We report the production of flexible, highly-conductive poly(vinylidene fluoride) (PVDF) and multi-walled carbon nanotube (MWCNT) composites as filament feedstock for 3D printing. This account further describes, for the first time, fused deposition modelling (FDM) derived 3D-printed objects with chemiresistive properties in response to volatile organic compounds. The typically prohibitive thermal expansion and die swell characteristics of PVDF were minimized by the presence of MWCNTs in the composites enabling straightforward processing and printing. The nanotubes form a dispersed network as characterized by helium ion microscopy, contributing to excellent conductivity (∼3 × 10 S cm). The printed composites contain little residual metal particulate relative to parts from commercial PLA-nanocomposite material visualized by micro-X-ray computed tomography (μ-CT) and corroborated with thermogravimetric analysis. Printed sensing strips, with MWCNT loadings up to 15% mass, function as reversible vapour sensors with the strongest responses arising with organic compounds capable of readily intercalating and subsequently swelling the PVDF matrix (acetone and ethyl acetate). A direct correlation between MWCNT concentration and resistance change was also observed, with larger responses (up to 161% after 3 minutes) being generated with decreased MWCNT loadings. These findings highlight the utility of FDM printing in generating low-cost sensors that respond strongly and reproducibly to target vapours. Furthermore, the sensors can be easily printed in different geometries, expanding their utility to wearable form factors. The proposed formulation strategy may be tailored to sense diverse sets of vapour classes through structural modification of the polymer backbone and/or functionalization of the nanotubes within the composite.
Metal-organic frameworks (MOFs) exhibit exceptional properties and are widely investigated because of their structural and functional versatility relevant to catalysis, separations, and sensing applications. However, their commercial or large-scale application is often limited by their powder forms which make integration into devices challenging. Here, we report the production of MOF-thermoplastic polymer composites in well-defined and customizable forms and with complex internal structural features accessed via a standard three-dimensional (3D) printer. MOFs (zeolitic imidazolate framework; ZIF-8) were incorporated homogeneously into both poly(lactic acid) (PLA) and thermoplastic polyurethane (TPU) matrices at high loadings (up to 50% by mass), extruded into filaments, and utilized for on-demand access to 3D structures by fused deposition modeling. Printed, rigid PLA/MOF composites display a large surface area (SA = 531 m g) and hierarchical pore features, whereas flexible TPU/MOF composites achieve a high surface area (SA = 706 m g) by employing a simple method developed to expose obstructed micropores postprinting. Critically, embedded particles in the plastic matrices retain their ability to participate in chemical interactions characteristic of the parent framework. The fabrication strategies were extended to other MOFs and illustrate the potential of 3D printing to create unique porous and high surface area chemically active structures.
A Round Robin study involving 19 coating suppliers and independent laboratories was conducted on tensile testing of thermally sprayed coatings to determine the accuracy and consistency of the tensile data among the participating labs and within a lab. One coating system (NiCrAl) and two adhesive types (film vs. liquid epoxy) were used. The results showed the average tensile strengths for the coating system using the liquid epoxy systems (EC2086/EC2214) were consistently higher than the average values which resulted using the film epoxy system (FMIOOO). However, less scatter in the results was observed when the FMIOOO film epoxy was used.
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