Results for “activity coefficient” — Page 35

NASA NTRS1997

The Effect of Temperature Dependent Material Nonlinearities on the Response of Piezoelectric Composite Plates

Previously developed analytical formulations for piezoelectric composite plates are extended to account for the nonlinear effects of temperature on material properties. The temperature dependence of the composite and piezoelectric properties are represented at the material level through the thermopiezoelectric constitutive equations. In addition to capturing thermal effects from temperature dependent material properties, this formulation also accounts for thermal effects arising from: (1) coefficient of thermal expansion mismatch between the various composite and piezoelectric plies and (2) pyroelectric effects on the piezoelectric material. The constitutive equations are incorporated into a layerwise laminate theory to provide a unified representation of the coupled mechanical, electrical, and thermal behavior of smart structures. Corresponding finite element equations are derived and implemented for a bilinear plate element with the inherent capability to model both the active and sensory response of piezoelectric composite laminates. Numerical studies are conducted on a simply supported composite plate with attached piezoceramic patches under thermal gradients to investigate the nonlinear effects of material property temperature dependence on the displacements, sensory voltages, active voltages required to minimize thermal deflections, and the resultant stress states.

Lee, Ho-Jun↗

NASA NTRS1961

Effect of Surface Preparation and Gas Flow on Nitrogen Atom Surface Recombination

The effects of surface preparation and gas flow on the recombination of nitrogen atoms at copper and platinum surfaces were determined. Atoms were generated by an electrodeless 2450-megacycle-per-second discharge, and their concentration was measured by gas-phase titration with nitric oxide. Test surfaces were either vacuum-evaporated films or spheres machined from bulk metal and cemented around small glass-bead thermistors. Heat released by recombination was measured as the difference in electrical energy required to maintain a given thermistor temperature with and without a catalytic surface exposed. Recombination coefficients measured at flow velocities of 1120, 1790, 2250, and 3460 centimeters per second and at pressures of 0.42 and 0.59 millimeter of mercury showed that flow conditions had no effect. The results were also independent of atom concentration. A rough indication of the temperature dependence was obtained; it was greater for copper than for platinum. Platinum films deposited on platinum or on glass had the same activity - about 3 percent of the atoms impinging recombined. With copper, however, the glass substrate greatly reduced the percent of atoms recombining over that of a bulk copper substrate where 4 percent of the impinging atoms recombined. This effect could be overcome by depositing a second film on top of the first. Bulk metal samples were subjected to various surface treatments including polishing, degreasing with a chlorinated hydrocarbon, washing with nitric acid, and rinsing with water. Polished, degreased platinum had low activity compared to an evaporated film, but nitric acid treatment made it equivalent. Polished, degreased copper was only slightly less active than a copper film; nitric acid etching decreased the activity still further, probably by preferentially exposing facets of low catalytic efficiency.

Prok, George M.↗

NASA NTRS2001

Atomic Data and Spectral Line Intensities for Ne III

Electron impact collision strengths, energy levels, oscillator strengths and spontaneous radiative decay rates are calculated for Ne III. The configurations used are 2s(sup 2) 2p(sup 4),2s2p(sup 5),2s(sup 2) 2p(sup 3)3s, and 2s(sup 2)3p(sup 3)3d giving rise to 57 fine-structure levels in intermediate coupling. Collision strengths are calculated at five incident energies, 5, 10, 15, 20, and 25 Ry. Excitation rate coefficients are calculated by assuming a Maxwellian electron velocity distribution at an electron temperature of logT,(K)=5.0, corresponding to maximum abundance of Ne III. Using the excitation rate coefficients and the radiative transition rates, statistical equilibrium equations for level populations are solved at electron densities covering the range of 10(exp 8)-10(exp 14) per cubic centimeter. Relative spectral line intensities are calculated. Proton excitation rates between the lowest three levels have been included in the statistical equilibrium equations. The predicted Ne III line intensities are compared with SERTS rocket measurements of a solar active region and of a laboratory EUV light source.

Bhatia, A. K.↗

NASA NTRS2012

Structures and Mechanisms Design Concepts for Adaptive Deployable Entry Placement Technology

System studies have shown that large deployable aerodynamic decelerators such as the Adaptive Deployable Entry and Placement Technology (ADEPT) concept can revolutionize future robotic and human exploration missions involving atmospheric entry, descent and landing by significantly reducing the maximum heating rate, total heat load, and deceleration loads experienced by the spacecraft during entry [1-3]. ADEPT and the Hypersonic Inflatable Aerodynamic Decelerator (HIAD) [4] share the approach of stowing the entry system in the shroud of the launch vehicle and deploying it to a much larger diameter prior to entry. The ADEPT concept provides a low ballistic coefficient for planetary entry by employing an umbrella-like deployable structure consisting of ribs, struts and a fabric cover that form an aerodynamic decelerator capable of undergoing hypersonic flight. The ADEPT "skin" is a 3-D woven carbon cloth that serves as a thermal protection system (TPS) and as a structural surface that transfers aerodynamic forces to the underlying ribs [5]. This paper focuses on design activities associated with integrating ADEPT components (cloth, ribs, struts and mechanisms) into a system that can function across all configurations and environments of a typical mission concept: stowed during launch, in-space deployment, entry, descent, parachute deployment and separation from the landing payload. The baseline structures and mechanisms were selected via trade studies conducted during the summer and fall of 2012. They are now being incorporated into the design of a ground test article (GTA) that will be fabricated in 2013. It will be used to evaluate retention of the stowed configuration in a launch environment, mechanism operation for release, deployment and locking, and static strength of the deployed decelerator. Of particular interest are the carbon cloth interfaces, underlying hot structure, (Advanced Carbon- Carbon ribs) and other structural components (nose cap, struts, and main body) designed to withstand the pressure and extremely high heating experienced during planetary entry.

Yount, Bryan C.↗

NASA NTRS2011

Attitude Determination and Control Subsystem (ADCS) Preparations for the EPOXI Flyby of Comet Hartley 2

On November 4, 2010 the former "Deep Impact" spacecraft, renamed "EPOXI" for its extended mission, flew within 700km of comet 103P/Hartley 2. In July 2005, the spacecraft had previously imaged a probe impact of comet Tempel 1. The EPOXI flyby was the fifth close encounter of a spacecraft with a comet nucleus and marked the first time in history that two comet nuclei were imaged at close range with the same suite of onboard science instruments. This challenging objective made the function of the attitude determination and control subsystem (ADCS) critical to the successful execution of the EPOXI flyby.As part of the spacecraft flyby preparations, the ADCS operations team had to perform meticulous sequence reviews, implement complex spacecraft engineering and science activities and perform numerous onboard calibrations. ADCS contributions included design and execution of 10 trajectory correction maneuvers, the science calibration of the two telescopic instruments, an in-flight demonstration of high-rate turns between Earth and comet point, and an ongoing assessment of reaction wheel health. The ADCS team was also responsible for command sequences that included updates to the onboard ephemeris and sun sensor coefficients and implementation of reaction wheel assembly (RWA) de-saturations.

attitude determination and control↗

NASA NTRS1982

The composition and vertical structure of the lower cloud deck on Venus

Excluding the insertion of a probe into the lower Venus atmosphere, the only means of examining the atmospheric properties below the upper cloud layer are by passive or active radio techniques. Particularly, in a radio occultation experiment, the amplitude and Doppler data of a signal which has been refracted by the dense Venus atmosphere provide temperature, pressure, atmospheric density, cloud mass content, and some information about the cloud composition. The Venus orbiting spacecraft Pioneer Venus has provided radio occultation data for more than two years. The present investigation has the primary goal to use the absorption coefficient profiles derived from the radio occultation experiment to determine the mass content and composition of the Venusian lower deck. Attention is given to an experiment description, liquid content calculations, the mass content equation, the subtraction of gaseous absorbers, dielectric constant measurements, the concentration profile, the spherical shell model, and mass content profiles for all orbits.

Cimino, J.↗

NASA NTRS1985

Reentry guidance and control for an Aeroassist Flight

An Aeroassist Flight Experiment (AFE) is proposed to show how the use of an atmospheric braking device can reduce the perigee velocity of a vehicle upon its return from a mission to geosynchronous orbit. This braking device would be used to attain low earth orbit comparable with the STS Orbiter. The basic design of the AFE is presented and the guidance and control aspects of the design are discussed. The lifting-brake design selected for the AFE is a raked cone with a coefficient of drag of 1.5 and a lift to drag ratio of 0.3. The potential second flight of the AFE would have a ballute aerobraking device with a predictor/corrector guidance scheme. It is concluded that the approach described to implement the AFE is a feasible one and minimizes risk by having adequate margins wherever needed, by reducing error sources in sensitive areas, and by conducting an extensive simulation activity to verify the design.

Brandon, L. B.↗

NASA NTRS1991

Diffusion of water in rhyolitic glasses

The process of water diffusion in 11 natural rhyolitic glasses was considered using the results of measurements by FTIR spectroscopy of concentration profiles of both H2O and OH at different temperatures. The diffusion coefficients of H2O and OH, D(H2O) and D(OH), respectively, were calculated from concentration profiles. Results indicate that, at 400-530 C, the value of D(OH) is negligible compared to that of D(H2O), and that OH does not contribute significantly to the diffusion of total water even at water concentrations as low as 0.2 percent, which is minute compared to that of OH. In the activation energy vs radius plot, the D(H2O) followed the same trend as that of noble gases.

Zhang, Youxue↗

NASA NTRS1997

The Interplay Between Transpiration and Runoff Formulations in Land Surface Schemes Used with Atmospheric Models

The Project for Intercomparison of Land-surface Parameterization Schemes (PILPS) has shown that different land surface models (LSMS) driven by the same meteorological forcing can produce markedly different surface energy and water budgets, even when certain critical aspects of the LSMs (vegetation cover, albedo, turbulent drag coefficient, and snow cover) are carefully controlled. To help explain these differences, the authors devised a monthly water balance model that successfully reproduces the annual and seasonal water balances of the different PILPS schemes. Analysis of this model leads to the identification of two quantities that characterize an LSM's formulation of soil water balance dynamics: (1) the efficiency of the soil's evaporation sink integrated over the active soil moisture range, and (2) the fraction of this range over which runoff is generated. Regardless of the LSM's complexity, the combination of these two derived parameters with rates of interception loss, potential evaporation, and precipitation provides a reasonable estimate for the LSM's simulated annual water balance. The two derived parameters shed light on how evaporation and runoff formulations interact in an LSM, and the analysis as a whole underscores the need for compatibility in these formulations.

Koster, Rindal D.↗

DOE OSTI2025

Development of carbon nanosensor for vinpocetine at zinc oxide modified carbon matrix with anionic surfactant for clinical application

A nano-level sensing method was formulated for the trace-level detection and determination of vinpocetine (VIN) at a zinc oxide nanomaterial-based carbon matrix with immobilised anionic surfactant sodium dodecyl sulfate (ZnO-SDS/CPE) using cyclic voltammetry (CV) and square wave voltammetry (SWV) approaches. The catalytic properties of ZnO impact the electron rate of VIN activity, resulting in a threefold increase in the VIN peak response with the ZnO-SDS-modified sensor. Here, the effects of several factors, including scan rate, pH, accumulation length, modifier amount, and concentration, were investigated on the VIN peak current. The electro-oxidation of VIN by pH study involves one proton and one electron. The CV method also investigated the effect of scan rate. The charge transfer coefficient (α) is obtained to be 0.58, and the heterogeneous rate constant (k°) is estimated to be 4.46 s⁻¹. The concentration effect of VIN was studied using the SWV method. Specifically, the SWV methodology achieved the lowest detection limit compared to previously published approaches, with estimated values of the Limit of Detection (LOD) and Limit of Quantification (LOQ) being 2.2 × 10⁻⁸ M and 7.7 × 10⁻⁸ M, respectively. The trace level of VIN in tablet and urine samples was determined using the modified sensor. Moreover, the sensor demonstrates particular reproducibility and long-term stability, making it suitable for real-time applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

On the Stability of Power Transmission Systems Under Persistent Inverter Attacks: A Bi-Linear Matrix Approach

We investigate the stability and robustness properties of a power transmission system under persistent deceiving attacks on inverter-interfaced energy resources. The attacks can corrupt the damping coefficients in the inverters' controllers and measurements of the frequency at the points of coupling. Leveraging tools from hybrid dynamical systems theory, we characterize a broad family of persistent (and not necessarily periodic) attacks acting on the inverters, under which the stability properties of the transmission system can be shown to not be compromised. To address potentially conservative conditions identified through conventional bounding techniques, sufficient conditions on the average activation time of the attacks are identified via Lyapunov theory, as well as the formulation and solution of a class of bilinear matrix inequalities (BMI). The results are obtained for constant and slowly time-varying loads via input-to-state stability (ISS) tools. Numerical simulations on the IEEE 39-bus test system are also presented.

24 POWER TRANSMISSION AND DISTRIBUTION↗

NASA NTRS1998

Operational Data Reduction Procedure for Determining Density and Vertical Structure of the Martian Upper Atmosphere from Mars Global Surveyor Accelerometer Measurements

The success of aerobraking by the Mars Global Surveyor (MGS) spacecraft was partly due to the analysis of MGS accelerometer data. Accelerometer data was used to determine the effect of the atmosphere on each orbit, to characterize the nature of the atmosphere, and to predict the atmosphere for future orbits. To interpret the accelerometer data, a data reduction procedure was developed to produce density estimations utilizing inputs from the spacecraft, the Navigation Team, and pre-mission aerothermodynamic studies. This data reduction procedure was based on the calculation of aerodynamic forces from the accelerometer data by considering acceleration due to gravity gradient, solar pressure, angular motion of the MGS, instrument bias, thruster activity, and a vibration component due to the motion of the damaged solar array. Methods were developed to calculate all of the acceleration components including a 4 degree of freedom dynamics model used to gain a greater understanding of the damaged solar array. The total error inherent to the data reduction procedure was calculated as a function of altitude and density considering contributions from ephemeris errors, errors in force coefficient, and instrument errors due to bias and digitization. Comparing the results from this procedure to the data of other MGS Teams has demonstrated that this procedure can quickly and accurately describe the density and vertical structure of the Martian upper atmosphere.

Cancro, George J.↗

NASA NTRS2009

On-Orbit Calibration and Performance of Aqua MODIS Reflective Solar Bands

Aqua MODIS has successfully operated on-orbit for more than 6 years since its launch in May 2002, continuously making global observations and improving studies of changes in the Earth's climate and environment. 20 of the 36 MODIS spectral bands, covering wavelengths from 0.41 to 2.2 microns, are the reflective solar bands (RSB). They are calibrated on-orbit using an on-board solar diffuser (SD) and a solar diffuser stability monitor (SDSM). In addition, regularly scheduled lunar observations are made to track the RSB calibration stability. This paper presents Aqua MODIS RSB on-orbit calibration and characterization activities, methodologies, and performance. Included in this study are characterizations of detector signal-to-noise ratio (SNR), short-term stability, and long-term response change. Spectral wavelength dependent degradation of the SD bidirectional reflectance factor (BRF) and scan mirror reflectance, which also varies with angle of incidence (AOI), are examined. On-orbit results show that Aqua MODIS onboard calibrators have performed well, enabling accurate calibration coefficients to be derived and updated for the Level 1B (L1B) production and assuring high quality science data products to be continuously generated and distributed. Since launch, the short-term response, on a scan-by-scan basis, has remained extremely stable for most RSB detectors. With the exception of band 6, there have been no new RSB noisy or inoperable detectors. Like its predecessor, Terra MODIS, launched in December 1999, the Aqua MODIS visible (VIS) spectral bands have experienced relatively large changes, with an annual response decrease (mirror side 1) of 3.6% for band 8 at 0.412 microns, 2.3% for band 9 at 0.443 microns, 1.6% for band 3 at 0.469 microns, and 1.2% for band 10 at 0.488 microns. For other RSB bands with wavelengths greater than 0.5 microns, the annual response changes are typically less than 0.5%. In general, Aqua MODIS optics degradation is smaller than Terra MODIS and the mirror side differences are much smaller. Overall, Aqua MODIS RSB on-orbit performance is better than Terra MODIS.

Xiong, Xiaoxiong↗

NASA NTRS2022

Satellite Soil Moisture Data Assimilation Impacts on Modeling Weather Variables and Ozone in the Southeastern US – Part 2: Sensitivity to Dry-Deposition Parameterizations

Ozone (O3) dry deposition is a major O3 sink. As a follow-up study of Huang et al. (2021), we quantify the impact of satellite soil moisture (SM) on model representations of this process when different dry-deposition parameterizations are implemented, based on which the implications for interpreting O3 air pollution levels and assessing the O3 impacts on human and ecosystem health are provided. The SM data from NASA's Soil Moisture Active Passive mission are assimilated into the Noah-Multiparameterization (Noah-MP) land surface model within the NASA Land Information System framework, semicoupled with Weather Research and Forecasting model with online Chemistry (WRF-Chem) regional-scale simulations covering the southeastern US. Major changes in the modeling system used include enabling the dynamic vegetation option, adding the irrigation process, and updating the scheme for the surface exchange coefficient. Two dry-deposition schemes are implemented, i.e., the Wesely scheme and a “dynamic” scheme, in the latter of which dry-deposition parameterization is coupled with photosynthesis and vegetation dynamics. It is demonstrated that, when the dynamic scheme is applied, the simulated O3 dry-deposition velocities vd and their stomatal and cuticular portions, as well as the total O3 fluxes Ft, are larger overall; vd and Ft are 2–3 times more sensitive to the SM changes due to the data assimilation (DA). Further, through case studies at two forested sites with different soil types and hydrological regimes, we highlight that, applying the Community Land Model type of SM factor controlling stomatal resistance (i.e., β factor) scheme in replacement of the Noah-type β factor scheme reduced the v(d) sensitivity to SM changes by ∼75 % at one site, while it doubled this sensitivity at the other site. Referring to multiple evaluation datasets, which may be associated with variable extents of uncertainty, the model performance of vegetation, surface fluxes, weather, and surface O3 concentrations shows mixed responses to the DA, some of which display land cover dependency. Finally, using model-derived concentration- and flux-based policy-relevant O3 metrics as well as their matching exposure–response functions, the relative biomass/crop yield losses for several types of vegetation/crops are estimated to be within a wide range of 1 %–17 %. Their sensitivities to the model's dry-deposition scheme and the implementation of SM DA are discussed.

Min Huang↗

NASA NTRSDate not supplied

Enhancing Radiative Transfer Models for Optimized Assimilation of Microwave and Radar Observations

Radiative transfer models are extensively used for the assimilation of satellite observations into NWP models as well as retrieving geophysical products from satellite measurements. The Community Radiative Transfer Model (CRTM) is a community model developed by NOAA JCSDA and widely used for different purposes requiring RT calculations. CRTM requires bulk optical properties of hydrometeors in the form of lookup tables in order to perform all-sky RT calculations. However, the current cloud scattering lookup tables in CRTM assume spherical shapes for all frozen hydrometeors, whereas actual clouds contain frozen particles with diverse shapes. The first part of this talk presents the implementation and validation of a comprehensive Discrete Dipole Approximation (DDA) cloud scattering database into CRTM, specifically targeting microwave frequencies. The DDA technique proves effective in simulating the optical properties of non-spherical hydrometeors in the microwave region. The original DDA database assumes total random orientation in calculating single scattering properties. To generate the required mass scattering parameters for CRTM, the single scattering properties and water content dependent particle size distributions are used. The evaluation of results involved a collocated dataset comprising short-term forecasts from the Integrated Forecast System of the European Center for Medium-Range Weather Forecasts and satellite microwave data. The findings demonstrate that the DDA lookup tables significantly reduce discrepancies between simulated and observed values when compared to the Mie tables. Passive instruments lack the ability to provide vertically resolved measurements of clouds and precipitation, which can be obtained by active radar instruments. However, incorporating these active measurements into data assimilation systems presents challenges due to the absence of fast forward radiative transfer models and difficulties in error modeling. The second part of the talk focuses on the development, evaluation, and sensitivity analysis of a forward radar model integrated into CRTM. The forward radar model utilizes scattering properties obtained from hydrometeor lookup tables generated using the discrete dipole approximation. By utilizing CRTM instrument-specific coefficients, the model can calculate both reflectivity and attenuated reflectivity for any given radar instrument and zenith angles. Evaluation using CloudSat measurements demonstrates a strong agreement between simulations and observations when the input profiles of hydrometeors align with the measured reflectivity profiles.

Isaac Moradi↗

NASA NTRSDate not supplied

Optimizing Assimilation of Microwave and Radar Observations in the NWP Models

Radiative transfer models are extensively used for the assimilation of satellite observations into NWP models as well as retrieving geophysical products from satellite measurements. The Community Radiative Transfer Model (CRTM) is a community model developed by NOAA JCSDA and widely used for different purposes requiring RT calculations. CRTM requires bulk optical properties of hydrometeors in the form of lookup tables in order to perform all-sky RT calculations. However, the current cloud scattering lookup tables in CRTM assume spherical shapes for all frozen hydrometeors, whereas actual clouds contain frozen particles with diverse shapes. The first part of this talk presents the implementation and validation of a comprehensive Discrete Dipole Approximation (DDA) cloud scattering database into CRTM, specifically targeting microwave frequencies. The DDA technique proves effective in simulating the optical properties of non-spherical hydrometeors in the microwave region. The original DDA database assumes total random orientation in calculating single scattering properties. To generate the required mass scattering parameters for CRTM, the single scattering properties and water content dependent particle size distributions are used. The evaluation of results involved a collocated dataset comprising short-term forecasts from the Integrated Forecast System of the European Center for Medium-Range Weather Forecasts and satellite microwave data. The findings demonstrate that the DDA lookup tables significantly reduce discrepancies between simulated and observed values when compared to the Mie tables. Passive instruments lack the ability to provide vertically resolved measurements of clouds and precipitation, which can be obtained by active radar instruments. However, incorporating these active measurements into data assimilation systems presents challenges due to the absence of fast forward radiative transfer models and difficulties in error modeling. The second part of the talk focuses on the development, evaluation, and sensitivity analysis of a forward radar model integrated into CRTM. The forward radar model utilizes scattering properties obtained from hydrometeor lookup tables generated using the discrete dipole approximation. By utilizing CRTM instrument-specific coefficients, the model can calculate both reflectivity and attenuated reflectivity for any given radar instrument and zenith angles. Evaluation using CloudSat measurements demonstrates a strong agreement between simulations and observations when the input profiles of hydrometeors align with the measured reflectivity profiles.

Isaac Moradi↗

NASA NTRSDate not supplied

Assimilation of Spaceborne Microwave and Radar Observations

Radiative transfer models are extensively used for the assimilation of satellite observations into NWP models as well as retrieving geophysical products from satellite measurements. The Community Radiative Transfer Model (CRTM) is a community model developed by NOAA JCSDA and widely used for different purposes requiring RT calculations. CRTM requires bulk optical properties of hydrometeors in the form of lookup tables in order to perform all-sky RT calculations. However, the current cloud scattering lookup tables in CRTM assume spherical shapes for all frozen hydrometeors, whereas actual clouds contain frozen particles with diverse shapes. The first part of this talk presents the implementation and validation of a comprehensive Discrete Dipole Approximation (DDA) cloud scattering database into CRTM, specifically targeting microwave frequencies. The DDA technique proves effective in simulating the optical properties of non-spherical hydrometeors in the microwave region. The original DDA database assumes total random orientation in calculating single scattering properties. To generate the required mass scattering parameters for CRTM, the single scattering properties and water content dependent particle size distributions are used. The evaluation of results involved a collocated dataset comprising short-term forecasts from the Integrated Forecast System of the European Center for Medium-Range Weather Forecasts and satellite microwave data. The findings demonstrate that the DDA lookup tables significantly reduce discrepancies between simulated and observed values when compared to the Mie tables. Passive instruments lack the ability to provide vertically resolved measurements of clouds and precipitation, which can be obtained by active radar instruments. However, incorporating these active measurements into data assimilation systems presents challenges due to the absence of fast forward radiative transfer models and difficulties in error modeling. The second part of the talk focuses on the development, evaluation, and sensitivity analysis of a forward radar model integrated into CRTM. The forward radar model utilizes scattering properties obtained from hydrometeor lookup tables generated using the discrete dipole approximation. By utilizing CRTM instrument-specific coefficients, the model can calculate both reflectivity and attenuated reflectivity for any given radar instrument and zenith angles. Evaluation using CloudSat measurements demonstrates a strong agreement between simulations and observations when the input profiles of hydrometeors align with the measured reflectivity profiles.

Isaac Moradi↗

DOE OSTI2024

Correlation Between Microscopic Current Fluctuations Observed at Ultra-Microelectrodes and Macroscopic Bulk Electrolysis Performance in Redox-Active Microemulsions

Microemulsions (μEs) have been proposed as redox flow battery (RFB) electrolytes that maximize ionic conductivity and charge capacity by synergizing two immiscible phases. However, charge transfer during electrolysis in μEs is poorly understood. Here, we show that ultramicroelectrode electrolysis of ferrocene-loaded μEs –20%, 60%, and 90% water - reveals stochastic current fluctuations. These are differentiated in the scanning electrochemical microscopy (SECM) geometry, where power spectral density analysis showed distinct changes in the frequency contributions. SECM in the substrate generation-tip collection mode showed that fluctuations arise under mass-transfer control. Significant differences in the diffusion coefficient of ferrocene species were deducted from SECM approach curves, suggesting phase transfer behavior. Using bulk electrolysis, we calculated the charge accessibility and cycling behavior in the μEs. A decrease in the stochastic behavior of the μEs seems to correlate to a higher accessibility and cycling performance, with the 90% water μE displaying the best reversibility and the 60% the lowest. Altogether, these results suggest that Marangoni-type convection driven by concentration gradients and/or μE restructuring during charge transfer play a role in the electrochemical performance of μEs. This presents opportunities for screening and diagnosing the performance of these emerging RFB electrolytes.

25 ENERGY STORAGE↗