An official website of the United States government
Abstract An acoustic liquefaction approach to enhance the flow of yield stress fluids during Digital Light Processing (DLP)‐based 3D printing is reported. This enhanced flow enables processing of ultrahigh‐viscosity resins (μapp > 3700 Pa s at shear rates = 0.01 s–1) based on silica particles in a silicone photopolymer. Numerical simulations of the acousto–mechanical coupling in the DLP resin feed system at different agitation frequencies predict local resin flow velocities exceeding 100 mm s–1at acoustic transduction frequencies of 110 s–1. Under these conditions, highly loaded particle suspensions (weight fractions, ϕ = 0.23) can be printed successfully in complex geometries. Such mechanically reinforced composites possess a tensile toughness 2000% greater than the neat photopolymer. Beyond an increase in processible viscosities, acoustophoretic liquefaction DLP (AL‐DLP) creates a transient reduction in apparent viscosity that promotes resin recirculation and decreases viscous adhesion. As a result, acoustophoretic liquefaction Digital Light Processing (AL‐DLP) improves the printed feature resolution by more than 25%, increases printable object sizes by over 50 times, and can build parts >3 × faster when compared to conventional methodologies.
more »
« less
This content will become publicly available on September 11, 2025
Toughening and Imparting Deconstructability to 3D‐Printed Glassy Thermosets with “Transferinker” Additives
Abstract Thermoset toughness and deconstructability are often opposing features; simultaneously improving both without sacrificing other mechanical properties (e.g., stiffness and tensile strength) is difficult, but, if achieved, could enhance the usage lifetime and end‐of‐life options for these materials. Here, a strategy that addresses this challenge in the context of photopolymer resins commonly used for 3D printing of glassy, acrylic thermosets is introduced. It is shown that incorporating bis‐acrylate “transferinkers,” which are cross‐linkers capable of undergoing degenerative chain transfer and new strand growth, as additives (5–25 mol%) into homemade or commercially available photopolymer resins leads to photopolymer thermosets with substantially improved tensile toughness and triggered chemical deconstructability with minimal impacts on Young's moduli, tensile strengths, and glass transition temperatures. These properties result from a transferinker‐driven topological transition in network structure from the densely cross‐linked long, heterogeneous primary strands of traditional photopolymer networks to more uniform, star‐like networks with few dangling ends; the latter structure more effectively bear stress yet is also more easily depercolated via solvolysis. Thus, transferinkers represent a simple and effective strategy for improving the mechanical properties of photopolymer thermosets and providing a mechanism for their triggered deconstructability.
more »
« less
- Award ID(s):
- 2116298
- PAR ID:
- 10541213
- Publisher / Repository:
- Wiley
- Date Published:
- Journal Name:
- Advanced Materials
- ISSN:
- 0935-9648
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Additive manufacturing, otherwise known as three-dimensional (3D) printing, is a rapidly growing technique that is increasingly used for the production of polymer products, resulting in an associated increase in plastic waste generation. Waste from a particular class of 3D-printing, known as vat photopolymerization, is of particular concern, as these materials are typically thermosets that cannot be recycled or reused. Here, we report a mechanical recycling process that uses cryomilling to generate a thermoset powder from photocured parts that can be recycled back into the neat liquid monomer resin. Mechanical recycling with three different materials is demonstrated: two commercial resins with characteristic brittle and elastic mechanical properties and a third model material formulated in-house. Studies using photocured films showed that up to 30 wt% of the model material could be recycled producing a toughness of 2.01 ± 0.55 MJ/m3, within error of neat analogues (1.65 ± 0.27 MJ/m3). Using dynamic mechanical analysis and atomic force microscopy-based infrared spectroscopy, it was determined that monomers diffuse into the recycled powder particles, creating interpenetrating networks upon ultraviolet (UV) exposure. This process mechanically adheres the particles to the matrix, preventing them from acting as failure sites under a tensile load. Finally, 3D-printing of the commercial brittle material with 10 wt% recycle content produced high quality parts that were visually similar. The maximum stress (46.7 ± 6.2 MPa) and strain at break (11.6 ± 2.3%) of 3D-printed parts with recycle content were within error the same as neat analogues (52.0 ± 1.7 MPa; 13.4 ± 1.8%). Overall, this work demonstrates mechanical recycling of photopolymerized thermosets and shows promise for the reuse of photopolymerized 3D-printing waste.more » « less
-
Abstract The chemically crosslinked network structures make epoxies, the most common thermosets, unable or hard to be recycled, causing environmental problems and economic losses. Epoxy‐based vitrimers, polymer networks deriving from epoxy resins, can be thermally malleable according to bond exchange reactions (BERs), opening the door to recycle epoxy thermosets. Here a series of experiments were carried out to study the effects of processing conditions (such as particle size distributions, temperature, time, and pressure) on recycling of an epoxy‐anhydride vitrimer. Polymer powders from the epoxy‐anhydride vitrimer with different size distributions were prepared and characterized, and the influence of particle size on the mechanical performance of recycled epoxy‐anhydride vitrimers was investigated by dynamic mechanical analysis and uniaxial tensile test. Experimental results demonstrated that finer polymer powders can increase the contacting surfaces of recycled materials and thus result in high quality of recycled materials. In addition, the influences of other treating parameters, such as temperature, time, and pressure, were also discussed in this study. Adjusting these treating parameters can help the design of an optimized reprocessing procedure to meet practical engineering applications.more » « less
-
The structural similarities between lignin-derivable bisguaiacols and petroleum-derived bisphenol A/F (BPA/BPF) suggest that bisguaiacols could be ideal biobased alternatives to BPA/BPF in non-isocyanate polyurethane (NIPU) thermosets. Herein, bisguaiacol/bisphenol-derived cyclic carbonates with variations in methoxy content and bridging-carbon substitution were cured with two triamines of different chain lengths, and the impact of these differences on the thermomechanical properties of NIPU networks was examined. The methoxy groups present in the lignin-derivable cyclic carbonates led to thermosets with significantly improved toughness (∼49–59 MJ m −3 ) and elongation at break ( ε b ∼195–278%) vs. the BPA/BPF-based benchmarks (toughness ∼ 26–35 MJ m −3 , ε b ∼ 86–166%). Furthermore, the addition of dimethyl substitution on the bridging carbon resulted in increased yield strength ( σ y ) – from ∼28 MPa for networks with unsubstituted bridging carbons to ∼45 MPa for the dimethyl-substituted materials. These enhancements to mechanical properties were achieved while retaining essential thermoset properties, such as application-relevant moduli and thermal stabilities. Finally, the triamine crosslinkers provided substantial tunability of thermomechanical properties and produced NIPUs that ranged from rigid materials with a high yield strength ( σ y ∼ 65–88 MPa) to flexible and tough networks. Overall, the structure-property relationships presented highlight a promising framework for the design of versatile, bio-derivable, NIPU thermosets.more » « less
-
Abstract The incorporation of a secondary network into traditional single‐network hydrogels can enhance mechanical properties, such as toughness and loading to failure. These features are important for many applications, including as biomedical materials; however, the processing of interpenetrating polymer network (IPN) hydrogels is often limited by their multistep fabrication procedures. Here, a one‐pot scheme for the synthesis of biopolymer IPN hydrogels mediated by the simultaneous crosslinking of two independent networks with light, namely: i) free‐radical crosslinking of methacrylate‐modified hyaluronic acid (HA) to form the primary network and ii) thiol–ene crosslinking of norbornene‐modified HA with thiolated guest–host assemblies of adamantane and β‐cyclodextrin to form the secondary network, is reported. The mechanical properties of the IPN hydrogels are tuned by changing the network composition, with high water content (≈94%) hydrogels exhibiting excellent work of fracture, tensile strength, and low hysteresis. As proof‐of‐concept, the IPN hydrogels are implemented as low‐viscosity Digital Light Processing resins to fabricate complex structures that recover shape upon loading, as well as in microfluidic devices to form deformable microparticles. Further, the IPNs are cytocompatible with cell adhesion dependent on the inclusion of adhesive peptides. Overall, the enhanced processing of these IPN hydrogels will expand their utility across applications.more » « less
