ABSTRACT
Synthetic porous materials continue to garner attention as platforms for solid-state chemistry and as designer heterogeneous catalysts. Applications in photochemistry and photocatalysis, however, are plagued by poor light harvesting efficiency due to light scattering resulting from sample microcrystallinity and poor optical penetration that arises from inner filter effects. Here we demonstrate the layer-by-layer growth of optically transparent, photochemically active thin films of porous salts. Films are grown by sequential deposition of cationic Zr-based porous coordination cages and anionic Mn porphyrins. Photolysis facilitates the efficient reduction of Mn(III) sites to Mn(II) sites, which can be observed in real-time by transmission UV-vis spectroscopy. Film porosity enables substrate access to the Mn(II) sites and facilitates reversible O2 activation in the solid state. These results establish optically transparent, porous salt thin films as versatile platforms for solid-state photochemistry and in operando spectroscopy.
ABSTRACT
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.
ABSTRACT
Current thermally conductive and electrically insulating insulation systems are struggling to meet the needs of modern electronics due to increasing heat generation and power densities. Little research has focused on creating insulation systems that excel at both dissipating heat and withstanding high voltages (i.e., have both high thermal conductivity and a high breakdown strength). Herein, a polyelectrolyte-based multilayer nanocomposite is demonstrated to be a thermally conductive high-voltage insulation. Through inclusion of both boehmite and vermiculite clay, the breakdown strength of the nanocomposite was increased by ≈115%. It was also found that this unique nanocomposite has an increase in its breakdown strength, modulus, and hydrophobicity when exposed to elevated temperatures. This readily scalable insulation exhibits a remarkable combination of breakdown strength (250 kV/mm) and thermal conductivity (0.16 W m-1 K-1) for a polyelectrolyte-based nanocomposite. This dual clay insulation is a step toward meeting the needs of the next generation of high-performance insulation systems.
