Results of an interlaboratory study on the working curve in vat photopolymerization.

The working curve informs resin properties and print parameters for stereolithography, digital light processing, and other photopolymer additive manufacturing (PAM) technologies. First demonstrated in 1992, the working curve measurement of cure depth vs radiant exposure of light is now a foundational measurement in the field of PAM. Despite its widespread use in industry and academia, there is no formal method or procedure for performing the working curve measurement, raising questions about the utility of reported working curve parameters. Here, an interlaboratory study (ILS) is described in which 24 individual laboratories performed a working curve measurement on an aliquot from a single batch of PAM resin. The ILS reveals that there is enormous scatter in the working curve data and the key fit parameters derived from it. The measured depth of light penetration Dp varied by as much as 7x between participants, while the critical radiant exposure for gelation Ec varied by as much as 70x. This significant scatter is attributed to a lack of common procedure, variation in light engines, epistemic uncertainties from the Jacobs equation, and the use of measurement tools with insufficient precision. The ILS findings highlight an urgent need for procedural standardization and better hardware characterization in this rapidly growing field.

Influence of fluorescent dopants on the vat photopolymerization of acrylate-based plastic scintillators for application in neutron/gamma pulse shape discrimination.

Plastic scintillators, a class of solid-state materials used for radiation detection, were additively manufactured with vat photopolymerization. The photopolymer resins consisted of a primary dopant and a secondary dopant dissolved in a bisphenol A ethoxylate diacrylate-based matrix. The absorptive dopants significantly influence important print parameters, for example, secondary dopants decrease the light penetration depth by a factor > 12 ×. The primary dopant 2,5-diphenyloxazole had minimal impact on the printing process even when loaded at 25 % by mass of the resin. Working curve measurements, which relate energy dose to cure depth, were performed as a function of feature size to further assess the influence of dopants. Photopatterns smaller than 150 µm width had apparent increases in critical energy dose compared to larger photopatterns, while all resins maintained printed features in line gratings with 50 µm of separation. Printed scintillator monoliths were compared to scintillators cast by traditional molding, demonstrating that the layer-by-layer printing process does not decrease scintillation response. A maximum light output of 31 % of a benchmark plastic scintillator (EJ-200) and successful pulse shape discrimination were achieved with 20 % by mass 2,5-diphenyloxazole as the primary dopant and 0.1 % by mass 9,9-dimethyl-2,7-distyrylfluorene as the secondary dopant in printed scintillator samples.

A Data-Driven Approach to Complex Voxel Predictions in Grayscale Digital Light Processing Additive Manufacturing Using U-Nets and Generative Adversarial Networks.

Data-driven U-net machine learning (ML) models, including the pix2pix conditional generative adversarial network (cGAN), are shown to predict 3D printed voxel geometry in digital light processing (DLP) additive manufacturing. A confocal microscopy-based workflow allows for the high-throughput acquisition of data on thousands of voxel interactions arising from randomly gray-scaled digital photomasks. Validation between prints and predictions shows accurate predictions with sub-pixel scale resolution. The trained cGAN performs virtual DLP experiments such as feature size-dependent cure depth, anti-aliasing, and sub-pixel geometry control. The pix2pix model is also applicable to larger masks than it is trained on. To this end, the model can qualitatively inform layer-scale and voxel-scale print failures in real 3D-printed parts. Overall, machine learning models and the data-driven methodology, exemplified by U-nets and cGANs, show considerable promise for predicting and correcting photomasks to achieve increased precision in DLP additive manufacturing.

Synergistic Fire Resistance of Nanobrick Wall Coated 3D Printed Photopolymer Lattices.

Photopolymer additive manufacturing has become the subject of widespread interest in recent years due to its capacity to enable fabrication of difficult geometries that are impossible to build with traditional manufacturing methods. The flammability of photopolymer resin materials and the lattice structures enabled by 3D printing is a barrier to widespread adoption that has not yet been adequately addressed. Here, a water-based nanobrick wall coating is deposited on 3D printed parts with simple (i.e., dense solid) or complex (i.e., lattice) geometries. When subject to flammability testing, the printed parts exhibit no melt dripping and a propensity toward failure at the print layer interfaces. Moving from a simple solid geometry to a latticed geometry leads to reduced time to failure during flammability testing. For nonlatticed parts, the coating provides negligible improvement in fire resistance, but coating of the latticed structures significantly increases time to failure by up to ≈340% compared to the uncoated lattice. The synergistic effect of coating and latticing is attributed to the lattice structures' increased surface area to volume ratio, allowing for an increased coating:photopolymer ratio and the ability of the lattice to better accommodate thermal expansion strains. Overall, nanobrick wall coated lattices can serve as metamaterials to increase applications of polymer additive manufacturing in extreme environments.

Characterizing light engine uniformity and its influence on liquid crystal display based vat photopolymerization printing.

Vat photopolymerization (VP) is a rapidly growing category of additive manufacturing. As VP methods mature the expectation is that the quality of printed parts will be highly reproducible. At present, detailed characterization of the light engines used in liquid crystal display (LCD)-based VP systems is lacking and so it is unclear if they are built to sufficiently tight tolerances to meet the current and/or future needs of additive manufacturing. Herein, we map the irradiance, spectral characteristics, and optical divergence of a nominally 405 nm LCD-based VP light engine. We find that there is notable variation in all of these properties as a function of position on the light engine that cause changes in extent of polymerization and surface texture. We further demonstrate through a derived photon absorption figure of merit and through printed test parts that the spatial heterogeneity observed in the light engine is significant enough to affect part fidelity. These findings help to explain several possible causes of variable part quality and also highlight the need for improved optical performance on LCD-based VP printers.

Clay-Filled Polyelectrolyte Complex Nanocoating for Flame-Retardant Polyurethane Foam.

Polyurethane foam (PUF) is a highly flammable material typically used for cushioning in furniture and automobiles. A polyelectrolyte complex coating containing polyethylenimine, ammonium polyphosphate, and halloysite clay was applied to PUF using a two-step deposition process in an attempt to reduce its flammability. Electron microscopy confirms that this conformal thin film preserves the porous morphology of the foam and adds 20% to the foam's weight. Directly exposing coated foam to a butane torch flame yields a 73% residue after burning while keeping the internal structure of the foam intact. Cone calorimetry reveals a 52.5% reduction in the peak heat release rate (pkHRR) of the clay-based coating compared to that of the uncoated foam. This significant reduction in pkHRR and preservation of the porous structure of the foam highlights the utility of this easy-to-deposit, environmentally benign treatment to reduce the foam's flammability.

Super Gas Barrier of a Polyelectrolyte/Clay Coacervate Thin Film.

Transparent polymeric thin films with high oxygen barrier are important for extending the shelf life of food and protecting flexible organic electronic devices. Polyelectrolyte/clay multilayer nanocoatings are shown to exhibit super gas barrier performance, but the layer-by-layer assembly process requires numerous deposition steps. In an effort to more quickly fabricate this type of barrier, a polyelectrolyte/clay coacervate composed of branched polyethyleneimine (PEI), poly(acrylic acid) (PAA), and kaolinite (KAO) clay is prepared and deposited in a single step, followed by humidity and thermal post-treatments. When deposited onto a 179 µm poly(ethylene terephthalate) (PET) film, a 4 µm coacervate coating reduces the oxygen transmission rate (OTR) by more than three orders of magnitude, while maintaining high transparency. This single-step deposition process uses only low-cost, water-based components and ambient conditions, which can be used to for sensitive food and electronics packaging.

Environmentally Benign and Self-Extinguishing Multilayer Nanocoating for Protection of Flammable Foam.

Most current flame-retardant nanocoatings for flexible polyurethane foam (PUF) consist of passive barriers, such as clay, graphene oxide, or metal hydroxide. In an effort to develop a polymeric and environmentally benign nanocoating for PUF, positively charged chitosan (CH) and anionic sodium hexametaphosphate (PSP) were deposited using layer-by-layer (LbL) assembly. Only six bilayers of CH/PSP film can withstand flame penetration during exposure to a butane torch (∼1400 °C) for 10 s and stop flame spread on the foam. Additionally, cone calorimetry reveals that the fire growth rate, peak heat release rate, and maximum average rate of heat emission are reduced by 55, 43, and 38%, respectively, compared with uncoated foam. This multilayer thin film quickly dehydrates to form an intumescent charred exoskeleton on the surface of the open-celled structure of polyurethane, inhibiting heat transfer and completely eliminating melt dripping. This entirely polymeric nanocoating provides a safe and effective alternative for reducing the fire hazard of polyurethane foam that is widely used for cushioning and insulation.

UV-protection from chitosan derivatized lignin multilayer thin film.

Lignin is one of the most abundant renewable materials on the earth. Despite possessing useful antioxidant and UV absorbing properties, its effective utilization in technology has been hampered by its relative insolubility and difficulty to process. In this work, a simple chemical derivatization process is utilized which yields water-soluble lignin possessing anionic carboxylate groups. These carboxylate groups give lignin polyanionic behavior and enable its utilization in the growth of a functional film via layer-by-layer (LbL) assembly with biologically sourced chitosan. The growth mechanism of this film is hypothesized to be a result of both hydrogen bonding and ionic interactions. The film demonstrates excellent UV-absorptive capability. A 100 nm thick chitosan/lignin coating was applied to a poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) film and shown to reduce its degradation sixfold over the course of a 1 hour exposure to harsh UV light. This is the first demonstration of lignin being utilized in a fully biologically derived LbL film. Utilization of lignin in LbL assembly is an important step in the development of renewable nanotechnology.