Results for “Porous flow” — Page 71

DOE OSTI2020

Pronghorn Theory Manual

This manual is intended to provide a thorough description of the governing equations; the relations used for material, heat transfer, and fluid flow parameters; and the numerical method utilized in Pronghorn. Detailed derivations of the governing equations are given, beginning from first principles in order to be as explicit as possible about assumptions made along the way and guide any future methods extensions. Additional explanatory or tangential information that is not required for detailed understanding of the governing equations used in Pronghorn is shown in gray boxes in the text. The convention used in this document is to represent all class names (or file names) in typewriter font.

42 ENGINEERING↗

DOE OSTI2019

Inertial Effects During the Process of Supercritical CO 2 Displacing Brine in a Sandstone: Lattice Boltzmann Simulations Based on the Continuum-Surface-Force and Geometrical Wetting Models

Inertial effects during the process of supercritical CO 2 displacing brine in porous media may not be negligible according to recent studies. Capturing the inertial effects of the physical CO 2 -brine system imposes a requirement on the grid resolution and viscosity to surface tension ratio for pore-scale simulations, which some commonly used simulators may not be able to meet. To fulfill the parameter requirement, we combine the continuum-surface-force based color-gradient lattice Boltzmann (LB) multiphase model and the geometrical wetting model and extend the model to 3D under the multiple-relaxation-time framework. We validate the model via simple benchmarks which show significant improvement over the traditional models. Furthermore, we perform 3D drainage simulations in a heterogeneous micromodel where the simulation result agrees well with experimental data, while our previous work fails to reproduce certain displacement patterns in the experiment due to the use of a traditional LB model that cannot fulfill the parameter requirement. Finally, we perform high-fidelity 3D drainage simulations to study the inertial effects in a Bentheimer sandstone sample. These findings show that stronger inertial effects generally help develop more CO 2 flow pathways for the same capillary number which results in higher CO 2 saturation, consistent with the micromodel results. The phenomena can be found in both low and high capillary number cases, indicating that the inertial effects are not dependent on the mean velocity. In addition, the change of the invasion patterns is not proportional to the change of inertial effects, thus exhibiting threshold behavior.

58 GEOSCIENCES↗

DOE OSTI2021

Pore-Scale Oil Connectivity and Displacement by Controlled-Ionic-Composition Waterflooding Using Synchrotron X-Ray Microtomography

Controlled-ionic-composition waterflooding is an economic and effective method to improve oil recovery in carbonate oil reservoirs. Recent studies show controlling the salinity and ionic composition of injection water can alter the wettability of carbonate mineral surfaces. The pore-scale oil connectivity and displacement by controlled-ionic-composition waterflooding in heterogeneous carbonate reservoirs, especially at the early stage, is still unclear. The goal of this study is to examine the role of ion concentrations and types in the oil displacement efficiency and investigate the impact of the waterflooding on the pore-scale oil displacement using the national synchrotron facility. A carbonate rock sample was flooded with synthetic high-salinity water and other water solutions with different sulfate concentrations. The waterflooding processes were visualized with synchrotron X-ray microtomography to follow the evolution of pore-scale oil/brine interactions at typical field flow rates. Experimental results show that the water with lower sulfate concentration and higher salinity did not change the wettability of the pore surfaces. Higher sulfate ion concentrations in the water, in contrast, altered the wettability of carbonate pore surfaces from oil-wet to neutral-wet within the first few minutes of waterflooding. Finally, novel insight was gained on the ability of water with high-sulfate concentration to displace oil in the small pores and through abundant oil channels, which could consequently lead to higher oil recovery from the carbonate rock.

04 OIL SHALES AND TAR SANDS↗

NASA NTRS1995

Low-speed wind-tunnel investigation of a porous forebody and nose strakes for yaw control of a multirole fighter aircraft

Low-speed wind-tunnel tests were conducted in the Langley 12-Foot Low-Speed Tunnel on a model of the Boeing Multirole Fighter (BMRF) aircraft. This single-seat, single-engine configuration was intended to be an F-16 replacement that would incorporate many of the design goals and advanced technologies of the F-22. Its mission requirements included supersonic cruise without afterburner, reduced observability, and the ability to attack both air-to-air and air-to-ground targets. So that it would be effective in all phases of air combat, the ability to maneuver at angles of attack up to and beyond maximum lift was also desired. Traditional aerodynamic yaw controls, such as rudders, are typically ineffective at these higher angles of attack because they are usually located in the wake from the wings and fuselage. For this reason, this study focused on investigating forebody-mounted controls that produces yawing moments by modifying the strong vortex flowfield being shed from the forebody at high angles of attack. Two forebody strakes were tested that varied in planform and chordwise location. Various patterns of porosity in the forebody skin were also tested that differed in their radial coverage and chordwise location. The tests were performed at a dynamic pressure of 4 lb/ft(exp 2) over an angle-of-attack range of -4 deg to 72 deg and a sideslip range of -10 deg to 10 deg. Static force data, static pressures on the surface of the forebody, and videotapes of flow-visualization using laser-illuminated smoke were obtained.

Fears, Scott P.↗

NASA NTRS2001

Novel Shapes of Miscible Interfaces Observed

The dynamics of miscible displacements in a cylindrical tube are being investigated experimentally and numerically, with a view to understand the complex processes that occur, for example, in enhanced oil recovery, hydrology, and filtration. We have observed complex shapes of the interface between two liquids that mix with each other when the less viscous liquid is displaced by the more viscous one in a tube. A less viscous fluid that displaces a more viscous fluid is known to propagate in the form of a "finger," and a flight experiment proposed by Maxworthy et al. to investigate the miscible-interface dynamics is currently being developed by NASA. From the current theory of miscible displacements, which was developed for a porous medium satisfying Darcy's law, it can be shown that in the absence of gravity the interface between the fluids is destabilized and thus susceptible to fingering only when a more viscous fluid is displaced by a less viscous one. Therefore, if the interface is initially flat and the more viscous fluid displaces the less viscous fluid, the interface ought to be stable and remain flat. However, numerical simulations by Chen and Meiburg for such displacement in a cylindrical tube show that the interface is unstable and a finger of the more viscous fluid is indeed formed. Preliminary experiments performed at the NASA Glenn Research Center show that not only can fingering occur when the more viscous fluid displaces a less viscous one in a cylindrical tube, but also that under certain conditions the advancing finger achieves a sinuous or snakelike shape. These experiments were performed using silicone oils in a vertical pipette of small diameter. In the initial configuration, the more viscous fluid rested on top of the less viscous one, and the interface was nominally flat. A dye was added to the upper liquid for ease of observation of the interface between the fluids. The flow was initiated by draining the lower fluid from the bottom of the pipette, at speeds less than 0.1 mm/sec.

Balasubramaniam, Ramaswamy↗

NASA NTRS2022

On the Stability and Phase Behavior of Titan's Subsurface Liquid Columns

On Titan, liquid hydrocarbon may stay in the subsurface porous permeable crust known as the alkanofer, analogous to water in Earth’s aquifer. In addition to pressure gradient, the subsurface liquid in alkanofers is subject to vertical compositional grading due to the gravity and temperature gradient. The common wisdom is that the liquid would normally stay underground in a stability established by the pressure that increases with depth as observed in aquifers on Earth. However, Titan’s liquids consist of nitrogen and hydrocarbons, mainly methane and ethane, the behavior of which is very sensitive to temperature and pressure. Consequently, the liquid density does not always increase with depth, thus may introduce a reverse density profile that leads to vertical convective instability of the liquid column. If reverse density profiles are present, capillary pressures arising from liquid trapped within small pores in the crust can help with the column stability. The liquid held in the capillaries can seal the space below it thus helping with the stability, unless the overpressure built from underneath becomes larger than the capillary pressure, which causes leakage to allow the liquids to seep upward from the deep. This situation is analogous to hydrocarbon seeps on Earth, where oil and natural gas escape the reservoir and flow slowly through network of cracks to the surface. An algorithm based on an extended Gibbs equation commonly used in petroleum reservoir engineering is employed in this work to produce pressure, density, and compositional profiles for evaluating the stability and phase behavior of Titan’s subsurface fluids.

Sugata Tan↗

NASA NTRS2014

Influential Factors for Liquid Acquisition Device Screen Selection for Cryogenic Propulsion Systems

This paper presents the influential factors which govern screen selection for liquid acquisition devices (LADs) operating in microgravity conditions for future in-space cryogenic propulsion engines and cryogenic propellant depots. Space flight requirements, which include mass flow rate, acceleration level and direction, and thermal environment, dictate screen selection for a particular mission. The five influential factors include bubble point pressure, flow-through-screen pressure drop, wicking rate, screen compliance, and material compatibility. Governing equations and analytical models for these parameters are developed from first principles. A comprehensive survey of the historical data on coarser LAD meshes over four decades of work is conducted, and liquid hydrogen data for finer Dutch Twill meshes (325 x 2300, 450 x 2750, 510 x 3600) from recently concluded experiments is also presented to validate analytical models. Each of these parameters is measurable from ground based tests, making it facile to predict flight system performance. Therefore analytical models in this paper will be valuable for future LAD designs for both cryogenic and storable propulsion systems. Additionally, analysis will be given on the impact of the factors on liquid hydrogen systems.

Fuel Depot↗

DOE OSTI2026

Organic colloid composition in variable-redox porewaters within a mountainous floodplain

Redox gradients, often driven by changes in sediment moisture levels in porous, heterogeneous groundwater systems, create dynamic conditions that may promote the production and transport of colloids within natural waters. While much research has focused on the inorganic composition of colloids, the organic composition remains less well understood. Organic matter (OM) in colloids may associate with minerals, complex metal ions, and serve as an electron donor for microbial respiration; therefore, its composition is of high interest. We examined the composition of porewater OM along a redox gradient in a riparian soil located along the Slate River in Crested Butte, Colorado, USA as a function of depth (90, 130, 200, and 350 cm below ground surface). All depths were oxic to suboxic, except 200 cm, where the products of iron and sulfate reduction were observed concomitant with an increase in dissolved and/or colloidal OM, pH, alkalinity, and conductivity. We investigated the composition of porewater using correlated scanning transmission X-ray microscopy and transmission electron microscopy. We observed a change in the OM chemistry from carboxylate-rich at the 200 cm depth (where it was also enmeshed with non-crystalline iron) to phenol- and substituted-aromatic-rich at other depths. Radiocarbon dating revealed carbon in porewater at 200 cm was younger than depths above and below. Soil porewater can flow down into the underlaying gravel bed during baseflow conditions, thus we speculate whether riparian porewater could transport iron- and carboxylate-rich organic colloids into surrounding surface waters through the gravel bed conduit.

Alpine floodplain↗

DOE OSTI2026

Data from Stewart et al. 2026 "Organic Colloid Composition in Variable-Redox Porewaters within a Mountainous Floodplain"

Redox gradients, often driven by changes in sediment moisture levels in porous, heterogeneous groundwater systems, create dynamic conditions that may promote the production and transport of colloids within natural waters. While much research has focused on the inorganic composition of colloids, the organic composition remains less well understood. Organic matter (OM) in colloids may associate with minerals, complex metal ions, and serve as an electron donor for microbial respiration; therefore, its composition is of high interest. We examined the composition of porewater OM along a redox gradient in a riparian soil located along the Slate River in Crested Butte, Colorado, USA as a function of depth (90, 130, 200, and 350 cm below ground surface). All depths were oxic to suboxic, except 200 cm, where the products of iron and sulfate reduction were observed concomitant with an increase in dissolved and/or colloidal OM, pH, alkalinity, and conductivity. We investigated the composition of porewater using correlated scanning transmission X-ray microscopy and transmission electron microscopy. We observed a change in the OM chemistry from carboxylate-rich at the 200 cm depth (where it was also enmeshed with non-crystalline iron) to phenol- and substituted-aromatic-rich at other depths. Radiocarbon dating revealed carbon in porewater at 200 cm was younger than depths above and below. Soil porewater can flow down into the underlaying gravel bed during baseflow conditions, thus we speculate whether riparian porewater could transport iron- and carboxylate-rich organic colloids into surrounding surface waters through the gravel bed conduit. This data package includes geochemical data (.csv) as a function of depth from porewaters in OBJ1. Measurements included are pH, conductivity, TOC, Fe concentration, sulfate concentration, dissolved oxygen. Additionally radiocarbon dating age of carbon in samples is provided. Additionally, this dataset contains metadata files (.csv) describing the methods, file contents, and column headers.

alpine floodplain↗

DOE OSTI2022

Thermal Modeling and Simulation of the Packed-bed Thermal Energy Storage Combined with INL Thermal Energy Distribution System

Dynamic Energy Transport and Integration Lab (DETAIL) at Idaho National Laboratory is to support experimental demonstration and validation research on Nuclear-Renewable Hybrid Energy System [1]. The Thermal Energy Distribution System (TEDS) is a thermal-hydraulic flow loop in DETAIL with its own dedicated control system to support the integration of co-located multiple experimental systems, where a packed-bed thermal energy storage (TES) is installed as a thermal buffer and storage unit. Among various TES options, the packed-bed TES is adopted in TEDS because it offers a low-cost single-tank thermal storage option compared to the traditional two-tank TES. However, since the TES tank is filled with granular fillers having different thermophysical properties from those of TES tank wall, there is a potential thermo-mechanical issue to be carefully addressed like thermal ratcheting which may pose a significant design concern for the packed-bed TES tank. Thermal ratcheting is a thermomechanical process caused by the repeated rearrangement of granular filler inside a TES tank during continuous thermal cycling operation of the packed-bed TES system. If the thermally induced stress exceeds the yield strength of a TES tank wall, catastrophic consequences may happen like rupture of the TES tank. Thus, it is important to understand the phenomenon to ensure the robust operation of the packed-bed TES tank. Given that thermal ratcheting is caused by complex interaction of thermal transport in the porous bed and solid mechanics, the accurate prediction of transient thermal behavior of the packed-bed TES tank, which is the focus of this paper, is critical to the reliable thermal ratcheting analysis. This paper discusses the numerical modeling, simulation, and validation studies that are ongoing at INL to investigate the transient thermal behavior of the packed-bed TES. Of particular concern is the transient thermal process occurring in the packed-bed TES unit that is operated in conjunction with the INL TEDS. The main goal of this research is three-fold: (i) provide preliminary insights into the transient thermal behavior of the TEDS TES tank, (ii) support the thermal measurement and validation plan for TEDS experiment, and (iii) provide transient thermal boundary conditions to support the reliable thermal ratcheting analysis of the TEDS TES tank. For the transient thermal modeling and analysis, a CFD model was developed, and the validity of the modeling approach was examined via comparing the numerical simulation results with the experimental data obtained from various design characteristics of packed-bed TES tanks. Then, the present modeling method was applied for the transient thermal analysis of the TEDS TES tank, and the results are discussed along with the potential improvement of data acquisition strategy for the future TEDS experiments for more precise validation study.

25 ENERGY STORAGE↗

NASA NTRS2012

Supercritical CO2 Cleaning System for Planetary Protection and Contamination Control Applications

Current spacecraft-compatible cleaning protocols involve a vapor degreaser, liquid sonication, and alcohol wiping. These methods are not very effective in removing live and dead microbes from spacecraft piece parts of slightly complicated geometry, such as tubing and loosely fitted nuts and bolts. Contamination control practices are traditionally focused on cleaning and monitoring of particulate and oily residual. Vapor degreaser and outgassing bakeout have not been proven to be effective in removing some less volatile, hydrophilic biomolecules of significant relevance to life detection. A precision cleaning technology was developed using supercritical CO2 (SCC). SCC is used as both solvent and carrier for removing organic and particulate contaminants. Supercritical fluid, like SCC, is characterized by physical and thermal properties that are between those of the pure liquid and gas phases. The fluid density is a function of the temperature and pressure. Its solvating power can be adjusted by changing the pressure or temperature, or adding a secondary solvent such as alcohol or water. Unlike a regular organic solvent, SCC has higher diffusivities, lower viscosity, and lower surface tension. It readily penetrates porous and fibrous solids and can reach hard-to-reach surfaces of the parts with complex geometry. Importantly, the CO2 solvent does not leave any residue. The results using this new cleaning device demonstrated that both supercritical CO2 with 5% water as a co-solvent can achieve cleanliness levels of 0.01 mg/cm2 or less for contaminants of a wide range of hydrophobicities. Experiments under the same conditions using compressed Martian air mix, which consists of 95% CO2, produced similar cleaning effectiveness on the hydrophobic compounds. The main components of the SCC cleaning system are a high-pressure cleaning vessel, a boil-off vessel located downstream from the cleaning vessel, a syringe-type high-pressure pump, a heat exchanger, and a back pressure regulator (BPR). After soaking the parts to be cleaned in the clean vessel for a period, the CO2 with contaminants is flushed out of the cleaning vessel using fresh CO2 in a first-in-first-out (FIFO) method. The contaminants are either precipitating out in the boil-off container or being trapped in a filter subsystem. The parts to be cleaned are secured in a basket inside and can be rotated up to 1,400 rpm by a magnetic drive. The fluid flows within the vessel generate tangential forces on the parts surfaces, enhancing the cleaning effectiveness and shortening the soaking time. During the FIFO flushing, the pump subsystem pushes fresh CO2 into the cleaning vessel at a constant flow rate between 0.01 and 200 mL/min, while the BPR regulates the pressure in the cleaning vessel to within 0.1 bar by controlling the needle position in an outlet valve. The fresh CO2 gas flows through the heat exchanger at a given temperature before entering the cleaning vessel. A platinum resistance thermometer (PRT) reads the cleaning vessel interior temperature that can be controlled to within 0.1 K. As a result, cleaning vessel temperature remains constant during the FIFO flushing. There is no change in solvent power during FIFO flushing since both temperature and pressure inside the cleaning vessel remain unchanged, thus minimizing contaminants left behind. During decompression, both temperature and pressure are strictly controlled to prevent bubbles from generating in the cleaning vessel that could stir up the contaminants that sank to the bottom by gravity.

Lin, Ying↗

DOE OSTI2021

Rapid charging made practical in graphite-based lithium batteries: surface-acoustic wave turbulent electrolyte mixing to overcome diffusion limited charging rates [Final Report]

One of the key limits in rapidly recharging a lithium-ion battery is the depletion of lithium ions within the electrolyte adjacent the anode during charging and long diffusion time to overcome this depletion. It also causes dendrite formation, inefficient use of the lithium, and battery degradation over many charge-discharge cycles. Because the liquid electrolyte remains quiescent and unmixed, this depletion layer’s depth rapidly grows to match the anode-cathode separation distance at even modest charge rates. The solution proposed by PI Prof. James Friend and Co-PI Prof. Ping Liu, both from the University of California, San Diego, is to mix the electrolyte and minimize the Li+ ion concentration gradient during charging. Even in the presence of the separator, the charging rate could then be significantly increased. They propose to accomplish this using surface acoustic wave (SAW)-driven acoustic streaming, a technique employing 10-mW fingernail-sized solid-state devices from the telecommunications industry to drive turbulent mixing to submicron length scales in a manner completely compatible with the typical 20700 and 18650 cells used in electric vehicles. 0.1. Turbulent acoustic streaming mixes the electrolyte during charging—even with separator Our proposed 100-MHz SAW device used to recirculate the electrolyte is compatible with lithium- ion battery electrochemistry, as it is made in our lab of single-crystal lithium niobate. Their solution is straightforward to drive from a DC power source alongside the signal provided during battery charging. The device is only needed during charging and does not consume power dur- ing battery discharge. Uniquely, SAW generates extreme accelerations of over 1 billion meters per second squared in the fluid, driving turbulent mixing from centimeter to submicron length scales, even through the porous separator materials that tend to be used in batteries, all while avoiding interfering with the anode’s solid electrolyte interphase layer that forms during use. By employing novel fluid mechanics, the investigators are proposing a new direction for battery research away from direct use of materials science and electrochemistry. The chemistry agnostic solution may be employed in any battery chemistry that makes use of liquid electrolytes, providing a broader transformative benefit to the battery research community. They are to produce a series of prismatic and 20700-cell sized 2 Ah batteries capable of being charged and discharged at least 500 times without more than 20% loss in battery capacity, and to provide analysis tools useful to the battery research and development community for adopting this approach for other battery chemistries and configurations.

25 ENERGY STORAGE↗

NASA NTRSDate not supplied

Degradation of Carbon Fiber Microstructures Due to Oxidative Etch Pitting

In order to understand the influence of etch pits on the material properties of carbon fiber microstructures, we use the Porous Microstructure Analysis (PuMA) software to create realistic pitted structures from virgin fiber structures and then analyze their degradation as the degree of pitting increases. For that purpose, we developed a pitting module within PuMA that creates pits with user-defined geometry (shape, size) and distribution (defect density) on the surface of arbitrary microstructures. In this work, we consider FiberForm microstructures, which are commonly used as the base material for ablative thermal protection systems (TPS). Using the new pitting module, we mimic the evolution of etch pits on FiberForm as it occurs from oxidation in ablative heating environments, by first importing the virgin FiberForm structure from a micrograph scan and then imposing different pitting conditions by varying pit radii and defect densities. We then leverage PuMA’s capabilities to calculate material properties for each structure. The results clearly show the degradation of thermal conductivity and structural integrity as etch pits grow, and furthermore highlight the complex evolution of the surface topology, which results in significant changes of the flowgeometry and chemical gas-surface interactions. Furthermore, a comparison of these changes with the case of shrinking fibers, which has heretofore been the standard for modelling ablation of carbon structures, yields significant differences. For example, we observe the formation of small chunks of fibers as pits grow in size, which could be released into the surrounding flow environment as spallation particles. This motivates us to continue our efforts of modelling pitting as an integral part of the structural degradation of carbon fiber structures in oxidation environments, which will ultimately improve our understanding of failure mechanisms in those materials.

PuMA↗

NASA NTRSDate not supplied

Degradation of Carbon Fiber Microstructures Due to Oxidative Etch Pitting

In order to understand the influence of etch pits on the material properties of carbon fiber microstructures, we use the Porous Microstructure Analysis (PuMA) software to create realistic pitted structures from virgin fiber structures and then analyze their degradation as the degree of pitting increases. For that purpose, we developed a pitting module within PuMA that creates pits with user-defined geometry (shape, size) and distribution (defect density) on the surface of arbitrary microstructures. In this work, we consider FiberForm microstructures, which are commonly used as the base material for ablative thermal protection systems (TPS). Using the new pitting module, we mimic the evolution of etch pits on FiberForm as it occurs from oxidation in ablative heating environments, by first importing the virgin FiberForm structure from a micrograph scan and then imposing different pitting conditions by varying pit radii and defect densities. We then leverage PuMA’s capabilities to calculate material properties for each structure. The results clearly show the degradation of thermal conductivity and structural integrity as etch pits grow, and furthermore highlight the complex evolution of the surface topology, which results in significant changes of the flowgeometry and chemical gas-surface interactions. Furthermore, a comparison of these changes with the case of shrinking fibers, which has heretofore been the standard for modelling ablation of carbon structures, yields significant differences. For example, we observe the formation of small chunks of fibers as pits grow in size, which could be released into the surrounding flow environment as spallation particles. This motivates us to continue our efforts of modelling pitting as an integral part of the structural degradation of carbon fiber structures in oxidation environments, which will ultimately improve our understanding of failure mechanisms in those materials.

PuMA↗

DOE OSTI2022

A Geo‐Structurally Based Correction Factor for Apparent Dissolution Rates in Fractured Media

Abstract Field measurements of apparent geochemical weathering reaction rates in subsurface fractured porous media are known to deviate from laboratory measurements by multiple orders of magnitude. To date, there is no geologically based explanation for this discrepancy that can be used to predict reaction rates in field systems. Proposed correction factors are typically based on ad hoc characterizations related to geochemical kinetic models. Through a series of high‐fidelity reactive transport simulations of mineral dissolution within explicit 3D discrete fracture networks, we are able to link the geo‐structural attributes with reactive transport observations. We develop a correction factor to linear transition state theory for the prediction of the apparent dissolution rate based on measurable geological properties. The modified rate law shows excellent agreement with numerical simulations, indicating that geological structure could be a primary reason for the discrepancy between laboratory and field observations of apparent dissolution rates in fractured media.

58 GEOSCIENCES↗

DOE OSTI2020

A mass-transfer particle-tracking method for simulating transport with discontinuous diffusion coefficients

The problem of a spatially discontinuous diffusion coefficient (D(x)) is one that may be encountered in hydrogeologic systems due to natural geological features or as a consequence of numerical discretization of flow properties. To date, mass-transfer particle-tracking (MTPT) methods, a family of Lagrangian methods in which diffusion is jointly simulated by random walk and diffusive mass transfers, have been unable to solve this problem. This manuscript presents a new mass-transfer (MT) algorithm that enables MTPT methods to accurately solve the problem of discontinuous D(x). To achieve this, we derive a semi-analytical solution to the discontinuous D(x) problem by employing a predictor-corrector approach, and we use this semi-analytical solution as the weighting function in a reformulated MT algorithm. Furthermore, this semi-analytical solution is generalized for cases with multiple 1D interfaces as well as for 2D cases, including a 2 × 2 tiling of 4 subdomains that corresponds to a numerically-generated diffusion field. The solutions generated by this new mass-transfer algorithm closely agree with an analytical 1D solution or, in more complicated cases, trusted numerical results, demonstrating the success of our proposed approach.

42 ENGINEERING↗

DOE OSTI2020

Liquid–Solid Boundaries Dominate Activity of CO 2 Reduction on Gas-Diffusion Electrodes

Electrochemical CO 2 electrolysis to produce hydrocarbon fuels or material feedstocks offers a renewable alternative to fossilized carbon sources. Gas-diffusion electrodes (GDEs), composed of solid electrocatalysts on porous supports positioned near the interface of a conducting electrolyte and CO 2 gas, have been able to demonstrate the substantial current densities needed for future commercialization. These higher reaction rates have often been ascribed to the presence of a three-phase interface, where solid, liquid, and gas provide electrons, water, and CO 2 , respectively. Conversely, mechanistic work on electrochemical reactions implicates a fully two-phase reaction interface, where gas molecules reach the electrocatalyst’s surface by dissolution and diffusion through the electrolyte. Because the discrepancy between an atomistic three-phase versus two-phase reaction has substantial implications for the design of catalysts, gas-diffusion layers, and cell architectures, the nuances of nomenclatures and governing phenomena surrounding the three-phase-region require clarification. In this paper we outline the macro, micro, and atomistic phenomena occurring within a gas-diffusion electrode to provide a focused discussion on the architecture of the often-discussed three-phase region for CO 2 electrolysis. From this information, we comment on the outlook for the broader CO 2 electroreduction GDE cell architecture.

CO2 reduction↗

DOE OSTI2020

Progression to Compatibility Evaluations in Flowing Molten Salts

Molten salt compatibility with structural alloys has been identified as a key issue for the development of Generation 3 concentrating solar power (CSP) systems with thermal storage. To accelerate this evaluation to pumped systems, the goal of this project was to conduct thermal convection loop (TCL) experiments with a peak temperature of ≥700°C and a typical temperature gradient of ~100°C. The experiments indicated that conventional ~16wt.%Cr Ni-based alloys are compatible up to 700°C with purified (i.e. low O) or dried (low H₂O) industrial-sourced Mg-K-Na chloride salt with <10 μm/yr loss. This two-year project was conducted based on the experimental and mechanistic understanding developed more than 60 years ago at Oak Ridge National Laboratory (ORNL). The first TCL experiment met the <15 μm/yr corrosion metric for this project with specimens of Ni-based alloy 600 exposed at 580°-700°C for 1000 h and post-exposure room temperature tensile tests showed minimal degradation. The second TCL experiment successfully deployed an electrochemical sensor from Argonne National Laboratory and had a peak temperature of 750°C but only ran for ~110 h due to a furnace failure. Both experiments used highly purified industrial-sourced salt with an O content of ~3 μg O/g salt and a Mg addition of 0.04 wt.%. In the second year, the Chloride Collective developed a more economical drying procedure such that the O content was much higher (>20,000 μg O/g salt). A third TCL experiment was conducted with a sensor and a peak temperature of 700°C using dried salt from the same industrial source and increased NaCl content (~20 wt.%). In addition to a 0.05% Mg addition to the salt, a Mg coupon was added in the coldest part of the loop which dissolved during the experiment. Again, small mass changes were noted for specimens of alloys 600 and C276 but the values were slightly higher than those measured in purified salt with Mg. A thin non-continuous and non-adherent oxide layer was deposited on most specimens containing Mg, Si and Al but Cr depletion also was observed. Both years included facilities qualification crucible experiments and then capsule experiments to confirm a baseline isothermal reaction rate. The first year capsule experiment led to the conclusion that the two-stage ORNL purification process using NH₄Cl and CCl₄ left the salt with a high Cl potential and a Mg addition (~0.05wt.%) was needed to lower the potential. The second year capsule experiments at 600° and 700°C found little difference in depth of attack for 0-0.25%Mg additions. In general, the complex reactions where salt can be trapped in the porous surface layer of metal indicated that mass change is an unreliable metric and average depth of Cr depletion is a better metric for assessing the extent of attack. These results have created a new baseline that is contrary to the recent published literature for chloride salts where mass losses have been reported that can be extrapolated to very significant annual metal loss rates. Chloride salt corrosion can be controlled and the results also indicate that salt purification to low O levels may not be necessary. However, additional TCL experiments are needed at different times and temperatures to generate important engineering information such as temperature dependent corrosion rates and reaction rate laws for extrapolation to long-term behavior and isolate the effect of salt additives and impurities.

36 MATERIALS SCIENCE↗