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.
- Award ID(s):
- 1809841
- NSF-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
More Like this
-
more » « less
-
null (Ed.)The development of tunable and degradable crosslinked-polyanhydride networks from renewably derived itaconic anhydrides and multifunctional thiols is presented. Itaconic acid was initially converted to ethyl itaconic anhydride and isoamyl itaconic anhydride via a two-step synthetic procedure on hundred-gram scale with minimal purification. Dinorbornene-functionalized derivatives were prepared via cycloaddition chemistry, and photoinitiated thiol–ene polymerization reactions were explored using commercially available tetra- and hexa-functional thiols, all using solvent-free syntheses. The thiol–ene reaction kinetics of different monomer compositions were characterized by real-time Fourier transform infrared (RT-FTIR) spectroscopy, with the norbornene functionalized derivatives exhibiting the highest reactivity towards thiol–ene photopolymerizations. The thermal and mechanical characteristics of the thermosets were analyzed and the viscoelastic behavior was investigated by dynamic mechanical analysis to understand the influence of the ester functionality and choice of crosslinker on the material properties. The anhydride backbone was found to be susceptible to controlled degradation under physiologically-(phosphate-buffered saline) and environmentally-relevant (artificial seawater) testing conditions over a period of 60 days at 50 °C. This work demonstrates that itaconic acid may be a useful feedstock in the generation of degradable polyanhydride networks via thiol–ene photopolymerization.more » « less
-
more » « less
Abstract Current thoroughly described biodegradable and cross‐linkable polymers mainly rely on acrylate cross‐linking. However, despite the swift cross‐linking kinetics of acrylates, the concomitant brittleness of the resulting materials limits their applicability. Here, photo‐cross‐linkable poly(ε‐caprolactone) networks through orthogonal thiol‐ene chemistry are introduced. The step‐growth polymerized networks are tunable, predictable by means of the rubber elasticity theory and it is shown that their mechanical properties are significantly improved over their acrylate cross‐linked counterparts. Tunability is introduced to the materials, by altering
M c(or the molar mass between cross‐links), and its effect on the thermal properties, mechanical strength and degradability of the materials is evaluated. Moreover, excellent volumetric printability is illustrated and the smallest features obtained via volumetric 3D‐printing to date are reported, for thiol‐ene systems. Finally, by means of in vitro and in vivo characterization of 3D‐printed constructs, it is illustrated that the volumetrically 3D‐printed materials are biocompatible. This combination of mechanical stability, tunability, biocompatibility, and rapid fabrication by volumetric 3D‐printing charts a new path toward bedside manufacturing of biodegradable patient‐specific implants. -
more » « less
Abstract Photopolymerization is a ubiquitous, indispensable technique widely applied in applications from coatings, inks, and adhesives to thermosetting restorative materials for medical implants, and the fabrication of complex macroscale, microscale, and nanoscale 3D architectures via additive manufacturing. However, due to the brittleness inherent in the dominant acrylate‐based photopolymerized networks, a significant need exists for higher performance resin/oligomer formulations to create tough, defect‐free, mechanically ductile, thermally and chemically resistant, high modulus network polymers with rapid photocuring kinetics. This study presents densely cross‐linked triazole‐based glassy photopolymers capable of achieving preeminent toughness of ≈70 MJ m−3and 200% strain at ambient temperature, comparable to conventional tough thermoplastics. Formed either via photoinitiated copper(I)‐catalyzed cycloaddition of monomers containing azide and alkyne groups (CuAAC) or via photoinitiated thiol‐ene reactions from monomers containing triazole rings, these triazole‐containing thermosets completely recover their original dimensions and mechanical behavior after repeated deformations of 50% strain in the glassy state over multiple thermal recovery–strain cycles.
-
Print conditions for thermoplastics by filament-based material extrusion (MatEx) are commonly optimized to maximize the elastic modulus. However, these optimizations tend to ignore the impact of thermal history that depends on the specimen size and print path selection. Here, we investigate the effect of size print path (raster angle and build orientation) and print sequence on the mechanical properties of polycarbonate (PC) and polypropylene (PP). Examination of parallel and series printing of flat (XY) and stand-on (YZ) orientation of Type V specimens demonstrated that to observe statistical differences in the mechanical response that the interlayer time between printed roads should be approximately 5 s or less. The print time for a single layer in XY orientation is much longer than that for a single layer in YZ orientation, so print sequence only impacts the mechanical response in the YZ orientation. However, the specimen size and raster angle did influence the mechanical properties in XY orientation due to the differences in thermal history associated with intralayer time between adjacent roads. Moreover, all of these effects are significantly larger when printing PC than PP. These differences between PP and PC are mostly attributed to the mechanism of interface consolidation (crystallization vs. glass formation), which changes the requirements for a strong interface between roads (crystals vs. entanglements). These results illustrate how the print times dictated by the print path layout impact observed mechanical properties. This work also demonstrated that the options available in some standards developed for traditional manufacturing will change the quantitative results when applied to 3D printed parts.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/c9py01452g
