Deconvolution volumetric additive manufacturing.

Volumetric additive manufacturing techniques are a promising pathway to ultra-rapid light-based 3D fabrication. Their widespread adoption, however, demands significant improvement in print fidelity. Currently, volumetric additive manufacturing prints suffer from systematic undercuring of fine features, making it impossible to print objects containing a wide range of feature sizes, precluding effective adoption in many applications. Here, we uncover the reason for this limitation: light dose spread in the resin due to chemical diffusion and optical blurring, which becomes significant for features ⪅0.5 mm. We develop a model that quantitatively predicts the variation of print time with feature size and demonstrate a deconvolution method to correct for this error. This enables prints previously beyond the capabilities of volumetric additive manufacturing, such as a complex gyroid structure with variable thickness and a fine-toothed gear. These results position volumetric additive manufacturing as a mature 3D printing method, all but eliminating the gap to industry-standard print fidelity.

Versatile volumetric additive manufacturing with 3D ray tracing.

Tomographic volumetric additive manufacturing (VAM) is an optical 3D printing technique where an object is formed by photopolymerizing resin via tomographic projections. Currently, these projections are calculated using the Radon transform from computed tomography but it ignores two fundamental properties of real optical projection systems: finite etendue and non-telecentricity. In this work, we introduce 3D ray tracing as a new method of computing projections in tomographic VAM and demonstrate high fidelity printing in non-telecentric and higher etendue systems, leading to a 3x increase in vertical build volume than the standard Radon method. The method introduced here expands the possible tomographic VAM printing configurations, enabling faster, cheaper, and higher fidelity printing.

Correcting ray distortion in tomographic additive manufacturing.

Light-based additive manufacturing techniques enable a rapid transition from object design to production. In these approaches, a 3D object is typically built by successive polymerization of 2D layers in a photocurable resin. A recently demonstrated technique, however, uses tomographic dose patterning to establish a 3D light dose distribution within a cylindrical glass vial of photoresin. Lensing distortion from the cylindrical vial is currently mitigated by either an index matching bath around the print volume or a cylindrical lens. In this work, we show that these hardware approaches to distortion correction are unnecessary. Instead, we demonstrate how the lensing effect can be computationally corrected by resampling the parallel-beam radon transform into an aberrated geometry. We also demonstrate a more general application of our computational approach by correcting for non-telecentricity inherent in most optical projection systems. We expect that our results will underpin a more simple and flexible class of tomographic 3D printers where deviations from the assumed parallel-beam projection geometry are rectified computationally.

Direct printing of functional 3D objects using polymerization-induced phase separation.

3D printing has enabled materials, geometries and functional properties to be combined in unique ways otherwise unattainable via traditional manufacturing techniques, yet its adoption as a mainstream manufacturing platform for functional objects is hindered by the physical challenges in printing multiple materials. Vat polymerization offers a polymer chemistry-based approach to generating smart objects, in which phase separation is used to control the spatial positioning of materials and thus at once, achieve desirable morphological and functional properties of final 3D printed objects. This study demonstrates how the spatial distribution of different material phases can be modulated by controlling the kinetics of gelation, cross-linking density and material diffusivity through the judicious selection of photoresin components. A continuum of morphologies, ranging from functional coatings, gradients and composites are generated, enabling the fabrication of 3D piezoresistive sensors, 5G antennas and antimicrobial objects and thus illustrating a promising way forward in the integration of dissimilar materials in 3D printing of smart or functional parts.

Mechanistic Insight into Bis(amino) Copper Formate Thermochemistry for Conductive Molecular Ink Design.

Increasing attention has been given to amine-copper formate complexes for their use as low-cost printable conductive inks. The structure of amine ligands coordinated to copper centers has been reported to dictate the properties of copper molecular inks, such as stability and printability, thereby influencing the copper reduction pathway during the thermolysis. Yet, the underlying mechanism by which formate is oxidized when complexed with amine ligands is still not fully understood. Here, we propose a mechanistic pathway of copper formate dehydrogenation and decarboxylation and examine the critical role that amine ligands play in their thermal decomposition by employing first-principles electronic structure computations and experimental analyses of thermolysis reactions. Based on the computational characterization of the relevant reaction pathways for a number of primary and secondary amines as well as pyridine ligand complexes, we are the first to show that the hydrogen bonds formed between the amine ligand and formate are the key factors governing the activation energy, providing a design principle for the synthesis of organic ligands that can tune the height of the reaction barriers of the dehydrogenation and decarboxylation reactions. The calculations, confirmed by NMR studies, show that the reduction of Cu(II) to Cu(I) occurs in concert with the release of H2 via the dimerization of Cu(II) hydride. This result suggests that the monomeric elimination of H2 is not favorable for the Cu(II) to Cu(I) reduction and thus identifies dimeric amino copper formate as an important intermediate for copper reduction whose thermodynamic stabilities are also dictated by the nature of the amine ligands.

Formulation of Screen-Printable Cu Molecular Ink for Conductive/Flexible/Solderable Cu Traces.

Screen printing is the most common method used for the production of printed electronics. Formulating copper (Cu) inks that yield conductive fine features with oxidation and mechanical robustness on low-temperature substrates will open up opportunities to fabricate cost-effective devices. We have formulated a screen-printable Cu metal-organic decomposition (MOD) ink comprising Cu formate coordinated to 3-(diethylamino)-1,2-propanediol, a fractional amount of Cu nanoparticles (CuNPs), and a binder. This simple formulation enables ∼70-550 µm trace widths with excellent electrical [∼8-15 mΩ/□/mil or 20-38 µΩ·cm] and mechanical properties with submicron-thick traces obtained by intense pulse light (IPL) sintering on Kapton and poly(ethylene terephthalate) (PET) substrates. These traces are mechanically robust to flexing and creasing where less than 10% change in resistance is observed on Kapton and ∼20% change is observed on PET. Solderable Cu traces were obtained only with the combination of the Cu MOD precursor, CuNP, and polymer binder. Both thermally and IPL sintered traces showed shelf stability (<10% change in resistance) of over a month in ambient conditions and 10-70% relative humidity, suitable for day-to-day fabrication. To demonstrate utility, light-emitting diodes (LEDs) were directly soldered to IPL sintered Cu traces in a reflow oven without the need for a precious metal interlayer. The LEDs were functional not only during bending and creasing of the Cu traces but even after 180 min at 140 °C in ambient air without losing illumination intensity. High definition television antennas printed on Kapton and PET were found to perform well in the ultrahigh frequency region. Lastly, single-walled carbon nanotube-based thin-film transistors on a silicon wafer were fabricated with a screen-printed Cu source and drain electrodes, which performed comparably to silver electrodes with mobility values of 12-15 cm2 V-1 s-1 and current on/off ratios of ∼105 and as effective ammonia sensors providing parts per billion-level detection.

The role of amine ligands in governing film morphology and electrical properties of copper films derived from copper formate-based molecular inks.

Copper formate complexes with various primary amines, secondary amines and pyridines were prepared, and their decomposition into conductive films was characterized. A comparison of the various complexes reveals that the temperature of thermolysis depends on the number of hydrogen bonds that can be formed between the amine and formate ligands. The particle size resulting from sintering of the copper complexes is shown to depend on the fraction of amine ligand released during the thermolysis reaction. The particle size in turn is shown to govern the electrical properties of the copper films. Correlations between the properties of the amines, such as boiling point and coordination strength, with the morphology and electrical performance of the copper films were established and provide a basis for the molecular design of copper formate molecular inks.

Versatile Molecular Silver Ink Platform for Printed Flexible Electronics.

A silver molecular ink platform formulated for screen, inkjet, and aerosol jet printing is presented. A simple formulation comprising silver neodecanoate, ethyl cellulose, and solvent provides improved performance versus that of established inks, yet with improved economics. Thin, screen-printed traces with exceptional electrical (<10 mΩ/□/mil or 12 µΩ·cm) and mechanical properties are achieved following thermal or photonic sintering, the latter having never been demonstrated for silver-salt-based inks. Low surface roughness, submicron thicknesses, and line widths as narrow as 41 µm outperform commercial ink benchmarks based on flakes or nanoparticles. These traces are mechanically robust to flexing and creasing (less than 10% change in resistance) and bind strongly to epoxy-based adhesives. Thin traces are remarkably conformal, enabling fully printed metal-insulator-metal band-pass filters. The versatility of the molecular ink platform enables an aerosol jet-compatible ink that yields conductive features on glass with 2× bulk resistivity and strong adhesion to various plastic substrates. An inkjet formulation is also used to print top source/drain contacts and demonstrate printed high-mobility thin film transistors (TFTs) based on semiconducting single-walled carbon nanotubes. TFTs with mobility values of ∼25 cm2 V-1 s-1 and current on/off ratios >104 were obtained, performance similar to that of evaporated metal contacts in analogous devices.

Rapid Detection and Identification of Yersinia pestis from Food Using Immunomagnetic Separation and Pyrosequencing.

Interest has recently been renewed in the possible use of Y. pestis, the causative agent of plague, as a biological weapon by terrorists. The vulnerability of food to intentional contamination coupled with reports of humans having acquired plague through eating infected animals that were not adequately cooked or handling of meat from infected animals makes the possible use of Y. pestis in a foodborne bioterrorism attack a reality. Rapid, efficient food sample preparation and detection systems that will help overcome the problem associated with the complexity of the different matrices and also remove any ambiguity in results will enable rapid informed decisions to be made regarding contamination of food with biothreat agents. We have developed a rapid detection assay that combines the use of immunomagnetic separation and pyrosequencing in generating results for the unambiguous identification of Y. pestis from milk (0.9 CFU/mL), bagged salad (1.6 CFU/g), and processed meat (10 CFU/g). The low detection limits demonstrated in this assay provide a novel tool for the rapid detection and confirmation of Y. pestis in food without the need for enrichment. The combined use of the iCropTheBug system and pyrosequencing for efficient capture and detection of Y. pestis is novel and has potential applications in food biodefence.

Immunomagnetic capture of Bacillus anthracis spores from food.

Food is a vulnerable target for potential bioterrorist attacks; therefore, a critical mitigation strategy is needed for the rapid concentration and detection of biothreat agents from food matrices. Magnetic beads offer a unique advantage in that they have a large surface area for efficient capture of bacteria. We have demonstrated the efficient capture and concentration of Bacillus anthracis (Sterne) spores using immunomagnetic beads for a potential food application. Magnetic beads from three different sources, with varying sizes and surface chemistries, were functionalized with monoclonal antibodies and polyclonal antibodies from commercial sources and used to capture and concentrate anthrax spores from spiked food matrices, including milk, apple juice, bagged salad, processed meat, and bottled water. The results indicated that the Pathatrix beads were more effective in the binding and capture of anthrax spores than the other two bead types investigated. Furthermore, it was observed that the use of polyclonal antibodies resulted in a more efficient recovery of anthrax spores than the use of monoclonal antibodies. Three different magnetic capture methods, inversion, the Pathatrix Auto system, and the new i CropTheBug system, were investigated. The i CropTheBug system yielded a much higher recovery of spores than the Pathatrix Auto system. Spore recoveries ranged from 80 to 100% for the i CropTheBug system when using pure spore preparations, whereas the Pathatrix Auto system had recoveries from 20 to 30%. Spore capture from food samples inoculated at a level of 1 CFU/ml resulted in 80 to 100% capture for milk, bottled water, and juice samples and 60 to 80% for processed meat and bagged salad when using the i CropTheBug system. This efficient capture of anthrax spores at very low concentrations without enrichment has the potential to enhance the sensitivity of downstream detection technologies and will be a useful method in a foodborne bioterrorism response.

Superparamagnetic microspheres with controlled macroporosity generated in microfluidic devices.

A microfluidic approach to preparing superparamagnetic microspheres with tunable porosity is described. In this method, droplets consisting of iron oxide nanoparticles, a functional polymer and solvent are formed in a microfluidic channel. The droplets are subsequently collected in solutions of sodium dodecyl sulfate (SDS) where the solvent is left to diffuse out of the droplet phase. By adjusting the concentration of the SDS and the polarity of the solvent of the dispersed phase, the porosity of the microparticles is controlled from non porous to porous structure. The formation of the pores is shown to depend on the rate at which solvent diffuses out of the droplet phase and the availability of SDS to adsorb at the droplet interface.

Multifunctional nanoprobes for pathogen-selective capture and detection.

The synthesis of magnetic and fluorescent particles is described. The particles are biofunctionalized by binding pathogen-specific proteins to the particles via interactions between His-tags of proteins and zinc of the quantum dots. Detection of Salmonella and Staphylococcus aureus (S. aureus) by these particles is demonstrated.

Enhancement and degradation of the R2* relaxation rate resulting from the encapsulation of magnetic particles with hydrophilic coatings.

The effects of including a hydrophilic coating around the particles are studied across a wide range of particle sizes by performing Monte Carlo simulations of protons diffusing through a system of magnetic particles. A physically realistic methodology of implementing the coating by cross boundary jump scaling and transition probabilities at the coating surface is developed. Using this formulation, the coating has three distinct impacts on the relaxation rate: an enhancement at small particle sizes, a degradation at intermediate particle sizes, and no effect at large particles sizes. These varied effects are reconciled with the underlying dephasing mechanisms by using the concept of a full dephasing zone to present a physical picture of the dephasing process with and without the coating for all sizes. The enhancement at small particle sizes is studied systemically to demonstrate the existence of an optimal ratio of diffusion coefficients inside/outside the coating to achieve maximal increase in the relaxation rate.

Clusters of superparamagnetic iron oxide nanoparticles encapsulated in a hydrogel: a particle architecture generating a synergistic enhancement of the T2 relaxation.

Clusters of iron oxide nanoparticles encapsulated in a pH-responsive hydrogel are synthesized and studied for their ability to alter the T(2)-relaxivity of protons. Encapsulation of the clusters with the hydrophilic coating is shown to enhance the transverse relaxation rate by up to 85% compared to clusters with no coating. With the use of pH-sensitive hydrogel, difficulties inherent in comparing particle samples are eliminated and a clear increase in relaxivity as the coating swells is demonstrated. Agreement with Monte Carlo simulations indicates that the lower diffusivity of water inside the coating and near the particle surface leads to the enhancement. This demonstration of a surface-active particle structure opens new possibilities in using similar structures for nanoparticle-based diagnostics using magnetic resonance imaging.

Nanobeads highly loaded with superparamagnetic nanoparticles prepared by emulsification and seeded-emulsion polymerization.

Functional superparamagnetic colloids possessing high saturation magnetization are prepared by emulsification of superparamagnetic nanoparticles (SPM NPs) and heterogeneous polymerization. The colloids consist of a core of densely packed NPs encapsulated within a thin polymer shell. The cores are made by emulsifying SPM NPs and toluene into an aqueous surfactant solution, and subsequently condensing the emulsion droplets by removal of the solvent generating clusters of SPM NPs. By tuning the emulsification condition, this approach allows for control over the size of the clusters from approximately 40 to 200 nm. The polymer shells encapsulating the clusters are made by using seeded-emulsion polymerization concepts. Control over the thickness of the shell and the incorporation of functional groups to the colloid is achieved. Characterization by thermogravimetric analysis (TGA) and magnetometry shows that these colloids have 66 wt % of magnetic material and saturation magnetization of 47 emu/g, confirming that this route generates colloids with a high loading of SPM NPs and high saturation magnetizations.

A study of simultaneous patterning and alignment of semiconductor nanorods via polymerization-induced phase separation.

We report simultaneous patterning and alignment of semiconductor nanorods (NRs) in nanorod-polymer films by using photolithographic polymerization-induced phase separation (PIPS). Exposure of the nanoparticle-monomer mixture to UV irradiation through a mask resulted in the site-specific photoinitiated polymerization of the monomer, which was followed with flow of the NRs from the areas rich in polymer to the areas rich in monomer. The orientation of NRs in the direction of flow was trapped in the polymerized films and characterized in polarization absorption experiments.

Screening of the effect of surface energy of microchannels on microfluidic emulsification.

We report the results of a systematic study of the effect of the surface energy of the walls of microchannels on emulsification in parallel flow-focusing microfluidic devices. We investigated the formation of water-in-oil (W/O) and oil-in-water (O/W) emulsions and found that the stability of microfluidic emulsification depends critically on the preferential wetting of the walls of the microfluidic device by the continuous phase. The condition for stable operation of the device is, however, different than that of complete wetting of the walls by the continuous phase at equilibrium. We found that W/O emulsions form when the advancing contact angle of water on the channel wall exceeds theta approximately 92 degrees. This result is unexpected because at equilibrium even for theta < 92 degrees the microchannels would be completely wet by the organic phase. The criterion for the formation of W/O emulsions (theta > 92 degrees) is thus more stringent than the equilibrium conditions. Conversely, we observed the stable formation of O/W emulsions for theta < 92 degrees, that is, when the nonequilibrium transition to complete wetting by oil takes place. These results underlie the importance of pinning and the kinetic wetting effects in microfluidic emulsification. The results suggest that the use of parallel devices can facilitate fast screening of physicochemical conditions for emulsification.

Microfluidic consecutive flow-focusing droplet generators.

This article describes emulsification in a microfluidic double droplet generator (DDR) comprising two consecutive flow-focusing devices with locally modified surface chemistry. We generated W/O/W, O/O/W and O/W/O double emulsions with precisely controlled sizes and morphology of droplets. Secondly, by combining two mechanisms of droplet formation (the flow-focusing mechanism and the break up of liquid threads at T-junction) we produced multiple populations of droplets with varying size and/or composition. These droplets were used as the structural units for the formation of complex dynamic lattices.

Guest-host colloid crystals: experimental study and simulations.

Disorder in colloid crystals was induced by doping them with a different number of large or small guest particles, which had a different deviation in size from the host colloids. The change in optical properties of the guest-host colloid crystals was assessed by using optical transmission spectroscopy while the variation in crystal structure was examined using scanning electron microscopy (SEM). The disruption in the crystalline lattices depended on the relative deviation in sizes of the guest and host particles and the concentration of the guest colloids. In parallel with experiments, the packing of spheres in guest-host crystals was modeled with a simulated annealing algorithm. A good correlation was found between the changes in crystal structure observed by SEM imaging and the simulated sphere packing. The experimental and simulated changes in the transmission spectra of guest-host colloid crystals were in good agreement.

Size-selected synthesis of PtRu nano-catalysts: reaction and size control mechanism.

A rapid synthesis method for the preparation of PtRu colloids and their subsequent deposition on high surface area carbons is presented. The reaction mechanism is shown to involve the oxidation of the solvent, ethylene glycol, to mainly glycolic acid or, depending on the pH, its anion, glycolate, while the Pt(+IV) and Ru(+III) precursor salts are reduced. Glycolate acts as a stabilizer for the PtRu colloids and the glycolate concentration, and hence the size of the resulting noble metal colloids is controlled via the pH of the synthesis solution. Carbon-supported PtRu catalysts of controlled size can be prepared within the range of 0.7-4 nm. Slow scan X-ray diffraction and high-resolution transmission electron microscopy show the PtRu catalysts to be crystalline. The Ru is partly dissolved in the face-centered cubic Pt lattice, but the catalysts also consist of a separate, hexagonal Ru phase. The PtRu catalysts appear to be of the same composition independent of the catalyst size in the range of 1.2-4 nm. Particular PtRu catalysts prepared in this work display enhanced activities for the CH(3)OH electro-oxidation reaction when compared to two commercial catalysts.