Engineering heterogeneous micro-mechano-microenvironments of extracellular matrix is of great interest in tissue engineering, but spatial control over mechanical heterogeneity in three dimensions is still challenging given the fact that geometry and stiffness are inherently intertwined in fabrication. Here, we develop a layer-by-layer three-dimensional (3D) printing paradigm which achieves orthogonal control of stiffness and geometry by capitalizing on the conventionally adverse effect of oxygen inhibition on free-radical polymerization. Controlled oxygen permeation and inhibition result in photo-cured hydrogel layers with thicknesses only weakly dependent to the ultraviolet exposure dosage. The dosage is instead leveraged to program the crosslink density and stiffness of the cured structures. The programmable stiffness spans nearly an order of magnitude (
Vat polymerization is a type of additive manufacturing that is used extensively to produce micro‐architected structures for mechanical applications, which brings the mechanical properties of photopolymerized resins into sharp focus. However, it is known that photopolymerization is sensitive to a number of factors, perhaps the most notorious of which is oxygen inhibition. Herein, the degree to which oxygen inhibition influences the macroscopic and microscopic properties of structures made using vat polymerization is explored. This work is motivated by an observation of lattices being >4 times softer in the experiment than predicted by simulation, which is hypothesized to be due to the material at the surface being incompletely cured. This hypothesis is supported by four‐point bending tests in which flexural modulus is found to increase with beam thickness. Nanoindentation and bulk compression studies show that this surface softening is present for three distinct resins. Importantly, it is observed that structures post‐print cured in nitrogen are stiffer than those post‐print cured in air, however, regardless of the post‐print curing environment, printing samples in the presence of oxygen makes them softer than samples photocured in nitrogen. Collectively, these results show the outsized influence of oxygen inhibition on micro‐architected structures realized using vat polymerization.
more » « less- NSF-PAR ID:
- 10419264
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Materials Technologies
- Volume:
- 8
- Issue:
- 12
- ISSN:
- 2365-709X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract E ~ 2–15 kPa) within the physiologically relevant range. We further demonstrate that extracellular matrices with programmed micro-mechano-environments can dictate 3D cellular organization, enabling in vitro tissue reconstruction. -
more » « less
Abstract Stretchable conductive materials have attracted great attention due to their potential applications as strain sensors, wearable electronics, soft robotics, and medical devices. The fabrication of these materials with customized object geometries is desirable, but the methods to achieve them are still highly limited. Additive manufacturing via vat photopolymerization can generate sophisticated object geometries, but there is still a significant need to print with materials that afford improved conductivity, mechanical properties, elastic recovery, and durability. Herein, stretchable strain sensors with a range of 3D printed designs are reported using vat photopolymerization. Ionic liquid resins are optimized for their printability using Sudan‐I as a photoabsorber and used to fabricate 3D objects that are subjected to compression, stretching, and bending loads that are detected as real‐time changes in current. Additionally, the self‐adhesive nature of these materials enables mechanically damaged structures to be mended together to regain its function as a strain sensor. These ionic liquid resins are compatible with commercial 3D printers, which enhances their applicability for on‐demand production of customized devices.
-
more » « less
Abstract Three-dimensional (3D) printing of metal components through powder bed fusion, material extrusion, and vat photopolymerization, has attracted interest continuously. Particularly, extrusion-based and photopolymerization-based processes employ metal particle-reinforced polymer matrix composites (PMCs) as raw materials. However, the resolution for extrusion-based printing is limited by the speed-accuracy tradeoff. In contrast, photopolymerization-based processes can significantly improve the printing resolution, but the filler loading of the PMC is typically low due to the critical requirement on raw materials’ rheological properties. Herein, we develop a new metal 3D printing strategy by utilizing micro-continuous liquid interface printing (μCLIP) to print PMC resins comprising nanoporous copper (NP-Cu) powders. By balancing the need for higher filler loading and the requirements on rheological properties to enable printability for the μCLIP, the compositions of PMC resin were optimized. In detail, the concentration of the NP-Cu powders in the resins can reach up to 40 wt% without sacrificing the printability and printing speed (10 μm·s−1). After sintering, 3D copper structures with microscale features (470 ± 140 μm in diameter) manifesting an average resistivity of 150 kΩ·mm can be realized. In summary, this new strategy potentially benefits the rapid prototyping of metal components with higher resolution at faster speeds.
-
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.more » « less
-
more » « less
Recent developments in micro-scale additive manufacturing (AM) have opened new possibilities in state-of-the-art areas, including microelectromechanical systems (MEMS) with intrinsically soft and compliant components. While fabrication with soft materials further complicates micro-scale AM, a soft photocurable polydimethylsiloxane (PDMS) resin, IP-PDMS, has recently entered the market of two-photon polymerization (2PP) AM. To facilitate the development of microdevices with soft components through the application of 2PP technique and IP-PDMS material, this research paper presents a comprehensive material characterization of IP-PDMS. The significance of this study lies in the scarcity of existing research on this material and the thorough investigation of its properties, many of which are reported here for the first time. Particularly, for uncured IP-PDMS resin, this work evaluates a surface tension of 26.7 ± 4.2 mN/m, a contact angle with glass of 11.5 ± 0.6°, spin-coating behavior, a transmittance of more than 90% above 440 nm wavelength, and FTIR with all the properties reported for the first time. For cured IP-PDMS, novel characterizations include a small mechanical creep, a velocity-dependent friction coefficient with glass, a typical dielectric permittivity value of 2.63 ± 0.02, a high dielectric/breakdown strength for 3D-printed elastomers of up to 73.3 ± 13.3 V/µm and typical values for a spin coated elastomer of 85.7 ± 12.4 V/µm, while the measured contact angle with water of 103.7 ± 0.5°, Young’s modulus of 5.96 ± 0.2 MPa, and viscoelastic DMA mechanical characterization are compared with the previously reported values. Friction, permittivity, contact angle with water, and some of the breakdown strength measurements were performed with spin-coated cured IP-PDMS samples. Based on the performed characterization, IP-PDMS shows itself to be a promising material for micro-scale soft MEMS, including microfluidics, storage devices, and micro-scale smart material technologies.
