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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Role of humidity and surface roughness on direct wafer bonding

Bodies made from elastically stiff material usually bind very weakly unless the surfaces are flat and extremely smooth. In direct wafer bonding flat surfaces bind by capillary bridges and by the van der Waals interaction, which act between all solid objects. Here we study the dependency of the work of adhesion on the humidity and surface roughness in hydrophilic direct wafer bonding. We show that the long-wavelength roughness (usually denoted waviness) has a negligible influence on the strength of wafer bonding (the work of adhesion) from the menisci that form from capillary condensation of water vapor.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Anolyte Enhances Catalyst Utilization and Ion Transport Inside a CO 2 Electrolyzer Cathode

Electrochemical CO 2 reduction is a promising technology to capture and convert CO 2 to valuable chemicals. High Faradaic efficiencies of CO 2 reduction products are achieved with zero-gap alkaline CO 2 electrolyzers with a supporting electrolyte at the anode (anolyte). Herein, we investigate the effect of anolyte on the electrode properties such as catalyst utilization, ionic accessibility etc. of a CO 2 reduction cathode using electrochemical techniques and cell configurations that avoid the complexities related to co-electrolysis. Using 1M KOH as the anolyte and a Cu gas-diffusion-electrode with low Nafion content as the model CO 2 reduction electrode, we find that electrode capacitance (proxy for electrochemically active surface area) and ionic conductivity inside the cathode increase approximately 4 and 447 times, respectively, in presence of KOH. Liquid anolyte wets the electrode’s pore structure more efficiently than capillary condensation of feed water vapor. The ionomer coverage is very low, and its distribution inside the electrode is highly fragmented. Surface ion conduction mechanisms inside the electrode are orders of magnitude lower than the bulk ion conduction in presence of anolyte. This study shows that when an anolyte (e.g., KOH) is used, catalyst utilization and ionic accessibility inside the electrode increase significantly.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2023

Electrospun Nanofiber Electrodes for High and Low Humidity PEMFC Operation

MEAs with nanofiber mat electrodes containing Pt/C catalyst and Nafion binder were fabricated and evaluated. The electrodes were prepared by electrospinning a solution of catalyst powder, salt-form Nafion (with Na + , Li + , or Cs + as the sulfonic acid counterion), and a carrier polymer of either polyethylene oxide or poly(acrylic acid). The carrier polymer was extracted prior to MEA testing by a hot water soaking step. The resulting fibers were 15%–17% porous, with a core–shell-like morphology (a coating of primarily Nafion on the fiber surface). MEAs with anode/cathode catalyst loadings of 0.1 mg Pt cm −2 each and a Nafion 211 membrane produced high power at both high and low relative humidity (RH) conditions in H 2 /air fuel cell tests, e.g., a maximum power density of 919 mW cm −2 at 100% RH and 832 mW cm −2 at 40% RH for a test at 80 °C and 200 kPa abs . The presence of nm-size pores within the fibers trapped water via capillary condensation during low RH feed gas testing, thus maintaining a high proton conductivity of the Nafion binder in the anode and cathode while minimizing/eliminating ionic isolation of catalyst particles in low water content, poorly conductive binder.

25 ENERGY STORAGE↗
DOE OSTI2023

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

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

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Fuel Cell Membrane Electrode Assemblies with Ultra-Low Pt Nanofiber Electrodes (Final Report)

H 2 /air fuel cell membrane-electrode-assemblies (MEAs) were fabricated with electrospun particle/polymer nanofiber mat cathodes (0.1 mg Pt /cm 2 or 0.2 mg Pt /cm 2 Pt/C, PtCo/C or PtNi/C) and anodes (0.1 mg/cm 2 Pt/C), where the binder was a mixture of acid-form perfluorosulfonic acid ionomer (e.g., Nafion™) and poly(acrylic acid) (PAA) carrier polymer or sodium-form PFSA with a carrier polymer of either PAA or polyethylene oxide (PEO). For the latter two cases, the water-soluble carrier was removed from the fibers after electrospinning. MEAs with Pt/C anode/cathode catalyst loadings of 0.1 mg Pt /cm2 each, an 1100 EW PFSA binder (Nafion™ dispersion), and a Nafion 211 membrane produced high power at both high and low relative humidity (RH) conditions, e.g., a maximum power density of 919 mW/cm 2 at 100% RH and 832 mW/cm 2 at 40% RH for a test at 80 °C and 200 kPa abs . The high power at low RH was attributed to nm-size pores within the fibers that trap water via capillary condensation thus maintaining a high proton conductivity of the PFSA binder in the cathode and especially the anode while minimizing/eliminating ionic isolation of catalyst particles in low water content, poorly conductive binder. At the same time, micro-porosity between fibers in the cathode allows for fast removal of electrogenerated water, thus minimizing cathode flooding. Nanofiber MEAs with Pt alloy catalyst cathodes also performed well, where a fibrous PtCo/C catalyst cathode at a loading of 0.1 mg/cm 2 produced 20% more power than a conventional powder cathode MEA, e.g., a maximum power density of 1,045 mW/cm 2 vs. 869 mW/cm 2 at 80 °C, 100% RH, and 200 kPa abs , and a PtNi/C fiber cathode MEAs prepared with Na+-form Nafion + PEO generated a maximum power of 820 mW/cm 2 at 40% RH. Fiber electrode MEAs with a neat Nafion binder (prepared from Na+-form Nafion + PEO or PAA) where the cathode Pt loading was ~0.1 mg/cm 2 exhibited a 25% loss in maximum power at 30,000 metal dissolution cycles, as compared to a 12% loss when the cathode binder was H+-form Nafion + PAA. The performance of a fiber mat electrode MEA with Pt/C catalyst (0.2 mg/cm 2 cathode loading and 0.1 mg/cm 2 anode loading) was excellent. At 80 oC and 200 kPa abs , the maximum power density was 1104 mW/cm 2 . The maximum power was independent of feed gas humidity for 40 < RH < 100%. The power loss after a metal dissolution AST (30,000 voltage cycles) was only 13%.

08 HYDROGEN↗
DOE OSTI2020

Water separation device for engine exhaust gas

A system includes an engine and an exhaust conduit in communication with the engine. A water separation device has exhaust gas passageways in communication with the exhaust conduit. The water separation device has a substrate and a membrane on the substrate. The substrate has inner walls surrounding the exhaust gas passageways with at least one of the inner walls being common to at least two of the exhaust gas passageways. The membrane is between the exhaust gas passageways and the substrate and has capillary condensation pores extending from the exhaust gas passageways to the substrate.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2021

Experimental Investigation of a Novel Membrane-Based Condensing Heat Exchanger for High Efficiency Furnaces

Building space heating consumes approximately one-third of all global natural gas end use. Higher-efficiency (i.e., condensing) furnaces constitute only about 30% of the annual furnace shipments in the United States because the condensing heat exchangers must use highly expensive, corrosion-resistant materials to be protected from acidic components in the furnace flue gas stream. Increasing the market share of high-efficiency furnaces will reduce greenhouse gas emissions. This study developed and tested a benchtop prototype of a novel membrane-based heat exchanger (MHX) for high-efficiency furnaces to achieve nonacidic condensation via nanoporous membranes. Test results show that both sensible and latent heat were recovered by the MHX, and the fraction of latent heat recovery ranged from about 25% to 45% over the range of operating conditions evaluated. The amount of water condensed through the MHX increased with the increase of flue gas flow rate and decreased with increasing coolant temperature. The fraction of latent heat recovery decreased with the increase of flue gas flow rate and coolant temperature. The pH value of condensed water from the MHX was only mildly acidic, varying from 5.3 to 5.6 without any additional treatment, about 2.0 to 2.3 pH points higher (i.e., less acidic) than typical values for the condensate from conventional condensing furnaces. Therefore, feasibility of the MHX was experimentally verified, and the MHX could enable wider market penetration of highly energy-efficient condensing furnaces by reducing costs associated with managing the acid condensation compared with conventional condensing furnaces, possibly enabling the use of existing vent systems when replacing noncondensing furnaces (due to higher flue gas exit temperatures), and possibly reducing furnace first costs.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2020

Detection of Polar Compounds Condensed on Particulate Matter Using Capillary Electrophoresis-Mass Spectrometry

A new analytical method to aid in the understanding of the organic carbon (OC) phase of particulate matter (PM) from advanced compression ignition (ACI) operating modes, is presented. The presence of NO2 and unburned fuel aromatics in ACI emissions, and the low exhaust temperatures that result from this low temperature combustion strategy, provide the right conditions for the formation of carboxylic acids and nitroaromatic compounds. These polar compounds contribute to OC in the PM and are not typically measured using nonpolar solvent extraction methods such as the soluble organic fraction (SOF) method. The new extraction and detection method employs capillary electrophoresis with electrospray ionization mass spectrometry (CE-ESI MS) and was specifically developed to determine polar organic compounds in the ACI PM emissions. The new method identified both nitrophenols and aromatic carboxylic acids in the ACI PM. The ACI air-fuel stratification mode and NOx emissions were found to correlate with the presence and amount of the individual polar species identified.

Lewis Sr, Samuel↗
DOE OSTI2026

Experimental investigation of a closed vapour box module for a divertor-like configuration in Magnum-PSI

Efficient management of extreme heat fluxes in the divertor region to extend the lifetime of the components remains a critical challenge for the realization of nuclear fusion-based power plants. Among the alternative concepts explored for the divertor region, the use of liquid metals, particularly lithium, is of interest due its ability to dissipate the incoming plasma heat flux through the vapour shielding effect (VS). In this work, we experimentally investigated a ‘closed’ configuration of a dedicated Vapour Box Module (VBM) in the linear plasma device Magnum-PSI. The goal of the experiments is to simulate the vapour box divertor environment conditions and assess its performance in terms of power mitigation and redistribution and lithium confinement. Initial testing without Li demonstrated the efficacy of a closed VBM structure in inducing detachment via neutral gas accumulation. Apertures which enabled non-condensing gas to be effectively pumped while ensuring lithium condensed on the inner surfaces were therefore added. With a lithium capillary porous structure target used, lithium is directly vaporized by the plasma, forming a dense lithium vapour cloud that interacts with the incoming plasma. This resulted in a significant reduction of the target temperature of at least 48%, together with a temperature locking effect, a phenomenon typically observed in the VS regime. Lithium vapour confinement within the VBM was strongly correlated with the wall temperature. Relatively cold walls promoted Li re-condensation and therefore improved Li confinement, although with the expected trade-off of increased hydrogenic retention on lithium-wetted surfaces. As the wall temperature increased, the confinement efficiency decreased, consistent with reduced Li re-condensation and thermally activated Li–H chemistry and remobilization at the walls. Diagnostic measurements through embedded thermocouples and calorimetry revealed that lithium vaporization and re-condensation processes also playedsignificant roles in plasma power dissipation. The results advance the case for a closed divertor chamber with direct lithium evaporation from the strike-points as a viable method to manage divertor heat fluxes in future fusion reactors.

Romano, Fabio [Dutch Institute for Fundamental Ene↗
DOE OSTI2020

Modeling Efforts to Gain Insight into Historical Leak Events from the Single-Shell Tank A-105 in the Hanford 241-A Tank Farm - 20113

The 241-A Tank Farm is a single-shell tank (SST) farm constructed to store process waste from Hanford nuclear operations. Millions of gallons of nuclear waste were stored in the 241-A Tank Farm SSTs and some of the SSTs leaked in the past. In addition, spills and pipeline leaks during transfers and storage and intentional discharges to cribs and trenches resulted in releasing waste to the ground. Tank liner leaks are referred to as 'leaks' and all other discharges to the soil are referred to as 'releases.' Liquid waste that could be removed by pumping has been removed from all of the SSTs to reduce the potential for future leaks. The most significant historical leak event in 241-A Tank Farm occurred in 1965 when tank A-105 experienced a pressurized steam event. This event resulted in damage to the inner steel liner flooring of A-105, which was separated from the sidewalls over part of its circumference and buckled up to 2.5 m, vertically. During this event up to 7,570 L of contaminated liquid may have leaked to the adjacent soil. This leak occurred under extreme temperature and pressure conditions. Modeling efforts to better understand the nature and extent of historical leaks from subsurface SSTs that were used to store highly radioactive, self-boiling liquid wastes at 241-A Tank Farm have recently been undertaken. These efforts have compiled the available historical information to support a preliminary non-isothermal, multiphase flow and chemical transport modeling effort to re-create the conditions under which the leaks occurred and to formulate a conceptual model as to the extent and distribution of leaked radioactive contaminants in the adjacent soil material. The focus of this work was on developing an understanding of the key features, processes and bounding conditions related to tank A-105 leak events that occurred in the 1960's. The activities include estimation of leak composition, non-isothermal multiphase flow and transport modeling, and geochemical modeling. The STOMP{sup C} Water-Air-Energy modeling code was utilized to implement the three-dimensional representation of the subsurface tank and the surrounding flow field. Once constructed, the model was used to evaluate the conceptual understanding of leaks originating from different parts of the tank under the elevated temperature boundary conditions that were imposed by surrounding tanks at the time of the historical leaks. The chemical evolution of the liquid waste was also evaluated as it leaked from the tank under transient pressure and temperature gradients. The results of the preliminary evaluation suggested the presence of a heat-pipe effect beneath tank A-105 in which water vapor at an elevated temperature is driven away from the base of the tank to a position where water vapor cools, condenses and is then drawn back toward the tank by the strong capillary attraction of the dry soil. A non-sorbing contaminant (Tc-99) was introduced into this flow field to better understand the potential distribution patterns of leaked contaminants that may have occurred during the historical leak events. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Simple Heat Pipe Model

This is a simple model designed to run fast but still maintain the key physics and feedback mechanisms of a heat pipe. First, the capillary pressure is a function of the liquid working fluid volume fraction. Second, the boiling and condensation are based on the saturation temperature that is based on the heat pipe pressure. When the pressure goes up, the saturation temperature goes up and the vapor rains on the wick. When the pressure goes down, the saturation temperature goes down and the liquid in the entire wick boils. This is how the heat pipe adjusts to stay robust under different temperatures and heat fluxes.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2020

Thermocatalytic Heat Pipes for Geothermal Resource Recovery

Heat pipes are an important technology that allow orders of magnitude faster heat transfer than simple conduction. However, operating principles in heat pipes place fundamental bounds on their performance (critical heat flux and efficiency). Conventional heat pipe functionality is inherently tied to vaporization and condensation of the working fluid charged in the heat pipe. These fluids each have different operating temperature ranges based on the capillary, entrainment, sonic, and boiling limits of the heat pipe design. These limits, typically the capillary limit, dictate the maximum heat flux a heat pipe can carry, and most importantly for geothermal systems, the distance over which the pipes can operate (100 to 200 m maximum under optimum conditions). A thermocatalytic heat pipe breaks the inherent limitations of phase change thermo- and hydrodynamics and can transform heat pipe technology as a potentially more efficient means of extracting heat from a geothermal resource. The thermocatalytic heat pipe uses a working fluid to transport both sensible and chemical heat. An endothermic chemical reaction at depth removes heat from the reservoir and produces reactive intermediates, which are transported to the surface and used to run a reverse exothermic reaction that releases heat for use in power generation or other useful purposes. This technology offers two distinct advantages over conventional geothermal heat recovery technologies: (1) lower heat loss to the rock outside of the geothermal reservoir, and (2) higher heat transfer rates to the well field within the geothermal reservoir. Both advantages offer opportunity to reduce risks and lower costs of geothermal energy recovery. In this report, we discuss an initial effort to assess the efficacy and limitations of this technology for extracting heat from both porous/permeable and nominally impermeable geothermal reservoirs. Numerical simulation capabilities of the STOMP-GT code were enhanced to enable simulations of thermochemical heat pipes traversing geothermal reservoirs. An array of potential thermochemical reaction systems was evaluated and screened. Of these, an ethanol dehydration reaction was most promising in the vapor-liquid reaction set. A solid-phase dehydration reaction (CuSO4·5H2O) showed the highest reaction enthalpy per unit volume but would require development of a nonaqueous carrier fluid to implement it in a heat pipe. Subsurface reservoir simulations predicted long-term performance of the heat pipes for each geothermal reservoir type. The performance of U-shaped wells and coaxial wells was evaluated for a suite of reactions for both hydrothermal and hot dry rock reservoirs and was compared with a baseline case of simply pumping water through the wells. The heat pipe technology was additionally evaluated for an enhanced geothermal system (EGS) with an injection borehole, production borehole, and intervening hydraulically conductive fracture. All reservoir types showed significant improvement in heat recovered over a 20-year operating period ranging from a 1.8X increase for the hot dry rock case to more than 2.5X more energy recovered for the EGS case.

15 GEOTHERMAL ENERGY↗
DOE OSTI2022

Experimental Investigation of the Effect of Atomizing Electrospray Nozzles on the Cooling and Reduced Humidification of Air

Separating sensible and latent cooling have shown the potential to reduce energy consumption in A/C systems for building HVAC applications. Several technologies exist based on vapor-compression refrigeration, enthalpy wheels, chemical adsorption and absorption materials, and mechanical cooling. However, their thermodynamics limits and high energy consumption hinder their deployment in hot and humid climatic regions. This paper focuses on separating sensible and latent cooling by using a new thermodynamics process and in-kind (i.e., non-vapor compression-based) technology. Highly electrically charged water droplets were sprayed in the airflow. These droplets attracted water vapor molecules to their surfaces and promoted condensation. The phenomenon was the result of simultaneous dielectrophoresis and electro-diffusion interactions. Studies in the literature have shown that using multiple capillary electrodes reduced air moisture by up to 5% when using nanometer-size droplets in the spray. Unfortunately, these studies were limited to low airflow rates, and the objective of this paper was to investigate how to scale up this in-kind approach to airflows typical of buildings. In the present paper, droplets of micrometer size were utilized to control the humidity for a 5-cfm flow rate. While this airflow was still low for building applications, it was 100 times fold the airflows in the literature studies. The air was tested at 20°C and at 50 and 80% relative humidity. A two-fluid atomizing nozzle produced the droplets in the spray, and high DC electric potential, up to 25 kV, was used to charge the fine droplets electrically. The air atomizing nozzle with high voltage potential resembled an evaporative cooler process. However, a measurable reduction of the absolute humidity of up to 2% was observed compared to the case of the nozzle with no high voltage potential. The entire device had one small nozzle selected from off-the-shelf components and had less than a 9 cm2 footprint area.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2020

Estimating diffusion coefficients of shale oil, gas, and condensate with nano-confinement effect

Molecular diffusion plays an important role in oil and gas migration in tight shale formations. However, there are insufficient reference data in the literature to specify the diffusion coefficients within porous media. This study aims at calculating diffusion coefficients of shale gas, shale condensate, and shale oil at reservoir conditions with CO 2 injection for EOR/EGR. The large nano-confinement effects including large gas-oil capillary pressure and critical property shifts could alter the phase behaviors. This paper estimates the diffusivities of shale fluids in nanometer-scale shale rock from two perspectives: 1) examining the shift of diffusivity caused by nanopore confinement effects from phase change (phase composition and fluid property) perspective, and 2) calculating the effective diffusion coefficient in porous media by incorporating rock intrinsic properties (porosity and tortuosity factor). The tortuosity is obtained by using tortuosity-porosity relations as well as the measured tortuosity of shale from 3D imaging techniques. The results indicated that nano-confinement effects could affect the diffusion coefficient through altering the phase properties, such as phase compositions and densities. Compared to bulk phase diffusivity, the effective diffusion coefficient in porous shale rock is reduced by 10 2 to 10 4 times as porosity decreases from 0.1 to 0.03.

04 OIL SHALES AND TAR SANDS↗
DOE OSTI2024

High Performance Heat Pipe Power Transient Testing at SPHERE Facility

Microreactors are being researched, designed, and built at Idaho National Laboratory (INL). Microreactors are small reactors defined at less than 20MW of power. These reactor concepts are also being looked at throughout industry for various applications. An important aspect of these reactor designs is economic feasibility i.e. lower overnight capital cost. The driving factors for implementing microreactors are quick setup and takedown, minimal operators, and the ability to manufacture them readily and to fit in mid-sized containers for transport. A specific area of research to aid in successful integration of these factors within the designs is passive heat removal of the core’s thermal power. Interest in heat pipes to achieve this passive heat removal has been shown across multiple industry partners. Because of this interest, INL has developed a test facility to facilitate experimental tests for sodium filled heat pipes. INL has developed the Single Primary Heat Extraction and Removal Emulator (SPHERE) facility to run experiments on high performance, sodium filled heat pipes. As mentioned above, heat pipes are passive heat transfer devices. Radially, heat pipes are broken up into an outer wall, a small annular gap, a wick structure, and a centerline gap. They function by utilizing latent heat transfer. Heat pipes are traditionally separated into three regions, an evaporator (heat input), an adiabatic region, and finally a condenser region (heat removal). As heat is being applied to the evaporator, the working fluid undergoes a phase change to a vapor. This phase change causes a differential pressure across the axial length of the pipe driving flow down the center gap of the heat pipe. The vapor flows down past the adiabatic region to the condenser where the heat is removed. This heat removal forces the working fluid to phase change back to a liquid. The wick structure is then utilized to drive the flow back towards the evaporator by capillary forces. This backflow is aided by the annular gap. Because this heat transfer mechanism functions with latent heat transfer, the heat pipe is close to isothermal down the axial length. Heat pipes can operate under a wide range of working fluids. Considerations for these working fluids are primarily driven by operating temperatures amongst other important factors based around overall performance. Sodium filled heat pipes operate from 450°C up to 900°C. This temperature range works well for the current microreactor designs. In conjunction with this experimental capability, INL has developed a modeling software to simulate heat pipe physics within reactor cores. This modeling software is called Sockeye and functions under the established INL Multiphysics Object Oriented Simulation Environment (MOOSE). SPHERE also supports Sockeye development by providing the modeling team with experimental data on an array of setups and operating parameters to support validation efforts. A power transient experiment was performed utilizing the SPHERE facility to continue to aid with Sockeye development. The testing followed a proposed test plan to ramp up and down the temperature of the heat pipe. Sockeye models steady state heat pipe operation with high accuracy, the data provided by the power transient testing aims to assist with the validation efforts and further enhance transient modeling capability of the tool [2].

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2025

Chemical Imaging of Atmospheric Biomass Burning Particles from North American Wildfires

The effects of biomass burning aerosols (BBA) on radiative forcing and cloud formation depend on chemical composition and the internal structures of individual particles within smoke plumes. To improve our understanding of the chemical and physical properties of BBA emitted at different times of the day and their evolution during atmospheric aging, we conducted a study as a part of the Fire Influence on Regional to Global Environments and Air Quality field campaign. Particle samples were collected onboard a research aircraft from smoke plumes from a wildfire in eastern Oregon during late afternoon and nighttime flights on August 28, 2019. A time-resolved aerosol collector was used to collect samples on substrates for offline spectromicroscopic imaging to investigate the single-particle characteristics of BBA particles. Approximately 20,400 individual particles from 10 selected samples were analyzed using computer-controlled scanning electron microscopy coupled with energy-dispersive X-ray microanalysis, revealing their elemental composition, morphology, and viscosity. Elemental microanalysis indicated that aged potassium is likely found in the form of K 2 SO 4 , KNO 3 , and possible K-organic salts. Further chemical speciation and carbon bonding mapping within individual particles were conducted using synchrotron-based scanning transmission X-ray microscopy (STXM) coupled with near edge X-ray absorption fine structure (NEXAFS) spectroscopy. Real-time, water-soluble light absorption measurements were acquired using a particle-into-liquid sampler instrument coupled to a liquid waveguide capillary cell and total organic analyzer. In the late afternoon samples, 65% of the total particle number population consisted entirely of organic components, compared to 46% in the nighttime particles. These differences were attributed to discrepancies in composition at the time of emission and to the daytime condensation and accumulation of photochemically formed secondary organic material on existing BBA particles, a process that halts at night. Microscopy images indicated that particle viscosity was lower in the nighttime particles (<10 1 Pa·s), likely due to increased relative humidity and a higher contribution from hygroscopic inorganic components. The chemical heterogeneity of individual particles was quantified using STXM-derived mixing state parameters. The nature of carbon bonding within individual particles was inferred from the extent of carbon sp 2 hybridization derived from NEXAFS spectra. Average percentages of sp 2 hybridization range between 40% and 60%, with no noticeable differences between late afternoon and nighttime flights. These findings were compared with the online optical properties of both late afternoon and nighttime smoke plumes, providing valuable insights into the complex relationship between chemical composition and optical properties of BBA particles at different times of the day.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Pore accessibility and trapping of methane in Marcellus shale

Accessibility of pore space in unconventional reservoirs is an important factor influencing both methane storage capacity and the kinetics of methane desorption. The determination of open (accessible) versus closed (inaccessible) porosity is therefore vital for the prediction of gas production potential. This study investigates accessibility of pores to methane in overmature middle Devonian Marcellus shale samples (cut parallel and perpendicular to bedding) using small and ultra-small neutron scattering (SANS and USANS) with contrast matching (CM), supplemented by other complementary techniques, such as mercury injection capillary pressure (MICP) and low pressure gas (N2 and CO2) adsorption. Our results demonstrate that for the samples studied, only about 6 % of pores with diameter 25-500 nm are accessible to methane. The accessibility fraction for pores larger than 500 nm is 35%. For nanopores smaller than 25 nm, pore accessibility could not be quantitatively determined due to increased methane density and condensation effects in confinement. Our observations indicate that methane penetrates the accessible small mesopores and micropores down to at least 1 nm in diameter, and the density of confined deuterated methane (CD4) is 0.68 g/cm3 for pores of diameter 25 nm and gradually increases with the decreased pore size. Moreover, elevated gas pressure causes formation of additional high-density methane nano-clusters. These clusters have a form of slightly anisotropic polydisperse discs oriented along bedding plane, about 1-12 nm in diameter and with average thickness of 3.6 nm. Utilizing samples cut parallel and perpendicular to the bedding, this study also briefly addresses anisotropy of pores. Based on the iso-size intensity ratio R, our SANS and USANS results demonstrate anisotropy in the out-of-bedding direction and suggest that the degree of anisotropy depends on the pore size. Specifically, for pore diameters ~2.5 to 250 nm, the extent of anisotropy is smaller than for pores ~500 nm to 6 µm in diameter. Finally, comparison of pore size distribution results calculated from SANS/USANS to those obtained using MICP shows good agreement at low pressures, but large difference at pressures above 1000 bar. Here, this discrepancy requires further testing; it is possible that the high mercury pressure used in MICP alters the mesopore and micropore structure of shales.

03 NATURAL GAS↗
DOE OSTI2023

Numerical investigation and experimental validation of water condensation in the gas diffusion layer with different properties

Liquid water in porous media hinders the transport of reactant to catalyst layer, where the electrochemical reactions occur, which in turn, reduces performance and lifetime of a proton exchange membrane fuel cell (PEMFC). In this study, two types of gas diffusion layer (GDL) materials are used to study the two-phase saturation distribution in a PEMFC. The correlations between the effective and anisotropic transport properties and porosity of the two GDLs are solved by the pore scale model. In addition, the anisotropic liquid water permeability and the relationship between saturation pressure and capillary pressure is determined by using the Lattice-Boltzmann method. Fuel cell performance as well as liquid water distribution in the GDL using neutron radiography are obtained for validation. Under wet conditions, the cell with Freudenberg GDL performs better than that using Toray GDL, especially at high current densities. The results of the two-phase model simulation show that the peak water saturation for Toray GDL occurs in the catalyst layer and can reach 40%, while the peak water saturation for Freudenberg GDL occurs inside the GDL directly under the ribs and only reaches 25% saturation. The combined results provide key insights to enable high power density operation of a PEMFC through GDL material optimization.

42 ENGINEERING↗