Solid-state conducting polymers usually have highly conjugated macromolecular backbones and require intentional doping in order to achieve high electrical conductivities. Conversely, single-component, charge-neutral macromolecules could be synthetically simpler and have improved processibility and ambient stability. We show that poly(4-glycidyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl), a nonconjugated radical polymer with a subambient glass transition temperature, underwent rapid solid-state charge transfer reactions and had an electrical conductivity of up to 28 siemens per meter over channel lengths up to 0.6 micrometers. The charge transport through the radical polymer film was enabled with thermal annealing at 80°C, which allowed for the formation of a percolating network of open-shell sites in electronic communication with one another. The electrical conductivity was not enhanced by intentional doping, and thin films of this material showed high optical transparency.
In this report, we merge block copolymers with vitrimers in an effort to realize the prospect of higher-order, nanoscale control over associative cross-link exchange and flow. We show the use of controlled polymerization as a vital tool to understand fundamental structure−property effects through the precise control of polymer architecture and molecular weight. Vitrimers derived from self-assembling block copolymers exhibit superior resistance to macroscopic deformation in comparison to their analogs generated from statistical copolymers. Our results suggest that the enhanced creep resistance achieved by control over chain topology in block vitrimers can be used to tune viscoelastic properties. The resistance to macroscopic deformation that arises from a microphase-separated structure in this new class of materials differentiates block vitrimers from their statistical counterparts and introduces the potential of topology-control over viscoelastic flow.
The optimization of ionic conductivity and lithium-ion battery stability can be achieved by independently tuning the ion transport and mechanical robustness of block polymer (BP) electrolytes. However, the ionic conductivity of BP electrolytes is inherently limited by the covalent attachment of the ionically conductive block to the mechanically robust block, among other factors. Herein, the BP electrolyte polystyrene-block-poly(oligo-oxyethylene methacrylate) [PS-b-POEM] was blended with POEM homopolymers of varying molecular weights. The incorporation of a higher molecular weight homopolymer additive (α > 1 state) promoted a "dry brush-like" homopolymer distribution within the BP self-assembly and led to higher lithium salt concentrations in the more mobile homopolymer-rich region, increasing overall ionic conductivity relative to the "wet brush-like" (α < 1 state) and unblended composites, where α is the molecular weight ratio between the POEM homopolymer and the POEM block in the copolymer. Neutron and X-ray reflectometry (NR and XRR, respectively) provided additional details on the lithium salt and polymer distributions. From XRR, the α > 1 blends showed increased interfacial widths in comparison to their BP (unblended) or α < 1 counterparts because of the more central distribution of the homopolymer. This result, paired with NR data that suggested even salt concentrations across the POEM domains, implied that there was a higher salt concentration in the homopolymer POEM-rich regions in the dry brush blend than in the wet brush blend. Furthermore, using 7 Li solid-state nuclear magnetic resonance spectroscopy, we found a temperature corresponding to a transition in lithium mobility (T Li mobility ) that was a function of blend type. T Li mobility was found to be 39 °C above T g in all cases. Interestingly, the ionic conductivity of the blended BPs was highest in the α > 1 composites, even though these composites had higher T g s than the α < 1 composites, demonstrating that homopolymer-rich conducting pathways formed in the α > 1 assemblies had a larger influence on conductivity than the greater lithium ion mobility in the α < 1 blends.
The 3 × 3 gas sensor array with different metal oxides and morphologies is fabricated to compare the sensitization effects of Au nanoparticles on various metal oxides and gases.The 3 × 3 gas sensor array with different metal oxides and morphologies is fabricated to compare the sensitization effects of Au nanoparticles on various metal oxides and gases.
The production of reusable stamps for the creation of high‐resolution patterns of functional nanoparticles is demonstrated. A patterned stamp is cleaned by removing nanoparticles in the recessed regions of the stamp, using a UV‐curable adhesive, before moving on to the next cycle of printing with the stamp. A high‐resolution patterning technique using rigid stamps with a low surface energy and the repeated use of the reusable stamps for defining sub‐100 nm scale features is demonstrated. Color patterning has also been performed using just one color per stamp, then by the use of one stamp for multiple colors.
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