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At least 613 records · Page 34

Switchable Charge Storage Mechanism via in Situ Activation of MXene Enables High Capacitance and Stability in Aqueous Electrolytes

The need for reliable renewable energy storage devices has become increasingly important. However, the performance of current electrochemical energy storage devices is limited by either low energy or power densities and short lifespans. Herein, we report the synthesis and characterization of multilayer Ti 4 N 3 T x MXene in various aqueous electrolytes. We demonstrate that Ti 4 N 3 T x can be electrochemically activated through continuous cation intercalation over a 10 day period using cyclic voltammetry. A wide operating window of 2 V is maintained throughout activation. After activation, capacitance at 2 mV s -1 increases by 300%, 140%, and 500% in 1 M H2SO4, 1 M MgSO4, and 1 M KOH, respectively, while maintaining ~600 F g -1 at 2 mV s–1 after 50000 cycles in 1 M H 2 SO 4 . This activation process is possibly attributed to the unique morphology of the multilayered material, allowing cation intercalation to increase access to redox-active sites between layers. This work adds to the growing repository of electrochemically stable MXenes reported for aqueous energy storage applications. These findings offer a reliable option for reliable energy storage devices with potential applications in large-scale grid storage and electric vehicles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Influence of Robotic Assistance on Reducing Neuromuscular Effort and Fatigue during Extravehicular Activity Glove Use

The three-layered, pressurized space suit glove worn by Extravehicular Activity (EVA) crew members during missions commonly causes hand and forearm fatigue. The Spacesuit RoboGlove (SSRG), a Phase VI EVA space suit glove modified with robotic grasp-assist capabilities, has been developed to augment grip strength in order to improve endurance and reduce the risk of injury in astronauts. The overall goals of this study were to i) quantify the neuromuscular modulations that occur in response to wearing a conventional Phase VI space suit glove (SSG) during a fatiguing task, and ii) determine the efficacy of Spacesuit RoboGlove (SSRG) in reversing the adverse neuromuscular modulations and restoring altered muscular activity to barehanded levels. Six subjects performed a fatigue sequence consisting of repetitive dynamic-gripping interspersed with isometric grip-holds under three conditions: barehanded, wearing pressurized SSG, and wearing pressurized SSRG. Surface electromyography (sEMG) from six forearm muscles (flexor digitorum superficialis (FDS), flexor carpi radialis (FCR), flexor carpi ulnaris (FCU), extensor digitorum (ED), extensor carpi radialis longus (ECRL), and extensor carpi ulnaris (ECU)) and subjective fatigue ratings were collected during each condition. Trends in amplitude and spectral distributions of the sEMG signals were used to derive metrics quantifying neuromuscular effort and fatigue that were compared across the glove conditions. Results showed that by augmenting finger flexion, the SSRG successfully reduced the neuromuscular effort needed to close the fingers of the space suit glove in more than half of subjects during two types of tasks. However, the SSRG required more neuromuscular effort to extend the fingers compared to a conventional SSG in many subjects. Psychologically, the SSRG aided subjects in feeling less fatigued during short periods of intense work compared to the SSG. The results of this study reveal the promise of the SSRG as a grasp-assist device that can improve astronaut performance and reduce the risk of injury by offsetting neuromuscular effort. Modifications to the experimental protocol are needed, however, to improve the outcome of the neuromuscular fatigue metrics and determine the effectiveness of SSRG in increasing astronaut endurance. Nevertheless, these findings will improve the understanding of astronaut-spacesuit interaction and provide direction toward designing improved spacesuit gloves and robotic-assist devices, like the SSRG.

Madden, Kaci E.↗

Development of solar active regions

The birth, growth, and decay of solar active regions are described. The appearance of active regions in different atmospheric layers is examined, and the coronal extension of active regions is considered. The use of Skylab soft X-ray and extreme UV observations for studying the complex loop structure of active regions in the solar corona and the sensitive reactions of the upper atmospheric layers to newly emerging flux is explained. It was found that well developed active regions are much bigger in the corona than in the underlying sunspot groups and plages, and that many of the active regions are connected with others through systems of magnetic field lines, occasionally visible in soft X-rays. These interconnections, which may survive several solar rotations, indicate bigger complexes on the sun than one individual active region.

Svestka, Z.↗

Development program for 1.93-micron lasers

For the first time lasers operating at 1.93 microns were demonstrated. The lasers were fabricated by Vapor Phase Epitaxial (VPE) growth techniques currently used for the fabrication of high power lasers at 1.3 microns. The structure of these laser diodes consisted of compositionally graded, sulfur-doped InAsP, grown on an InP substrate; a constant-composition n+InAs(0.27)P(0.73) layer, which is the first cladding layer; an In(0.66)Ga(0.34)As layer, which is the active region, and a second InAs(0.27)P(0.73) layer. The devices were oxide-stripe DH lasers (gain-guided only). The best devices had 80 K lasing thresholds in the range of from 80 to 150 mA, and T sub o (below 220 K) in the range of 60 to 90 K. The highest observed temperature of oscillation was 15.5 C. The highest observed power output at 80 K was in the range of 3 to 5 mW. The calculated delta I/delta T was 4.4 A/K. As a part of the materials development, PIN homojunction detectors having the band edge near 1.93 were also fabricated. The best devices (100 micron diameter, mesa structure) exhibited room temperature dark currents in the range of from 20 to 50 nA and had QE at 1.93 microns in the range of 35 to 40 percent. In addition to the device results, the InGaAs-InAsP materials system was extensively investigated and low defect density layers can now be grown allowing for significant device performance improvement.

Longeway, P.↗

Non-local large-strain FFT-based formulation and its application to interface-dominated plasticity of nano-metallic laminates

Here, this paper presents a novel formulation and its robust numerical implementation of strain-gradient (SG) crystal plasticity within a large-strain (LS) elasto-viscoplastic (EVP) fast Fourier transform (FFT)-based micromechanical model. The resulting non-local SG-LS-EVPFFT formulation is used to model and understand the process of kink band formation during layer-parallel compression of nano-metallic laminates (NMLs). NMLs are layered composites with nanoscale thicknesses, thus requiring consideration of the interaction between dislocations and interfaces within the micromechanical model. The length-scale parameter of the SG model is calibrated by simulating a double pile-up and comparing predictions to analytical solution. This required new expressions for the defect energy, resulting in more accurate double pile-up predictions. The calibrated SG-LS-EVPFFT model is then used to simulate layer-parallel compression of copper-niobium NML. Formation of kink bands is predicted, and the model is used to rationalize the microscopic mechanisms enabling the formation process. It is found that accumulation of dislocations at interfaces leads to activation of layer-parallel slip, which in turn leads to kink band formation.

36 MATERIALS SCIENCE↗

Candidate techniques for non-intrusive measurement of flight boundary-layer properties

Techniques to measure gas composition and chemical activity in the hypersonic boundary layer associated with entry research vehicles and with a tethered satellite deployed at 100-125 km altitude are currently being investigated at the NASA-Langley Research Center. These measurements are appropriate for the study of the aerothermodynamic properties of these vehicles when operating with controlled trajectories in the thermosphere between 125 and 55 km. A number of the required quantitative physical measurements have been identified, and candidate techniques to obtain the measurements without perturbing the flow are being considered. Two candidate techniques are discussed in this paper: a mass spectrometer to analyze the gas composition at the vehicle surface, and Rayleigh scattering to obtain density, velocity, and temperature gradients from the surface to the edge of the boundary layer.

Wood, G. M., Jr.↗

Large-Eddy Simulations of Marine Boundary-Layer Clouds Associated With Cold Air Outbreaks During the Activate Campaign – Part 1: Case Setup and Sensitivities to Large-Scale Forcings

Large-eddy simulation (LES) is able to capture key boundary-layer (BL) turbulence and cloud processes. Yet, large-scale forcing and surface turbulent fluxes of sensible and latent heat are often poorly prescribed for LES simulations. We derive these quantities from measurements and reanalysis obtained for two cold air outbreak (CAO) events during Phase I of the Aerosol Cloud meTeorology Interactions oVer the western ATlantic Experiment (ACTIVATE) in February-March 2020. We study the two contrasting CAO cases by performing LES and test the sensitivity of BL structure and clouds to large-scale forcings and turbulent heat fluxes. Profiles of atmospheric state and large-scale divergence and surface turbulent heat fluxes obtained from the reanalysis data ERA5 agree reasonablywell with those derived fromACTIVATE field measurements for both cases at the sampling time and location. Therefore, we adopt the time evolving heat fluxes, wind and advective tendencies profiles from ERA5 reanalysis data to drive the LES.We find that large-scale thermodynamic advective tendencies and wind relaxations are important for the LES to capture the evolving observed BL meteorological states characterized by the hourly ERA5 reanalysis data and validated by the observations. We show that the divergence (or vertical velocity) is important in regulating the BL growth driven by surface heat fluxes in LES simulations. The evolution of liquid water path is largely affected by the evolution of surface heat fluxes. The liquid water path imulated in LES agrees reasonably well with the ACTIVATE measurements. This study paves the path to investigate aerosol-cloud-meteorology interactions using LES informed and evaluated by ACTIVATE field measurements.

Large-eddy simulation↗

Oxophilicity Drives Oxygen Transfer at a Palladium–Silver Interface for Increased CO Oxidation Activity

A single-layer AgO x phase grown on Ag(111) efficiently transfers oxygen to Pd domains at room temperature, rendering the Pd-decorated surface highly reactive toward CO oxidation. Here, oxygen transfer from AgO x to Pd and the surface reactivity toward CO were investigated as a function of the Pd coverage using X-ray photoelectron spectroscopy, surface infrared spectroscopy of adsorbed CO, temperature-programmed reaction spectroscopy, and density functional theory (DFT) calculations. Our results show that all of the oxygen from the AgO x layer (~0.375 monolayer) migrates to the surface of Pd during formation of a nearly complete Pd bilayer at 300 K and that the oxygen coverages generated on Pd increase as the Pd cluster size decreases, reaching values that exceed the oxygen concentration in the AgO x layer by as much as a factor of 2. Experimental measurements and DFT calculations show that preferential binding of oxygen on the edges of the Pd clusters enhances the oxygen coverage on Pd clusters of decreasing size and produces a heterogeneous spatial distribution of oxygen. CO adsorbs in high coverages at 100 K by binding on both the terraces and O-rich edges of the Pd clusters. During subsequent heating, oxidation of the adsorbed CO consumes nearly all of the oxygen that transferred from AgO x to the Pd domains; in contrast, the pure AgO x layer exhibits limited reactivity toward CO adsorbed at 100 K. These results demonstrate that differences in oxophilicity drive facile oxygen transfer from Ag to the edges of Pd nanoclusters and thereby give rise to an efficient pathway for CO oxidation on bimetallic PdAg surfaces. The cooperation between the Pd and Ag domains results in near-interfacial chemistry that may be broadly important in catalysis by bimetallic alloys.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Relative-Humidity Dependence of Electrochemically Active Surface Area in Porous Carbon Catalyst Layers

Polymer-electrolyte fuel cells (PEFCs) utilize porous catalyst layers (CLs) formed of carbon supports on which Pt particles are deposited and ionomer films are distributed. Carbon supports themselves have varying degrees of porosity, where high-surface-area carbon (HSC) supports possess nanometer-sized interior pores that are suitable for Pt nanoparticle deposition but prevent deleterious ionomer penetration. However, this requires protons to transport through water pathways inside the pores. To understand the generation of such pathways, we examine the various mechanisms of water uptake by PEFC CLs, and the subsequent impact of water uptake on Pt utilization through developing a multiphysics model of the water wetting phenomena as a function of relative humidity. The model details water uptake via ionomer absorption, capillary condensation in the hydrophilic pores, and surface adsorption using molecular potential that account for various water and surface dipole interactions. The results quantify how mesoporous carbons with highly hydrophilic pores increase Pt utilization through the development of wetted layers, which at the same time enable optimized gas-transport pathways. It also demonstrates the impact of pore-size distribution (PSD) and physical and chemical parameters on the water uptake phenomena, allowing for future CL particle and structure optimization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Relationship between Sodium Content and Copper Activity for High Voltage Stability in O3-Type Layered Oxide Cathodes

Layered oxides with an O3 framework have attracted attention as cathode materials for sodium-ion batteries due to their high discharge capacity. Yet they are hampered for commercialization by poor cyclability due to structural instability during the sodium (de)intercalation process. The introduction of Cu in small fractions to the transition metal layers has been empirically observed to improve reversible specific capacity and cycling stability. Understanding the redox activity of Cu in O3-type Na x TMO 2 materials is crucial, as it could directly influence the charge compensation mechanism, voltage profile, and structural stability. However, the precise role of Cu in O3-type sodium cathodes under high-voltage cycling conditions (>4.1 V) remains insufficiently understood. To close this gap of knowledge, we studied the effect of Cu in two representative layered oxides with the same O3 stacking but different sodium stoichiometry, Na 0.9 Mn 1/2 Fe 1/3 Cu 1/6 O 2 and NaMn 1/2 Fe 1/3 Cu 1/6 O 2 . X-ray spectroscopy reveals that in Na 0.9 Mn 1/2 Fe 1/3 Cu 1/6 O 2 , Cu exhibits dual redox activity, Cu + /Cu 2+ in the pristine state and Cu 2+ /Cu 3+ upon charging in the sodium-deficient material, whereas only the Cu + /Cu 2+ redox couple is observed in the fully stoichiometric layered oxide. Furthermore, the results indicate that even a slight deficiency in sodium can significantly impact the electrochemical performance and material stability and alter the elemental redox activity of Cu.

Batteries↗

Redox active polymer devices and methods of using and manufacturing the same

The disclosed technology relates generally to apparatus comprising conductive polymers and more particularly to tag and tag devices comprising a redox-active polymer film, and method of using and manufacturing the same. In one aspect, an apparatus includes a substrate and a conductive structure formed on the substrate which includes a layer of redox-active polymer film having mobile ions and electrons. The conductive structure further includes a first terminal and a second terminal configured to receive an electrical signal therebetween, where the layer of redox-active polymer is configured to conduct an electrical current generated by the mobile ions and the electrons in response to the electrical signal. The apparatus additionally includes a detection circuit operatively coupled to the conductive structure and configured to detect the electrical current flowing through the conductive structure.

Johnson, Paul B.↗

Redox active polymer devices and methods of using and manufacturing the same

The disclosed technology relates generally to apparatuses comprising conductive polymers and more particularly to tags and tag devices comprising a redox-active polymer film, and methods of using and manufacturing the same. In one aspect, an apparatus includes a substrate and a conductive structure formed on the substrate which includes a layer of redox-active polymer film having mobile ions and electrons. The conductive structure further includes a first terminal and a second terminal configured to receive an electrical signal therebetween, where the layer of redox-active polymer is configured to conduct an electrical current generated by the mobile ions and the electrons in response to the electrical signal. The apparatus additionally includes a detection circuit operatively coupled to the conductive structure and configured to detect the electrical current flowing through the conductive structure.

Friesen, Cody A.↗

Redox active polymer devices and methods of using and manufacturing the same

The disclosed technology relates generally to apparatus comprising conductive polymers and more particularly to tag and tag devices comprising a redox-active polymer film, and method of using and manufacturing the same. In one aspect, an apparatus includes a substrate and a conductive structure formed on the substrate which includes a layer of redox-active polymer film having mobile ions and electrons. The conductive structure further includes a first terminal and a second terminal configured to receive an electrical signal therebetween, where the layer of redox-active polymer is configured to conduct an electrical current generated by the mobile ions and the electrons in response to the electrical signal. The apparatus additionally includes a detection circuit operatively coupled to the conductive structure and configured to detect the electrical current flowing through the conductive structure.

Johnson, Paul B.↗

Wide Band Gap Chalcogenide Semiconductors

Wide band gap semiconductors are essential for today’s electronic devices and energy applications because of their high optical transparency, controllable carrier concentration, and tunable electrical conductivity. The most intensively investigated wide band gap semiconductors are transparent conductive oxides (TCOs), such as tin-doped indium oxide (ITO) and amorphous In–Ga–Zn–O (IGZO), used in displays and solar cells, carbides (e.g., SiC) and nitrides (e.g., GaN) used in power electronics, and emerging halides (e.g., γ-CuI) and 2D electronic materials (e.g., graphene) used in various optoelectronic devices. Compared to these prominent materials families, chalcogen-based (Ch = S, Se, Te) wide band gap semiconductors are less heavily investigated but stand out because of their propensity for p-type doping, high mobilities, high valence band positions (i.e., low ionization potentials), and broad applications in electronic devices such as CdTe solar cells. This manuscript provides a review of wide band gap chalcogenide semiconductors. First, we outline general materials design parameters of high performing transparent semiconductors, as well as the theoretical and experimental underpinnings of the corresponding research methods. We proceed to summarize progress in wide band gap (EG > 2 eV) chalcogenide materials—namely, II–VI MCh binaries, CuMCh 2 chalcopyrites, Cu 3 MCh 4 sulvanites, mixed-anion layered CuMCh(O,F), and 2D materials—and discuss computational predictions of potential new candidates in this family, highlighting their optical and electrical properties. Then, we finally review applications—for example, photovoltaic and photoelectrochemical solar cells, transistors, and light emitting diodes—that employ wide band gap chalcogenides as either an active or passive layer. Overall, by examining, categorizing, and discussing prospective directions in wide band gap chalcogenides, this Review aims to inspire continued research on this emerging class of transparent semiconductors and thereby enable future innovations for optoelectronic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical Measurement of Atmospheric Corrosion

Corrosion of Shuttle thruster components in atmospheres containing high concentrations of nitrogen tetroxide (NTO) and water is an important issue in ground operations of bipropellant systems in humid locations. Measurements of the corrosivities of NTO-containing atmospheres and the responses of different materials to these atmospheres have been accomplished using an electrochemical sensor. The sensor is composed of alternating aluminum/titanium strips separated by thin insulating layers. Under high humidity conditions a thin film of water covers the surface of the sensor. Added NTO vapor reacts with the water film to form a conductive medium and establishes a galvanic cell. The current from this cell can be integrated with respect to time and related to the corrosion activity. The surface layer formed from humid air/NTO reacts in the same way as an aqueous solution of nitric acid. Nitric acid is generally considered an important agent in NTO corrosion situations. The aluminum/titanium sensor is unresponsive to dry air, responds slightly to humid air (> 75% RH), and responds strongly to the combination of humid air and NTO. The sensor response is a power function (n = 2) of the NTO concentration. The sensor does not respond to NTO in dry air. The response of other materials in this type of sensor is related to position of the material in a galvanic series in aqueous nitric acid. The concept and operation of this electrochemical corrosion measurement is being applied to other corrosive atmospheric contaminants such as hydrogen chloride, hydrogen fluoride, sulfur dioxide, and acidic aerosols.

DeArmond, Anna H.↗

Refining Microstructures in Additively Manufactured Al/Cu Gradients Through TiB 2 Inclusions

Here, the additive manufacture of compositionally graded Al/Cu parts by laser engineered net shaping (LENS) is demonstrated. The use of a blue light build laser enabled deposition on a Cu substrate. The thermal gradient and rapid solidification inherent to selective laser melting enabled mass transport of Cu up to 4 mm from a Cu substrate through a pure Al deposition, providing a means of producing gradients with finer step sizes than the printed layer thicknesses. Divorcing gradient continuity from layer or particle size makes LENS a potentially enabling technology for the manufacture of graded density impactors for ramp compression experiments. Printing graded structures with pure Al, however, was prevented by the growth of Al 2 Cu 3 dendrites and acicular grains amid a matrix of Al 2 Cu. A combination of adding TiB 2 grain refining powder and actively varying print layer composition suppressed the dendritic growth mode and produced an equiaxed microstructure in a compositionally graded part. Material phase was characterized for crystal structure and nanoindentation hardness to enable a discussion of phase evolution in the rapidly solidifying melt pool of a LENS print.

36 MATERIALS SCIENCE↗

High temperature nanoindentation of Cu–TiN nanolaminates

Here, we examined the high temperature indentation response of physical vapor deposited Cu–TiN multilayered nanocomposites with layer thicknesses ranging from 5 nm to 200 nm. A decrease in hardness with increasing temperature was observed, along with a strong correlation between the hardness and the nanometer-level TiN grain sizes, rather than layer thickness. The apparent activation energies calculated from the high temperature indentation experiments indicated that, for all but the smallest layer thicknesses, the deformation of copper in the nanolaminates dominate the plastic response in these composites. In the finest layer thicknesses, a decrease in the apparent activation energy value indicated possible co-deformation of Cu and TiN.

36 MATERIALS SCIENCE↗