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At least 307 records · Page 17

Application of Smart Solid State Sensor Technology in Aerospace Applications

Aerospace applications require a range of chemical sensing technologies to monitor conditions in both space vehicles and aircraft operations. One example is the monitoring of oxygen. For example, monitoring of ambient oxygen (O2) levels is critical to ensuring the health, safety, and performance of humans living and working in space. Oxygen sensors can also be incorporated in detection systems to determine if hazardous leaks are occurring in space propulsion systems and storage facilities. In aeronautic applications, O2 detection has been investigated for fuel tank monitoring. However, as noted elsewhere, O2 is not the only species of interest in aerospace applications with a wide range of species of interest being relevant to understand an environmental or vehicle condition. These include combustion products such as CO, HF, HCN, and HCl, which are related to both the presence of a fire and monitoring of post-fire clean-up operations. This paper discusses the development of an electrochemical cell platform based on a polymer electrolyte, NAFION, and a three-electrode configuration. The approach has been to mature this basic platform for a range of applications and to test this system, combined with "Lick and Stick" electronics, for its viability to monitor an environment related to astronaut crew health and safety applications with an understanding that a broad range of applications can be addressed with a core technology.

Hunter, Gary W.↗

NASA Tech Briefs, July 2010

Topics covered include: Wirelessly Interrogated Wear or Temperature Sensors; Processing Nanostructured Sensors Using Microfabrication Techniques; Optical Pointing Sensor; Radio-Frequency Tank Eigenmode Sensor for Propellant Quantity Gauging; High-Temperature Optical Sensor; Integral Battery Power Limiting Circuit for Intrinsically Safe Applications; Configurable Multi-Purpose Processor; Squeezing Alters Frequency Tuning of WGM Optical Resonator; Automated Computer Access Request System; Range Safety for an Autonomous Flight Safety System; Fast and Easy Searching of Files in Unisys 2200 Computers; Parachute Drag Model; Evolutionary Scheduler for the Deep Space Network; Modular Habitats Comprising Rigid and Inflatable Modules; More About N2O-Based Propulsion and Breathable-Gas Systems; Ultrasonic/Sonic Rotary-Hammer Drills; Miniature Piezoelectric Shaker for Distribution of Unconsolidated Samples to Instrument Cells; Lunar Soil Particle Separator; Advanced Aerobots for Scientific Exploration; Miniature Bioreactor System for Long-Term Cell Culture; Electrochemical Detection of Multiple Bioprocess Analytes; Fabrication and Modification of Nanoporous Silicon Particles; High-Altitude Hydration System; Photon Counting Using Edge-Detection Algorithm; Holographic Vortex Coronagraph; Optical Structural Health Monitoring Device; Fuel-Cell Power Source Based on Onboard Rocket Propellants; Polar Lunar Regions: Exploiting Natural and Augmented Thermal Environments; Simultaneous Spectral Temporal Adaptive Raman Spectrometer - SSTARS; Improved Speed and Functionality of a 580-GHz Imaging Radar; Bolometric Device Based on Fluxoid Quantization; Algorithms for Learning Preferences for Sets of Objects; Model for Simulating a Spiral Software-Development Process; Algorithm That Synthesizes Other Algorithms for Hashing; Algorithms for High-Speed Noninvasive Eye-Tracking System; and Adapting ASPEN for Orbital Express.

Source record↗

Delineating Confinement Regimes for Nafion Thin Films via Simultaneous QCM-D and Spectroscopic Ellipsometry

Proton-conducting ionomers used in electrodes of electrochemical devices form nanometer-scale films covering metallic catalyst surfaces, wherein they experience confinement and interfacial effects absent in the bulk polymer. This confinement alters the physical properties of the ionomer film, which is postulated to increase the density and is attributed to the transport limitations observed in fuel-cell electrodes. Despite studies showing reduced swelling, no systematic measurement has validated this phenomenon by demonstrating both densification and stiffening as the film gets thinner. Here, this study aims to fill this gap by reporting the humidity-driven changes in swelling, mass uptake, and density of Nafion ionomer films cast at varying thicknesses (10–320 nm) onto a gold-plated sensor. The films were simultaneously probed during humidification using spectroscopic ellipsometry (SE) and a quartz crystal microbalance with dissipation (QCM-D), which allowed for determination of the density and shear stiffness. The effects of confinement were prominently observed below ∼30 nm, with films showing increased density along with decreased swelling and mass uptake during hydration. In addition, the confined films show a negative excess volume upon initial water sorption, implying a larger proportion of absorbed water might bound to ionic groups in accord with notion of localized densification.

Espinet, Kevin B. [University of California, Berke↗

Fully Inkjet‐Printed, 2D Materials‐Based Field‐Effect Transistor for Water Sensing

Abstract Despite significant progress in solution‐processing of 2D materials, it remains challenging to reliably print high‐performance semiconducting channels that can be efficiently modulated in a field‐effect transistor (FET). Herein, electrochemically exfoliated MoS 2 nanosheets are inkjet‐printed into ultrathin semiconducting channels, resulting in high on/off current ratios up to 10 3 . The reported printing strategy is reliable and general for thin film channel fabrication even in the presence of the ubiquitous coffee‐ring effect. Statistical modeling analysis on the printed pattern profiles suggests that a spaced parallel printing approach can overcome the coffee‐ring effect during inkjet printing, resulting in uniform 2D flake percolation networks. The uniformity of the printed features allows the MoS 2 channel to be hundreds of micrometers long, which easily accommodates the typical inkjet printing resolution of tens of micrometers, thereby enabling fully printed FETs. As a proof of concept, FET water sensors are demonstrated using printed MoS 2 as the FET channel, and printed graphene as the electrodes and the sensing area. After functionalization of the sensing area, the printed water sensor shows a selective response to Pb 2+ in water down to 2 ppb. This work paves the way for additive nanomanufacturing of FET‐based sensors and related devices using 2D nanomaterials.

36 MATERIALS SCIENCE↗

Carbon Nanomaterials for Biosensing Applications

Biosensing devices comprised of carbon nanotubes and nanofibers have been developed for astronaut crew point-of-care. Their inherent nanometer scale, high conductivity, wide potential window, good biocompatibility and well-defined surface chemistry make them ideal candidates as biosensor electrodes. Here, we report two studies using carbon nanotube and carbon nanofiber electrodes for biomedical applications. First, a 3x3 electrode device, with each electrode containing 40,000 carbon nanofiber nanoelectrodes was fabricated on silicon using traditional microfabrication processing. The device was demonstrated as a multiplexed immunosensor for simultaneous, label-free detection of cardiac troponin-I, C-reactive protein and myoglobin. Antibodies specific to cardiac troponin-I, C-reactive protein and myoglobin were covalently bound to the CNF surface and were characterized using electrochemical impedance spectroscopy and differential pulse voltammetry. Each step of the modification process resulted in changes in resistance to charge transfer due to the changes at the electrode surface upon antibody immobilization and binding to the specific cardiac protein. The real-time label free detection of the three cardiac markers from pure components and mixtures was demonstrated with high sensitivity, down to 0.2 ng/mL, and good selectivity. Detection in human blood serum did not present false positives from non-specific protein adsorption. More recently, this detection scheme has been applied to inkjet printed carbon nanotube electrodes on Kapton and paper. Printed devices have several unique advantages including simple and inexpensive fabrication. The results demonstrate that these sensors can serve a miniaturized, low cost device for detection of proteins in complex mixtures making this platform a good candidate for early stage diagnosis of myocardial infarction. Future inkjet printed devices can be fabricated have the added advantage in their suitability to be manufactured in an in-space, microgravity environment.

carbon nanotubes↗

In-situ electrochemical and water quality data; Slate River and East River floodplains, Crested Butte, CO; May 2022-September 2022

This data package includes a time-series of field measurements from May to September 2022 in groundwater and surface water from the Slate River and East River floodplains in Crested Butte, CO, a focus field site for the SLAC Floodplain Hydro-Biogeochemistry SFA. The data was generated as part of the work targeting the overarching research question for the SLAC SFA: How do ubiquitous subsurface interfaces mediate molecular-scale biogeochemical processes and groundwater quality in floodplains and watersheds? The data package includes 5 data files, one for each measured variable: specific conductivity, pH, dissolved oxygen, water temperature and alkalinity. All measurements were recorded in the field immediately after water sampling. Groundwater samples were extracted from a network of installed rhizons (Rhizosphere Research Products, part no. 19.60.21F, 0.6 micrometer mesh size) and piezometer wells within the floodplain. In addition to the data files, there is a terminology file explaining the terms used, a file level metadata file, and a sensor file with metadata about the sensors used.All files are in csv format.

54 ENVIRONMENTAL SCIENCES↗

Chemical Microsensor Development for Aerospace Applications

Numerous aerospace applications, including low-false-alarm fire detection, environmental monitoring, fuel leak detection, and engine emission monitoring, would benefit greatly from robust and low weight, cost, and power consumption chemical microsensors. NASA Glenn Research Center has been working to develop a variety of chemical microsensors with these attributes to address the aforementioned applications. Chemical microsensors using different material platforms and sensing mechanisms have been produced. Approaches using electrochemical cells, resistors, and Schottky diode platforms, combined with nano-based materials, high temperature solid electrolytes, and room temperature polymer electrolytes have been realized to enable different types of microsensors. By understanding the application needs and chemical gas species to be detected, sensing materials and unique microfabrication processes were selected and applied. The chemical microsensors were designed utilizing simple structures and the least number of microfabrication processes possible, while maintaining high yield and low cost. In this presentation, an overview of carbon dioxide (CO2), oxygen (O2), and hydrogen/hydrocarbons (H2/CxHy) microsensors and their fabrication, testing results, and applications will be described. Particular challenges associated with improving the H2/CxHy microsensor contact wire-bonding pad will be discussed. These microsensors represent our research approach and serve as major tools as we expand our sensor development toolbox. Our ultimate goal is to develop robust chemical microsensor systems for aerospace and commercial applications.

hydrogen sensors↗

Mediated Electrochemical Probing: A Systems-Level Tool for Redox Biology

Biology uses well-known redox mechanisms for energy harvesting (e.g., respiration), biosynthesis, and immune defense (e.g., oxidative burst), and now we know biology uses redox for systems-level communication. Currently, we have limited abilities to “eavesdrop” on this redox modality, which can be contrasted with our abilities to observe and actuate biology through its more familiar ionic electrical modality. In this Perspective, we argue that the coupling of electrochemistry with diffusible mediators (electron shuttles) provides a unique opportunity to access the redox communication modality through its electrical features. Here, we highlight previous studies showing that mediated electrochemical probing (MEP) can “communicate” with biology to acquire information and even to actuate specific biological responses (i.e., targeted gene expression). We suggest that MEP may reveal an extent of redox-based communication that has remained underappreciated in nature and that MEP could provide new technological approaches for redox biology, bioelectronics, clinical care, and environmental sciences.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A hybrid cyt c maturation system enhances the bioelectrical performance of engineered Escherichia coli by improving the rate-limiting step

Bioelectronic devices can use electron flux to enable communication between biotic components and abiotic electrodes. We have modified Escherichia coli to electrically interact with electrodes by expressing the cytochrome c from Shewanella oneidensis MR-1. However, we observe inefficient electrical performance, which we hypothesize is due to the limited compatibility of the E. coli cytochrome c maturation (Ccm) systems with MR-1 cytochrome c. Here we test whether the bioelectronic performance of E. coli can be improved by constructing hybrid Ccm systems containing protein domains from both E. coli and S. oneidensis MR-1. The hybrid CcmH increased cytochrome c expression by increasing the abundance of CymA 60%, while only slightly changing the abundance of the other cytochromes c. Electrochemical measurements showed that the overall current from the hybrid ccm strain increased 121% relative to the wildtype ccm strain, with an electron flux per cell of 12.3 ± 0.3 fA·cell -1 . Additionally, the hybrid ccm strain doubled its electrical response with the addition of exogenous flavin, and quantitative analysis of this demonstrates CymA is the rate-limiting step in this electron conduit. These results demonstrate that this hybrid Ccm system can enhance the bioelectrical performance of the cyt c expressing E. coli, allowing the construction of more efficient bioelectronic devices.

59 BASIC BIOLOGICAL SCIENCES↗

Ground Test Stand Development for One-step Electrochemical Production of High-Pressure Oxygen

NASA designed a test rig, High-Pressure Oxygen Generation Assembly (HPOGA) to test a novel method of electrolysis as an alternative technology to the state-of-the-art Oxygen Generation Assembly (OGA) currently on the International Space Station (ISS). This approach involves utilizing a specialized electrolysis cell stack designed to both generate and compress high-pressure oxygen up to 3600 PSIG. The design eliminates the need for an external compressor and hydrogen separator, streamlining the oxygen generation process. HPOGA tests the viability of an electrolysis cell stack for extended life usage. Within the system, there are several key subsystems: nitrogen, high/low pressure oxygen, hydrogen, water recirculation, and water injection. The water injection subsystem supplies deionized (DI) water to a centralized reservoir for consumption. Subsequently, a water recirculation loop transfers the DI water across the cathode side of the electrolysis cell stack with constant flow rate. The result is a supply of hydrogen in the water loop and oxygen accumulation on the anode side of the cell stack. Hydrogen is evaporated out as part of the hydrogen sub-system which also measures hydrogen/oxygen concentration for safety. The oxygen subsystem is responsible for managing high pressure oxygen, O2 exhaust, and conducting hydrogen/oxygen concentration measurements. The nitrogen subsystem serves dual functions, purging the hydrogen/oxygen subsystems, and regulating pressure in both high/low-pressure O2 sections via pneumatic back pressure regulators. Various sensors monitor pressure, temperature, humidity, gas concentration and flow rate in each subsystem. This paper presents the design and testing of a comprehensive test stand, which serves to operate and functionally verify the performance of the electrolysis cell while offering valuable lessons learned.

electrolysis↗

Sulfur Poisoning and Performance Recovery of SOFC Air Electrodes

The sulfur poisoning and performance recovery of the state-of-the-art SOFC cathodes (La 0 . 80 Sr 0 . 20 ) 0 . 95 MnO 3 ± δ (LSM) and (La 0 . 60 Sr 0 . 40 ) 0 . 95 Co 0 . 20 Fe 0 . 80 O 3 – δ (LSCF), have been studied. Electrochemical impedance spectroscopy measurements of LSCF|GDC and LSM|YSZ half-cells are carried out in alternating atmospheres of air and SO 2 –air at 700°C for hundreds of hours. In the presence of SO 2 , the electrochemical performance of both the cells decays with ohmic and non-ohmic losses, owing to the absorption and chemical interaction of SO 2 with the electrodes. In LSCF, the SrO segregated on the surface tends to absorb and react with SO 2 , forming SrSO 4 followed by the exsolution of Co-Fe. As for LSM, SO 2 is absorbed onto the Sr-rich areas of LSM, including the active reaction sites near the TPBs, leading to Sr exsolution and SrSO 4 formation, leaving a Sr-deficient LSM. During the subsequent exposure to air, the performance of the sulfur-contaminated LSM is almost restored. The LSM particles, exposed to alternating atmospheres of air and SO 2 -air during the electrochemical tests, show a relatively clean surface with sparsely distributed SrSO 4 particles, indicating a high stability against sulfur poisoning. It is suggested that the loosely adsorbed SO 2 at the TPBs is readily swept away by the SO 2 -free air flow, recovering its ORR activity, whereas the Sr-deficient LSM due to Sr-exsolution stays modified, contributing to the incomplete performance restoration. Unlike the case of LSM, the performance of the sulfur-poisoned LSCF partially recovers during the subsequent exposure to air. Correspondingly, the LSCF particles have a modified morphology covered with numerous nanoparticles, mostly SrSO 4 , showing the irreversible aspect of the sulfur poisoning. The morphology modification is not concentrated near the electrode/electrolyte interface but over the entire cathode, indicating that the degree of recovery from sulfur poisoning is closely related to the presence of SrO and chemical activity of Sr in the electrodes at the solid-gas interface. These results also show the potential application of LSM for a sulfur sensor available in high-temperature harsh conditions.

25 ENERGY STORAGE↗

NASA Tech Briefs, May 2012

Topics covered include: An "Inefficient Fin" Non-Dimensional Parameter to Measure Gas Temperatures Efficiently; On-Wafer Measurement of a Multi-Stage MMIC Amplifier with 10 dB of Gain at 475 GHz; Software to Control and Monitor Gas Streams; Miniaturized Laser Heterodyne Radiometer (LHR) for Measurements of Greenhouse Gases in the Atmospheric Column; Anomaly Detection in Test Equipment via Sliding Mode Observers; Absolute Position of Targets Measured Through a Chamber Window Using Lidar Metrology Systems; Goldstone Solar System Radar Waveform Generator; Fast and Adaptive Lossless Onboard Hyperspectral Data Compression System; Iridium Interfacial Stack - IrIS; Downsampling Photodetector Array with Windowing; Optical Phase Recovery and Locking in a PPM Laser Communication Link; High-Speed Edge-Detecting Line Scan Smart Camera; Optical Communications Channel Combiner; Development of Thermal Infrared Sensor to Supplement Operational Land Imager; Amplitude-Stabilized Oscillator for a Capacitance-Probe Electrometer; Automated Performance Characterization of DSN System Frequency Stability Using Spacecraft Tracking Data; Histogrammatic Method for Determining Relative Abundance of Input Gas Pulse; Predictive Sea State Estimation for Automated Ride Control and Handling - PSSEARCH; LEGION: Lightweight Expandable Group of Independently Operating Nodes; Real-Time Projection to Verify Plan Success During Execution; Automated Performance Characterization of DSN System Frequency Stability Using Spacecraft Tracking Data; Web-Based Customizable Viewer for Mars Network Overflight Opportunities; Fabrication of a Cryogenic Terahertz Emitter for Bolometer Focal Plane Calibrations; Fabrication of an Absorber-Coupled MKID Detector; Graphene Transparent Conductive Electrodes for Next- Generation Microshutter Arrays; Method of Bonding Optical Elements with Near-Zero Displacement; Free-Mass and Interface Configurations of Hammering Mechanisms; Wavefront Compensation Segmented Mirror Sensing and Control; Long-Life, Lightweight, Multi-Roller Traction Drives for Planetary Vehicle Surface Exploration; Reliable Optical Pump Architecture for Highly Coherent Lasers Used in Space Metrology Applications; Electrochemical Ultracapacitors Using Graphitic Nanostacks; Improved Whole-Blood-Staining Device; Monitoring Location and Angular Orientation of a Pill; Molecular Technique to Reduce PCR Bias for Deeper Understanding of Microbial Diversity; Laser Ablation Electrodynamic Ion Funnel for In Situ Mass Spectrometry on Mars; High-Altitude MMIC Sounding Radiometer for the Global Hawk Unmanned Aerial Vehicle; PRTs and Their Bonding for Long-Duration, Extreme-Temperature Environments; Mid- and Long-IR Broadband Quantum Well Photodetector; 3D Display Using Conjugated Multiband Bandpass Filters; Real-Time, Non-Intrusive Detection of Liquid Nitrogen in Liquid Oxygen at High Pressure and High Flow; Method to Enhance the Operation of an Optical Inspection Instrument Using Spatial Light Modulators; Dual-Compartment Inflatable Suitlock; Large-Strain Transparent Magnetoactive Polymer Nanocomposites; Thermodynamic Vent System for an On-Orbit Cryogenic Reaction Control Engine; Time Distribution Using SpaceWire in the SCaN Testbed on ISS; and Techniques for Solution- Assisted Optical Contacting.

Source record↗

First-principles Modeling and Design of Solid-State Interfaces for the Protection and Use of Lithium Metal Anodes

Li-ion batteries are one of the most advanced energy storage technologies in use today. Li-ion batteries are used in a multitude of applications ranging from consumer electronics, medical devices, sensors and grid storage. However, improving the capacity and energy density delivered by current Li-ion technology requires advanced materials research into novel chemical systems. In this project we have focused particularly in the use of solid-state electrolytes with lithium metal electrodes. Research into all solid-state batteries (ASSB) with Li metal electrodes has significantly expanded in recent years, however most studies reported experimental findings, which left substantial room for theoretical and modeling work as a tool to understand and determine design principles allowing reliable and safe use of ASSBs with Li metal. Among the remaining obstacles preventing reliable use of ASSBs with a Li metal electrode, the stability of the interface between the solid electrolyte and Li metal, and the propagation/dendrite formation of Li metal and resulting mechanical degradation of the electrolyte are key phenomenon that are yet to be fully understood. In the current project we have addressed these two coupled phenomena using first principles calculations and mesoscale continuum modeling. We have obtained chemical and electrochemical stability windows for several solid electrolyte materials. Additionally, from mathematical and numerical modeling of Li protrusion and dendrite initiation during plating and stripping we have determined design criteria in terms of chemical, electrochemical, and mechanical properties and operating conditions for which stable deposition can occur. We also considered the effects of mixed electronic-ionic conduction in solid electrolytes, which has more recently been suggested as another important mechanism involved in ASSB failure. Throughout our work we have successfully addressed important questions necessary for the use of ASSB’s. We have determined guiding principles for materials properties and operating conditions necessary to operate ASSB’s. And have proposed novel solid electrolyte materials with predicted chemical stability an ionic conductivity. Although this represents significant progress in our understanding, open questions remain in order to fully develop reliable and safely operate ASSBs with Li metal. Future work, building on this project will require further experimental, theoretical and simulation efforts to address remaining questions.

25 ENERGY STORAGE↗

Pyoverdine binding aptamers and label-free electrochemical detection of pseudomonads

Pyoverdines are iron-chelating siderophores employed by various pseudomonads to promote their growth in iron-limited environments, facilitating both beneficial and detrimental interactions with co-inhabiting microbes or hosts, including plants and animals. The fluorescent pseudomonads produce fluorescent pyoverdines comprised of a conserved central chromophore and a unique strain-specific peptidic side chain produced by non-ribosomal peptide synthetases. Pyoverdine Pf5 (PVD-Pf5) is produced by Pseudomonas protegens Pf-5, a species known for supporting plant growth and its involvement in plant pathogen control. To develop a means of exploring the dynamics of P. protegens activity in soil and in the rhizosphere, we selected DNA aptamers that specifically recognize PVD-Pf5 with high affinities. Two selected aptamers with only 16% identity in sequence were examined for structure and function. We found evidence that both aptamers form structures in their apo-forms and one aptamer has structural features suggesting the presence of a G-quadruplex. Although their tertiary structures are predicted to be different, both aptamers bind the target PVD-Pf5 with similar affinities and do not bind other siderophores, including the related pyoverdine, pseudobactin, produced by Pseudomonas sp. B10. One aptamer binds the pyoverdine peptide component and may also interact with the chromophore. This aptamer was integrated into a nanoporous aluminum oxide biosensor and demonstrated to successfully detect PVD-Pf5 and not to detect other siderophores that do not bind to the aptamer when evaluated in solution. This sensor provides a future opportunity to track the locations of P. protegens around plant roots and to monitor PVD-Pf5 production and movement through the soil.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Abisko: Deep codesign of an architecture for spiking neural networks using novel neuromorphic materials

The Abisko project aims to develop an energy-efficient spiking neural network (SNN) computing architecture and software system capable of autonomous learning and operation. The SNN architecture explores novel neuromorphic devices that are based on resistive-switching materials, such as memristors and electrochemical RAM. Equally important, Abisko uses a deep codesign approach to pursue this goal by engaging experts from across the entire range of disciplines: materials, devices and circuits, architectures and integration, software, and algorithms. Here, the key objectives of our Abisko project are threefold. First, we are designing an energy-optimized high-performance neuromorphic accelerator based on SNNs. This architecture is being designed as a chiplet that can be deployed in contemporary computer architectures and we are investigating novel neuromorphic materials to improve its design. Second, we are concurrently developing a productive software stack for the neuromorphic accelerator that will also be portable to other architectures, such as field-programmable gate arrays and GPUs. Third, we are creating a new deep codesign methodology and framework for developing clear interfaces, requirements, and metrics between each level of abstraction to enable the system design to be explored and implemented interchangeably with execution, measurement, a model, or simulation. As a motivating application for this codesign effort, we target the use of SNNs for an analog event detector for a high-energy physics sensor.

97 MATHEMATICS AND COMPUTING↗

Carbon nanospike coated nanoelectrodes for measurements of neurotransmitters

Here, carbon nanoelectrodes enable the detection of neurotransmitters at the level of single cells, vesicles, synapses and small brain structures. Previously, the etching of carbon fibers and 3D printing based on direct laser writing have been used to fabricate carbon nanoelectrodes, but these methods lack the ability of mass manufacturing. In this paper, we mass fabricate carbon nanoelectrodes by growing carbon nanospikes (CNSs) on metal wires. CNSs have a short, dense and defect-rich surface that produces remarkable electrochemical properties, and they can be mass fabricated on almost any substrate without using catalysts. Tungsten wires and niobium wires were electrochemically etched in batch to form sub micrometer sized tips, and a layer of CNSs was grown on the metal wires using plasma-enhanced chemical vapor deposition (PE-CVD). The thickness of the CNS layer was controlled by the deposition time, and a thin layer of CNSs can effectively cover the entire metal surface while maintaining the tip size within the sub micrometer scale. The etched tungsten wires produced tapered conical nanotips, while the etched niobium wires were long and thin. Both showed excellent sensitivity for the detection of outer sphere ruthenium hexamine and the inner sphere test compound ferricyanide. The CNS nanosensors were used for the measurement of dopamine, serotonin, ascorbic acid and DOPAC with fast-scan cyclic voltammetry. The CNS nanoelectrodes had a large surface area and numerous defect sites, which improved the sensitivity, electron transfer kinetics and adsorption. Finally, the CNS nanoelectrodes were compared with other nanoelectrode fabrication methods, including flame etching, 3D printing, and nanopipettes, which are slower to make and more difficult for mass fabrication. Thus, CNS nanoelectrodes are a promising strategy for the mass fabrication of nanoelectrode sensors for neurotransmitters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Voltammetry measurements in lithium chloride-lithium oxide (LiCl–Li 2 O) salt: An evaluation of working electrode materials

Instrumentation to provide process monitoring (PM) and safeguards for the oxide reduction (OR) step in the electrochemical processing of used oxide nuclear fuel is necessary to ensure equipment is operated as declared. Cyclic voltammetry (CV) has been proposed for real-time monitoring of the operation of an OR process for safeguards purposes. In this study, different materials including 316 stainless steel (SS), tantalum (Ta), molybdenum (Mo), tungsten (W), platinum (Pt), and iridium (Ir) were evaluated as potential working electrode (WE) materials based on their chemical inertness, corrosion resistance, and sensitivity in detecting Li 2 O and other chloride salts in the OR electrolyte. Of the electrodes evaluated, 316 SS, Ir, and Pt all performed reasonably well in the LiCl-Li 2 O electrolyte. Here, stainless steel was operated in the cathodic potential and had reasonable corrosion resistance and is relatively inexpensive. Iridium could be operated in both the cathodic and anodic potentials and was the most corrosion resistant of those evaluated. Platinum is limited to the anodic potential range, had reasonable corrosion resistance, and was the most sensitive to Li 2 O concentrations in the salt. In the development of a stand-alone safeguards instrumentation, our recommendation is a CV sensor fitted with both Ir and Pt WEs. The results in this study may also be helpful for anode material selection in other electrometallurgy industries, such as molten salt electrolysis.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

Application of Principal Component Analysis to Electrochemical Reprocessing PM and NMAC

In this report, data from an electrorefiner (ER) for nuclear fuel reprocessing is evaluated for process monitoring (PM) conclusions. This data comes from tests performed at the Idaho National Laboratory in 2022. Multivariate approaches utilizing methods of Principal Component Analysis (PCA) is applied. This is based off established work in process monitoring for fault detection in industrial facilities. This report will discuss the background, methods, and results of the application and some of the conclusions and applications that can be drawn from them. PCA is applied to two different electrorefiner (ER) operations that occurred at Idaho National Laboratory between August and October 2022. The first operation occurred with little incident while the second had several noted faults in the equipment in operational logs. The data from the first run was used to train the data for “normal” operations and applied to both sets of data to determine when operations were in an “off-normal” condition and identify where the fault occurs through PCA. PCA was able to identify off-normal events and identify the cause for off-normal operations. These identified off-normal events matched with the events and their causes in the operational logs. However, small amounts of variance in the data led to false detection of “off-normal” events. Thus, careful selection of training data and a-posteriori conclusions based off operator assessments will both be required for application of PCA to PM applications. This work demonstrated that multivariate approaches and latent variables are applicable to pyroprocessing PM applications and can be further expanded in future work as quality variables such as salt concentration from sensors and sampling become available.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗