Thermoplastic elastomers (TPEs) based on styrenic block copolymers constitute excellent examples of self‐networking macromolecules that are employed in a wide range of contemporary technologies as molded parts. In such applications, these TPEs exist as dense (nonporous) films or other shapes. Here, it is first demonstrated that a series of commercial TPEs possessing comparable compositions can be electrospun from solution to form microfibers that are arranged into nonwoven mats that are breathable. An important consideration for microfiber formation is the copolymer molecular weight, which regulates i) the viscosity of the parent solution prior to electrospinning, ii) the ability of these copolymers to self‐assemble during electrospinning, iii) the microfiber morphology, and iv) the mechanical properties of the resultant microfibers. The addition of a midblock‐selective aliphatic oil to these TPEs yields thermoplastic elastomer gels (TPEGs), wherein the copolymer morphology and mechanical properties become highly composition‐tunable. Electrospinning TPEGs from a binary oil+solvent solution introduces a micelle inversion mechanism that begins with an oil‐rich micellar core and ends with a styrene‐rich micellar core, required for network stabilization, as the solvent dries during microfiber solidification. This work has implications for the production of controllably low‐modulus microfibrous materials possessing modestly improved toughness but exceptional extensibility and enhanced optical transparency.
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null (Ed.)Our world today increasingly relies on the orchestration of digital and physical systems to ensure the successful operations of many complex and critical infrastructures. Simulation-based testbeds are useful tools for engineering those cyber-physical systems and evaluating their efficiency, security, and resilience. In this article, we present a cyber-physical system testing platform combining distributed physical computing and networking hardware and simulation models. A core component is the distributed virtual time system that enables the efficient synchronization of virtual clocks among distributed embedded Linux devices. Virtual clocks also enable high-fidelity experimentation by interrupting real and emulated cyber-physical applications to inject offline simulation data. We design and implement two modes of the distributed virtual time: periodic mode for scheduling repetitive events like sensor device measurements, and dynamic mode for on-demand interrupt-based synchronization. We also analyze the performance of both approaches to synchronization including overhead, accuracy, and error introduced from each approach. By interconnecting the embedded devices’ general purpose IO pins, they can coordinate and synchronize with low overhead, under 50 microseconds for eight processes across four embedded Linux devices. Finally, we demonstrate the usability of our testbed and the differences between both approaches in a power grid control application.more » « less
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Recently, metal–organic framework (MOF)-based polymeric substrates show promising performance in many engineering and technology fields. However, a commonly known drawback of MOF/polymer composites is MOF crystal encapsulation and reduced surface area. This work reports a facile and gentle strategy to produce self-supported MOF predominant hollow fiber mats. A wide range of hollow MOFs including MIL-53(Al)–NH 2 , Al-PMOF, and ZIF-8 are successfully fabricated by our synthetic method. The synthetic strategy combines atomic layer deposition (ALD) of metal oxides onto polymer fibers and subsequent selective removal of polymer components followed by conversion of remaining hollow metal oxides into freestanding MOF predominant hollow fiber structures. The hollow MOFs show boosted surface area, superb porosity, and excellent pore accessibility, and exhibit a significantly improved performance in CO 2 adsorption (3.30 mmol g −1 ), CO 2 /N 2 separation selectivity (24.9 and 21.2 for 15/85 and 50/50 CO 2 /N 2 mixtures), and catalytic removal of HCHO (complete oxidation of 150 ppm within 60 min).more » « less
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Abstract Styrenic thermoplastic elastomers (TPEs) in the form of triblock copolymers possessing glassy endblocks and a rubbery midblock account for the largest global market of TPEs worldwide, and typically rely on microphase separation of the endblocks and the subsequent formation of rigid microdomains to ensure satisfactory network stabilization. In this study, the morphological characteristics of a relatively new family of crystallizable TPEs that instead consist of polyethylene endblocks and a random‐copolymer midblock composed of styrene and (ethylene‐
co ‐butylene) moieties are investigated. Copolymer solutions prepared at logarithmic concentrations in a slightly endblock‐selective solvent are subjected to crystallization under different time and temperature conditions to ascertain if copolymer self‐assembly is directed by endblock crystallization or vice versa. According to transmission electron microscopy, semicrystalline aggregates develop at the lowest solution concentration examined (0.01 wt%), and the size and population of crystals, which dominate the copolymer morphologies, are observed to increase with increasing aging time. Real‐space results are correlated with small‐ and wide‐angle X‐ray scattering to elucidate the concurrent roles of endblock crystallization and self‐assembly of these unique TPEs in solution. -
Abstract Comprehensive treatment of indoor contaminants such as volatile organic compounds (VOCs) and fine particulate matter (PM2.5) using transition metal oxide catalysts or functional fibrous filters has gained substantial attention recently. However, coupling VOC oxidation catalysts into high‐performance filter systems remains a challenge. Herein, an overall solution to strongly bind manganese dioxide (MnO2) nanocrystals onto polypropylene (PP) nonwoven fabrics is provided. For the first time, uniform heterogeneous nucleation and growth of MnO2onto PP nonwoven fabrics using intermediate inorganic nucleation films, including Al2O3, TiO2, and ZnO, formed conformally on the fabrics via atomic layer deposition (ALD) are demonstrated. How different ALD thin films influence the crystallinity, morphology, surface area, and surface oxygen species of the MnO2grown ALD‐coated PP fibers is further investigated. In addition to uniformity and integrity, ZnO thin films give rise to MnO2crystals with the largest fraction of available surface oxygen, enabling 99.5% catalytic oxidation of formaldehyde within 60 min. Moreover, the metal oxide filters provide excellent PM removal efficiencies (
e PM), achievinge PM2.590% ande PM1098%, respectively, making the approach an outstanding method to produce fully dual‐functional filtration media.