ABSTRACT
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 (â¼3 × 10-2 S cm-1). 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.
ABSTRACT
Core-level and valence-band x-ray photoemission spectra measured for molecular-beam-epitaxy-grown LaCrO(3)/SrTiO(3)(001) yield band offsets and potential gradients within the LaCrO(3) sufficient to trigger an electronic reconstruction to alleviate the polarity mismatch. Yet, the interface is insulating. Based on first principles calculations, we attribute this unexpected result to interfacial cation mixing combined with charge redistribution within CrO(2) layers, enabled by low-lying d states within LaCrO(3), which suppresses an electronic reconstruction.
ABSTRACT
In an effort to improve the understanding of electron transfer mechanisms at the microbe-mineral interface, Shewanella oneidensis MR-1 mutants with in-frame deletions of outer-membrane cytochromes (OMCs), MtrC and OmcA, were characterized for the ability to reduce ferrihydrite (FH) using a suite of microscopic, spectroscopic, and biochemical techniques. Analysis of purified recombinant proteins demonstrated that both cytochromes undergo rapid electron exchange with FH in vitro with MtrC displaying faster transfer rates than OmcA. Immunomicroscopy with cytochrome-specific antibodies revealed that MtrC co-localizes with iron solids on the cell surface while OmcA exhibits a more diffuse distribution over the cell surface. After 3-day incubation of MR-1 with FH, pronounced reductive transformation mineral products were visible by electron microscopy. Upon further incubation, the predominant phases identified were ferrous phosphates including vivianite [Fe(3)(PO(4))(2)x8H(2)O] and a switzerite-like phase [Mn(3),Fe(3)(PO(4))(2)x7H(2)O] that were heavily colonized by MR-1 cells with surface-exposed outer-membrane cytochromes. In the absence of both MtrC and OmcA, the cells ability to reduce FH was significantly hindered and no mineral transformation products were detected. Collectively, these results highlight the importance of the outer-membrane cytochromes in the reductive transformation of FH and support a role for direct electron transfer from the OMCs at the cell surface to the mineral.
