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3D‐printed polymer blends with programmable mechanical and compositional heterogeneity were fabricated using grayscale digital light processing by spatially modulating the intensity of light during printing and swelling the resulting part with a second monomer. A rubbery poly(ethylene glycol) diacrylate functionally graded print is variably swollen with acrylamide monomer as a function of crosslinking density. Following a secondary polymerization, a 3D‐printed functionally graded blend with regions of varying composition and stiffness was formed. A deterministic model for polymer conversion informs printing conditions to correspond with predicted material properties based upon local volume fractions of the two materials. Upon the secondary polymerization, two networks are present within the printed structure including glassy and rubbery regions. The compressive moduli of local regions within prints ranges from 76 to 200 MPa and measured moduli of the structures agree with predicted values acquired using finite element analysis. A lattice structure with prescribed local stiffness printed using grayscale exposures deforms differentially when compressed. Advantageously, local dimensional deformations caused by the removal of the unreacted printing monomer are eliminated due to the introduction of the second polymer. This method provides predictive control over local mechanical properties and high shape precision while maintaining the simplicity of vat photopolymerization.
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Additive manufacture of lightly crosslinked semicrystalline thiol–enes for enhanced mechanical performance
Photopolymerizable semicrystalline thermoplastics resulting from thiol–ene polymerizations were formed via fast polymerizations and achieved excellent mechanical properties. These materials have been shown to produce materials desirable for additive manufacturing (3D printing), especially for recyclable printing and investment casting. However, while well-resolved prints were previously achieved with the thiol–ene thermoplastics, the remarkable elongation at break ( ε max ) and toughness ( T ) attained in bulk were not realized for 3D printed components ( ε max,bulk ∼ 790%, T bulk ∼ 102 MJ m −3 vs. ε max,print < 5%, T print < 0.5 MJ m −3 ). In this work, small concentrations (5–10 mol%) of a crosslinker were added to the original thiol–ene resin composition without sacrificing crystallization potential to achieve semicrystalline, covalently crosslinked networks with enhanced mechanical properties. Improvements in ductility and overall toughness were observed for printed crosslinked structures, and substantial mechanical augmentation was further demonstrated with post-manufacture thermal conditioning of printed materials above the melting temperature ( T m ). In some instances, this thermal conditioning to reset the crystalline component of the crosslinked prints yielded mechanical properties that were comparable or superior to its bulk counterpart ( ε max ∼ 790%, T ∼ 95 MJ m −3 ). These unique photopolymerizations and their corresponding monomer compositions exhibited concurrent polymerization and crystallization along with mechanical properties that were tunable by changes to the monomer composition, photopolymerization conditions, and post-polymerization conditioning. This is the first example of a 3D printed semicrystalline, crosslinked material with thermally tunable mechanical properties that are superior to many commercially-available resins.
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- Award ID(s):
- 1809841
- PAR ID:
- 10187897
- Date Published:
- Journal Name:
- Polymer Chemistry
- Volume:
- 11
- Issue:
- 1
- ISSN:
- 1759-9954
- Page Range / eLocation ID:
- 39 to 46
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/c9py01452g
