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Title: Highly Tunable Thiol-Ene Photoresins for Volumetric Additive Manufacturing

Abstract

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.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1];  [1];  [1];  [1];  [1];  [1];  [2];  [3];  [2]; ORCiD logo [1]
  1. Lawrence Livermore National Laboratory Livermore CA 94550 USA
  2. Electrical, Computer, and Energy Engineering Department University of Colorado Boulder CO 80309 USA
  3. Materials Science and Engineering Program University of Colorado Boulder CO 80303 USA
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1669190
Alternate Identifier(s):
OSTI ID: 1688590; OSTI ID: 1773263; OSTI ID: 1785782
Report Number(s):
LLNL-JRNL-809451; LLNL-JRNL-809858
Journal ID: ISSN 0935-9648
Grant/Contract Number:  
AC52-07NA27344
Resource Type:
Published Article
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Name: Advanced Materials; Journal ID: ISSN 0935-9648
Publisher:
Wiley
Country of Publication:
Germany
Language:
English
Subject:
42 ENGINEERING; 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; acrylate; photopolymerization; thiol‐ene; tomography; volumetric additive manufacturing

Citation Formats

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., and Shusteff, Maxim. Highly Tunable Thiol-Ene Photoresins for Volumetric Additive Manufacturing. Germany: N. p., 2020. Web. https://doi.org/10.1002/adma.202003376.
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. Highly Tunable Thiol-Ene Photoresins for Volumetric Additive Manufacturing. Germany. https://doi.org/10.1002/adma.202003376
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., and Shusteff, Maxim. Thu . "Highly Tunable Thiol-Ene Photoresins for Volumetric Additive Manufacturing". Germany. https://doi.org/10.1002/adma.202003376.
@article{osti_1669190,
title = {Highly Tunable Thiol-Ene Photoresins for Volumetric Additive Manufacturing},
author = {Cook, Caitlyn C. and Fong, Erika J. and Schwartz, Johanna J. and Porcincula, Dominique H. and Kaczmarek, Allison C. and Oakdale, James S. and Moran, Bryan D. and Champley, Kyle M. and Rackson, Charles M. and Muralidharan, Archish and McLeod, Robert R. and Shusteff, Maxim},
abstractNote = {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.},
doi = {10.1002/adma.202003376},
journal = {Advanced Materials},
number = ,
volume = ,
place = {Germany},
year = {2020},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
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https://doi.org/10.1002/adma.202003376

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