RESUMEN
High-entropy alloy (HEA) nanoparticles (NPs) exhibit unusual combinations of functional properties. However, their scalable synthesis remains a significant challenge requiring extreme fabrication conditions. Metal salts are often employed as precursors because of their low decomposition temperatures, yet contain potential impurities. Here, we propose an ultrafast (< 100 ms), one-step method that enables the continuous synthesis of HEA NPs directly from elemental metal powders via in-flight alloying. A high-temperature plasma jet ( > 5000 K) is employed for rapid heating/cooling (103 - 105 K s-1), and demonstrates the synthesis of CrFeCoNiMo HEA NPs ( ~ 50 nm) at a high rate approaching 35 g h-1 with a conversion efficiency of 42%. Our thermofluid simulation reveals that the properties of HEA NPs can be tailored by the plasma gas which affects the thermal history of NPs. The HEA NPs demonstrate an excellent light absorption of > 96% over a wide spectrum, representing great potential for photothermal conversion of solar energy at large scales. Our work shows that the thermal plasma process developed could provide a promising route towards industrial scale production of HEA NPs.
RESUMEN
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.
RESUMEN
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.
RESUMEN
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.
RESUMEN
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 â¼70-550 µm trace widths with excellent electrical [â¼8-15 mΩ/â¡/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 â¼20% 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 â¼105 and as effective ammonia sensors providing parts per billion-level detection.
RESUMEN
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.