI ID: 1785782
OSTI ID: 1688590

Report Number(s):: LLNL-JRNL--809451; LLNL-JRNL--809858; 2003376

Journal Information:: Advanced Materials, Journal Name: Advanced Materials; ISSN 0935-9648

Publisher:: WileyCopyright Statement

Country of Publication:: Germany

Language:: English

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36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
42 ENGINEERING
acrylate
photopolymerization
thiol‐ene
tomography
volumetric additive manufacturing

Highly Tunable Thiol-Ene Photoresins for Volumetric Additive Manufacturing

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