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Sulfur K-edge XAS data provide a unique tool to examine oxidation states and covalency in electronically complex S-based ligands. We present sulfur K-edge X-ray absorption spectroscopy on a discrete redox-series of Ni-based tetrathiafulvalene tetrathiolate (TTFtt) complexes as well as on a 1D coordination polymer (CP), NiTTFtt. Experiment and theory suggest that Ni–S covalency decreases with oxidation which has implications for charge transport pathways. 

Abstract Lanthanides in the trivalent oxidation state are typically described using an ionic picture that leads to localized magnetic moments. The hierarchical energy scales associated with trivalent lanthanides produce desirable properties for e.g., molecular magnetism, quantum materials, and quantum transduction. Here, we show that this traditional ionic paradigm breaks down for praseodymium in the tetravalent oxidation state. Synthetic, spectroscopic, and theoretical tools deployed on several solid-state Pr 4+ -oxides uncover the unusual participation of 4 f orbitals in bonding and the anomalous hybridization of the 4 f 1 configuration with ligand valence electrons, analogous to transition metals. The competition between crystal-field and spin-orbit-coupling interactions fundamentally transforms the spin-orbital magnetism of Pr 4+ , which departs from the J eff  = 1/2 limit and resembles that of high-valent actinides. Our results show that Pr 4+ ions are in a class on their own, where the hierarchy of single-ion energy scales can be tailored to explore new correlated phenomena in quantum materials. 

Demand is expected to accelerate for autonomous air vehicles that transport people and goods, making wind sensors on these vehicles and in the air space where they operate critical to ensure safe control of many simultaneous take-offs and landings. Conventional anemometers such as pitot tubes as well as rotating, heated-element, acoustic, and drag technologies have drawbacks for small and micro-aerial vehicles including high power consumption, high aerodynamic drag, complex signal processing, and high cost. This paper presents an airfoil-shaped anemometer that provides low drag while integrating sensors for measuring wind speed and direction on tethered kites, balloons, and drones. Wind speed is measured by an integrated dual-layer capacitive pressure sensor with a polyvinylidene fluoride (PVDF) diaphragm while wind direction is measured by a 3D digital magnetometer that senses the orientation of the airfoil relative to the earth’s magnetic field. A model is presented for a dual-layer capacitive sensor and validated through quasistatic pressure chamber testing. The capacitive sensor as well as a commercial digital magnetometer are integrated into a NACA 2412 profile airfoil and tested in a laboratory-scale wind tunnel. The capacitive sensor provides a sensitivity of 1.84 fF m 2 s −2 and the airfoil exhibits a unique stable angle-of-attack to within ±2° as measured by the magnetometer. 

Metal-matrix composites with active components have been investigated as a way to functionalize metals. As opposed to surface-mounted approaches, smart materials embedded in metals can be effectively shielded against the environment while providing in-situ sensing, health monitoring, actuation, or energy harvesting functions. Typical manufacturing approaches can be problematic, however, in that they may physically damage the smart material or degrade its electromechanical properties. For instance, non-resin-based embedment procedures such as powder metallurgy involve isostatic compression and diffusion bonding, leading to high process temperatures and breakdown of the electromechanical properties of the active component to be embedded. This paper presents the development and characterization of an aluminum-matrix composite embedded with piezoelectric polyvinylidene fluoride (PVDF) sensors using ultrasonic additive manufacturing (UAM). UAM incorporates the principles of solid-state, ultrasonic metal welding and subtractive processes to fabricate metal-matrices with seamlessly embedded smart materials and without thermal loading. As implemented in this study, the UAM process uses as-received, commercial Al 6061 tape foilstock and TE Connectivity PVDF film. In order to increase the mechanical coupling between the sensor and the metal-matrix without the aid of adhesives, the PVDF sensor is embedded with an empirically optimized pre-compression defined by the tape foils welded above the sensor. The specimen is characterized by tensile (d31 mode), bending (d31 mode), and compression tests (d33 mode) to evaluate its functional performance. Within the investigated load range, the specimen exhibits open-circuit sensitivities of 4.6 mV/N under uniaxial tension and 9.7 mV/N under compressive impulse tests with better than 95% linearity and frequency bandwidth of several kilohertz. The technology presented in this study could be applied for load and tactile sensing, impact detection and localization, thermal measurements, energy harvesting, and non-destructive testing applications. 

Reaction of the complexes [Fe 2 (μ 2 -NP(pip) 3 ) 2 (NP(pip) 3 ) 2 ] ( 1-Fe ) and [Co 2 (μ 2 -NP(pip) 3 ) 2 (NP(pip) 3 ) 2 ] ( 1-Co ), where [NP(pip) 3 ] 1− is tris(piperidinyl)imidophosphorane, with nitrous oxide, S 8 , or Se 0 results in divergent reactivity. With nitrous oxide, 1-Fe forms [Fe 2 (μ 2 -O)(μ 2 -NP(pip) 3 ) 2 (NP(pip) 3 ) 2 ] ( 2-Fe ), with a very short Fe 3+ –Fe 3+ distance. Reactions of 1-Fe with S 8 or Se 0 result in the bridging, side-on coordination (μ-κ 1 :κ 1 -E 2 2− ) of the heavy chalcogens in complexes [Fe 2 (μ-κ 1 :κ 1 -E 2 )(μ 2 -NP(pip) 3 ) 2 (NP(pip) 3 ) 2 ] (E = S, 3-Fe , or Se, 4-Fe ). In all cases, the complex 1-Co is inert.