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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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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Biomass char gasification kinetic rates compared to data, including ash effects

This investigation provides both experimental and theoretical analyses of biomass char gasification kinetics over 1150–1350 °C in the environment of CO 2 , H 2 O and combinations of these reactants. The experimental data include continuous measurements of particle mass, external and internal temperatures, shape, and size with periodic but not continuous measurements of char porosity, pore size distribution, and pore surface area. The model describes heterogeneous char gasification for poplar wood, corn stover and switchgrass in different shapes and industrially relevant sizes (12.5 mm and smaller). Nonlinear least-squares regression produces optimized power-law model parameters for global kinetics that describe biomass char gasification with respect to both CO 2 and H 2 O separately and in combination. A single set of kinetic parameters describes reaction rates for all three fuels. Model simulations agree with measured data at all stages of char conversion even though the observed mass loss rates change significantly with conversion. In conclusion, the change in rate with conversion depends strongly on ash content, and this investigation provides a simple and theoretically based reaction rate expression that includes the effect of inert ash occupying an increasing portion of the reactive surface with increased conversion.

09 BIOMASS FUELS↗
DOE OSTI2024

Thermally Insulating Transparent Barrier (THINNER) coatings on single pane windows

Conventional silica aerogel monoliths can provide remarkable thermal insulation but the presence of large pores (> 30 nm) tends to scatter visible light and render the material opaque or translucent instead of transparent. In addition, they are prone to cracking during synthesis and handling which makes them difficult to integrate in products and in particular in window solutions. This project developed two new solgel synthesis methods using silica precursors or preformed silica nanoparticles and ambient drying to produce mesoporous organo-silica monoliths. The monoliths were (i) thermally insulating, (ii) optically transparent, (iii) flexible, and (iv) hydrophobic. They feature porosity ranging from 50% to 90% with narrow pore size distribution with pore less than 20 nm resulting in excellent optical clarity (haze < 2%) and very low thermal conductivity (< 30 mW/mK). Interestingly, not only porosity but also pore size and mass fractal dimension were found to affect the thermal conductivity of the mesoporous silica. The superior transparency of the monoliths was shown to be attributed to dependent scattering among silica nanoparticles. Flexibility was achieved through trimethylchlorosilane surface modification. Furthermore, process scale-up and integration of the ambigel monoliths into window solutions using optically clear adhesives were also demonstrated in 6”x6” double-pane windows. The aerogel and the window solution were shown to be durable to accelerated aging under UV, moisture, and/or temperature gradient and thermal cycling. Overall, the window solution achieved the technical performance and the cost target of $10/sqft set for the SHIELD program. However, scaling to industry relevant scale (> 10’x10’) remains a challenge due to requirements on the drying process and fume hood size and to the propensity of large aerogel slab to crack during drying.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2021

Understanding Carbon Dioxide Transfer in Direct Methanol Fuel Cells Using a Pore-Scale Model

Abstract The gas flow of carbon dioxide from the catalyst layer (CL) through the microporous layer (MPL) and gas diffusion layer (GDL) has great impacts on the water and fuel management in direct methanol fuel cells (DMFCs). This work has developed a liquid–vapor two-phase model considering the counter flow of carbon dioxide gas, methanol, and water liquid solution in porous electrodes of DMFC. The model simulation includes the capillary pressure as well as the pressure drop due to flow resistance through the fuel cell components. The pressure drop of carbon dioxide flow is found to be about two to three orders of magnitude higher than the pressure drop of the liquid flow. The big difference between liquid and gas pressure drops can be explained by two reasons: volume flowrate of gas is three orders of magnitude higher than that of liquid; only a small fraction of pores (<5%) in hydrophilic fuel cell components are available for gas flow. Model results indicate that the gas pressure and the mass transfer resistance of liquid and gas are more sensitive to the pore size distribution than the thickness of porous components. To buildup high gas pressure and high mass transfer resistance of liquid, the MPL and CL should avoid micro-cracks during manufacture. Distributions of pore size and wettability of the GDL and MPL have been designed to reduce the methanol crossover and improve fuel efficiency. The model results provide design guidance to obtain superior DMFC performance using highly concentrated methanol solutions or even pure methanol.

Electrochemistry↗
DOE OSTI2021

Deformation of pores in response to uniaxial and hydrostatic stress cycling in Marcellus Shale: Implications for gas recovery

One of the main challenges during gas production from shale reservoirs is low recovery rate. One contributing factor to this outcome is an insufficient understanding of pore systems, especially pore behaviour following changes in reservoir conditions or resulting from gas production practices. Because the pressure in the producing well can be controlled, understanding the effects of pressure variation on the pore size distribution and methane trapping is necessary to help design optimal conditions to improve the gas recovery rate. This work is the first systematic study of sub-millimeter pore deformation in shale caused by uniaxial and hydrostatic stress up to 100 MPa. Overmature samples from the Middle Devonian Marcellus Shale were analyzed using neutron scattering (SANS and USANS) techniques to interpret the response of nanopores to stress cycling of magnitude and duration compatible with the hydraulic fracturing treatments. Experiments reported here are performed at a series of uniaxial pressures up to 100 MPa and at hydrostatic pressures of deuterated methane 0 and 50 MPa. Since at the original depth of the shale samples’ burial of 2184 m the hydrostatic pressure is approximately 27 MPa and the lithostatic pressure is about 55 MPa, the experimental conditions reasonably well simulate the reservoir pressure regime. Our SANS and USANS results show that different pore sizes are affected by uniaxial stress in different ways. Specifically, in the pore size range from 1 nm to 800 nm, a decrease of pore density with pressure is observed, with the most depleted being mesopores of about 100 nm in diameter. The observed decrease is likely related to deformation of kerogen, followed by a loss of pore nano-volume, as well as methane trapped in the micropores. For pores larger than 5 μm, USANS data suggest that the negative trend is reversed at above 74 MPa, and the number density of large macropores may increase with increased stress even above the original value. The increased number of macropores at high pressure may create new interconnected conduits for gas migration, resulting in a better recovery rate. Another important finding of this study is an irreversible rearrangement of pore size distribution taking place after pressure cycling. Furthermore, this irreversible reorganization of pore size distribution should be taken into account during management of well production to maximize recovery rate.

03 NATURAL GAS↗
DOE OSTI2021

Insight on electrolyte infiltration of lithium ion battery electrodes by means of a new three-dimensional-resolved lattice Boltzmann model

Electrolyte filling takes place between sealing and formation in Lithium Ion Battery (LIB) manufacturing process. This step is crucial as it is directly linked to LIB quality and affects the subsequent time consuming electrolyte wetting process. Although having fast, homogeneous and complete wetting is of paramount importance, this process has not been sufficiently examined and fully understood. For instance, experimentally available data is insufficient to fully capture the complex interplay upon filling between electrolyte and air inside the porous electrode. We report here for the first time a 3D-resolved Lattice Boltzmann Method (LBM) model able to simulate electrolyte filling upon applied pressure of LIB porous electrodes obtained both from experiments (micro X-ray tomography) and computations (stochastic generation, simulation of the manufacturing process using Coarse Grained Molecular Dynamics and Discrete Element Method). The model allows obtaining advanced insights about the impact of the electrode mesostructures on the speed of electrolyte impregnation and wetting, highlighting the importance of porosity, pore size distribution and pores interconnectivity on the filling dynamics. Furthermore, we identify scenarios where volumes with trapped air (dead zones) appear and evaluate the impact of those on the electrochemical behavior of the electrodes.

25 ENERGY STORAGE↗
DOE OSTI2021

Maximizing selectivity: An analysis of isoporous membranes

Membranes are compelling candidates for many separation-based industrial processes. However, all synthetic membranes are subject to well-recognized permeability-selectivity trade-offs that hinder their use in advanced applications. Having uniform nanoscale pore size, isoporous nanofiltration and ultrafiltration membranes have attracted wide research interest. However, quantitative analysis of isoporous membrane performance is lacking - particularly at module and system-level scales. In this study, an analytical model is built to investigate how membrane pore-size distribution affects the solute separation efficiency (i.e., rejection and selectivity). The model accounts for convective hindrance as well as concentration polarization and explores effects on separation from the solute-to-pore-size ratio and percent recovery (i.e., fraction of feed flow that passes through the membrane). At the module level, our analysis suggests that a notably sharper rejection vs. solute size curve can be obtained as the pore-size distribution becomes narrower. Additionally, as the recovery increases, the rejection of a solute is maintained at a high level using isoporous membranes while the rejection drops rapidly for membranes that possess a disperse pore-size distribution. Furthermore, in the separation of mixed solutes, isoporous membranes achieve a large selectivity with a modest loss of permeability. Overall, this study elaborates the unique role that isoporous membranes play within the permeability-selectivity trade-off relations and identifies the most exciting opportunities for their future applications.

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

Hierarchically porous electrospun carbon nanofiber for high-rate capacitive deionization electrodes

Capacitive deionization (CDI) is a promising technology that has gained interest for the desalination of brackish water. Hierarchically porous carbons are commonly used as electrodes for CDI due to their high surface areas and controlled pore size distributions that maximize ion adsorption capacity and rate. Electrospinning is an effective way of generating carbon nanofibers with high inter-fiber macroporosity that can be further modified to improve surface area, total pore volume, and pore size distribution. This work describes the use of sacrificial mesopore formers in tandem with a micropore etching technique to induce hierarchical porosity in electrospun fibers. Mesopores are formed via the dissolution of silica nanoparticles that are introduced into the fibers during the electrospinning step. After mesopore formation, micropores are etched into the resulting surface through KOH impregnation and thermal activation. This sequential technique creates a hierarchical network of pores from the inherent macroporosity of the fiber network, to the mesopores, and finally micropores to simultaneously maximize surface area and accessibility. Micropore formation is optimized to maximize specific surface area while maintaining physical integrity of the fibers. Further, the combination of mesopores and micropores enables fast ion adsorption rates and capacity. Carbon fiber electrodes fabricated in this method achieve specific surface areas exceeding 1400 m 2 g -1 , with pore volumes exceeding 1.0cc g -1 . The pore size distributions are highly controlled, with 80% of total pore volume coming from pores <20nm in radius. In 500 ppm constant voltage CDI tests, these fiber electrodes obtain a salt adsorption capacity of over 14 mg g -1 at a salt adsorption rate of ~4mg g -1 min -1 , showcasing the high capacity matched with high rate of these easily fabricated, inexpensive materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Stochastic generation of electrolyzer anode catalyst layers

Here, we introduce a stochastic methodology to reproduce the complex pore structure observed in commercial iridium catalyst layers. This method preserves the α pore (pores smaller than 250 nm) and β pore (pores greater than or equal to 250 nm) regions of the catalyst layer. The morphology of the generated materials was validated by comparing the pore size distributions of generated materials against those obtained from commercial materials imaged using x-ray nano computed tomography. We further demonstrate that the pore size distributions of the generated materials are statistically indistinguishable from the imaged catalyst layers, indicating that the stochastic methodology is capable of accurately reproducing catalyst layer morphology. Pore network modelling was conducted on the generated catalyst materials to simulate single-phase permeability, electrical conductivity, and ionic conductivity, and these properties were found to be within experimentally measured ranges for electrolyzer catalyst layers. Additionally, simulations were performed on the generated materials with varying ionomer and iridium catalyst loadings. As the ionomer loading is added, proton conductivity increases exponentially, which demonstrates the importance of optimizing ionomer loading, considering that these effects will be exacerbated in the hydration and temperature conditions of operating electrolyzers. The stochastic material generation method presented in this work is a powerful tool for the development of novel low loading catalyst layers, where the effect of various structural parameters on electrolyzer performance characteristics can be explored.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Synthesis and characterization of porous polydimethylsiloxane structures with adjustable porosity and pore morphology using emulsion templating technique

Abstract Porous polydimethylsiloxane (PDMS) framework with adjustable pore structures has been fabricated by polymerization of the continuous phase in the emulsion templates. Different types of surfactants, including nonionic (Triton X‐100), cationic (Benzalkonium chloride), anionic (sodium dodecyl sulfate), and silicone‐based block copolymer were used to stabilize the water‐in‐oil emulsion system. Deionized water with a wide range of internal phases varying from 10% to 60% by weight was employed to make the low internal phase emulsion and medium internal phase emulsion. The effect of surfactant type, surfactant concentration, and the internal phase volume on the stability of the emulsion, pore morphology, and pore size distribution was explored. The stability of the emulsion was investigated by comparing the pore morphology of the cured sample at different set times, such as 0, 6, and 72 h. Scanning electron microscopy was employed for the characterization of the porous structures. The image analysis was conducted, and the pore size distribution, porosity, and open‐cell ratio of each sample were calculated. Interconnected pores have been seen in the porous PDMS made from emulsions with an internal phase larger than 30%. The results demonstrated that the frequency of open‐cell pores and the pore size is dependent on the surfactant types.

Abshirini, Mohammad↗
DOE OSTI2021

Microstructure and water absorption of ancient concrete from Pompeii: An integrated synchrotron microtomography and neutron radiography characterization

There is renewed interest in using advanced techniques to characterize ancient Roman concrete due to its exceptional durability and low-carbon footprint. In the present work, samples were drilled from the “Hospitium” in Pompeii and were analyzed by synchrotron microtomography (μCT) and neutron radiography to study how the microstructure, including the presence of induced cracks, affects their water adsorption. The water distribution and absorptivity were quantified by neutron radiography. The 3D crack propagation, pore size distribution and orientation, tortuosity, and connectivity were analyzed from μCT results using advanced imaging methods. Porosity was also measured by mercury intrusion porosimetry (MIP) as a reference. Ductile fracture patterns were observed once cracks were introduced. Compared to Portland cement mortar/concrete, the Pompeii samples had relatively high porosity, low connectivity, and a similar coefficient of capillary penetration. In addition, permeability was predicted from models based on percolation theory and pore structure data to evaluate the fluid transport properties. Understanding the microstructure of ancient Pompeii concrete is important because it could inspire the development of modern concrete with high durability.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Insights into determining pore size properties of ultrafiltration membranes

The selectivity of porous membranes is often characterized using solute rejection tests, where membranes are challenged with dilute aqueous solutions of neutral solutes at operating conditions that minimize concentration polarization and fouling. In single solute tests, a membrane is challenged with one molecular weight (MW) solute at a time from low to high MW. Since single solute methods are time-intensive, mixed solute tests have become more common, where a mixture of several MW solutes challenges a membrane at once. However, the presence of large solutes in a mixture increases the rejection of smaller solutes. Furthermore, there are no universally accepted operating conditions or standard methods used by membrane manufacturers or researchers for the experiments, leading to difficulty in pore size and pore characteristic comparisons. In this paper, commercial ultrafiltration membranes were challenged with single and mixed solute polyethylene glycol (PEG) and dextran aqueous solutions. First, rejection values determined using total organic carbon (TOC) and high-performance liquid chromatography (HPLC) from single solute filtration experiments are compared. Differences in rejection curves obtained by the two techniques are attributed to solute polydispersity. Mixed solute filtration experiments with binary mixtures of solutes showcased co-solute interactions, which increase with both the size and weight percent of large solute in the mixture. Mixed solute filtration experiments at varying operating conditions (i.e., stir speed and flux) were conducted to determine operating conditions that mitigate co-solute interactions. Stir speed had a minimal effect on co-solute interactions. In contrast, low flux conditions can help minimize co-solute interactions, leading to pore size distributions that closely resemble results observed in single solute filtration using narrowly dispersed solutes. Additionally, at low flux conditions, the predicted membrane pore size distributions utilizing mixed solute experiments with PEG and dextran were similar.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Multifunctional transition metal doped titanium dioxide reduced graphene oxide composites as highly efficient adsorbents and photocatalysts

A series of novel, mesoporous transition metal doped titanium dioxide-reduced graphene oxide composites are synthesized where the dopants were Mn, Co, Ni, Mo, and W. An in-situ synthesis method was used which involves a green, economic, hydrothermal process which can be scaled up easily. The composites show high surface areas (165–245 m 2 /g) and monomodal pore size distributions with average pore diameters in the range of 3–5 nm. The homogeneous distributions of the dopants are seen in SEM-EDX mapping data. The indirect band gaps of the composite materials are in the range of 2.20–2.48 eV. The composites show excellent dye adsorption activities where 100% adsorption of Rhodamine B occurs within 5 min when Mo–TiO 2 /rGO composite is used. Furthermore, the adsorbed dye can either be desorbed or photocatalytically degraded and the composite is reusable up to 10 cycles without losing significant activity. Mo–TiO 2 /rGO composite showed excellent adsorption of both cationic and anionic dyes at neutral pH.

36 MATERIALS SCIENCE↗
DOE OSTI2026

A User-Friendly GUI Tool for Automated Microstructural Analysis of Fiber-Reinforced Composites and Porous Structures

Understanding and quantifying microstructural features such as fiber orientation and porosity is critical for predicting the mechanical behavior and performance of fiber-reinforced polymer composites. Traditional manual analysis is time-consuming, subjective, and unsuitable for high-throughput datasets. We present a graphical user interface (GUI) application that automates the analysis of microscopy images to extract key microstructural metrics, including fiber orientation tensors, fiber orientation distribution, porosity and pore size distribution. The app integrates multiple image segmentation techniques including global and local thresholding, clustering, and region-based approaches, offering flexibility for different types of image qualities and features. Users can load microstructural images, select regions of interest and segmentation techniques tailored to their image dataset. It also addresses a critical challenge in fiber orientation analysis: the ambiguities caused by touching, overlapping, or partially cut fibers. It supports autorun examples for standardized workflows, enabling reproducible analysis and facilitating training and benchmarking. This tool significantly reduces manual intervention, enhances consistency, and accelerates data generation for structure–property modeling, process optimization, and digital materials research. The tool is intended for use by materials scientists, engineers, and researchers engaged in composite characterization, quality control, and machine learning-based microstructural studies.

Chawla, Komal [ORNL] (ORCID:0000000190327565)↗
DOE OSTI2022

Reduced diffusion and enhanced retention of multiple radionuclides from pore structure characterization of barrier materials for enhanced repository performance

Fluid flow and chemical transport in porous media are the macroscopic consequences of pore structure, which integrates geometry (e.g., pore size and surface area, pore-size distribution) and topology (e.g., pore connectivity). Low-permeability geological media whose pores are poorly interconnected will exhibit the characteristics of anomalous diffusion and sample size-dependent effective porosity, which will strongly impact long-term net diffusion and retention of radionuclides in geological repository settings involving different host rocks and barrier materials. A suite of innovative and complementary experimental approaches is utilized to study the microscopic pore structure and macroscopic fluid flow & chemical transport for a range of host rocks and barrier materials, in addition to standard clay minerals and reference rocks. With a particular focus on quantifying the presence and magnitude of “isolated” pores for a reduced effective porosity in low-permeability geomedia, the integrated methodologies for basic properties and pore structure characterization of these geomedia include X-ray diffraction, thin section petrography, grain size distribution, water immersion porosimetry after vacuum-pulling for full saturation, mercury intrusion porosimetry, nitrogen physisorption, scanning electron microscopy, X-ray computed tomography, and (ultra-)small angle neutron (X-ray) scattering. In addition, custom-designed gas diffusion, tracer recipe involving a range of anionic and cationic chemicals with subsequent analyses by laser ablation and inductively coupled plasma-mass spectrometry, along with batch sorption, column transport, and imbibition tests were conducted for coupled effects of pore structure and chemical retention/transport. From the perspectives of pore structure in conjunction with multiple and complementary approaches to examining a range of sample sizes under different observational scales, we find that the poor pore connectivity is prevalent in low-permeability media (mudstone and crystalline rock) that is related to geological processes (e.g., compaction, diagenesis and thermal maturation). For example, the deep and organic matter-rich mudstones have a much smaller effective porosity than the total porosity (as a result of poor pore connectivity) and associated diffusion coefficient, and the effective porosity & diffusion coefficients are also dependent upon the sample sizes used in the measurement. Similarly, most of the pore space in the shallow mudstone is also controlled by pore-throat diameters in the 5-50 nm range of intergranular pore types from its fine-grained nature, but with an overall good pore connectivity. However, the nm-sized pore space (physically pore-network architecture) and strong sorption capacities (chemical retention from clay minerals) of both shallow and deep mudstones lead to the synergistic retention of cationic radionuclides and their utilities as effective host rocks and barrier materials. Our unique approaches of studying how the micro-scale pore structure affect macro-scale fluid flow, diffusion & retention, and chemical transport produce improved mechanistic understanding, and realistic quantification, of diffusion and retention of typical radionuclides in a range of generic host rocks and barrier materials (clay/shale, salt, crystalline rock, and tuff), with the overall results leading to scientifically-based understanding of enhanced isolation (from both diffusion and retention) of radionuclides and improved confidence on the long-term performance of geological repository to store high-level radioactive wastes. In addition to the training of 25 undergraduates, graduates, and postdocs of UTA, the scientists (organizations) involved in performing this work (e.g., discussion, sample sharing, and operation of SANS and SAXS instruments) include Ed Matteo, Yifeng Wang, and Kristopher Kuhlman (Sandia National Laboratories), Jens Birkholzer, Liange Zheng, Tim Kneafsey, and Sharon Borglin (Lawrence Berkeley National Laboratory), Mavrik Zavarin (Lawrence Livermore National Laboratory), Yukio Tachi and Yuta Fukatsu (Japan Atomic Energy Agency), Mieke de Craen (Euridice, Belgium), Markus Bleuel (NIST), Wei-Ren Chen, Gergely Nagy, Changwoo Do, William Heller, Larry Anovitz, and Kenneth Littrell (ORNL), as well as Jan Illvsky, Ivan Kuzmenko, Ju-Sang Park and Jon Almers (ANL). Key deliverables include a total of 13 peer-reviewed journal articles (nine published and three under review), 23 presentations at scientific conferences (AAPG, AAPG Southwest Section, AGU, Asian Clay Conference, GSA, GSA South-Central Section, IHLRWM, InterPore, International Conference on Chemistry and Migration Behavior of Actinides and Fission Products in the Geosphere, International Conference on Coupled Processes in Fractured Geological Media: Observation, Modeling and Application), and academic institutions (UTA, New Mexico State University; University of Poitiers, France; University of Helsinki, Finland; Uppsala University, Sweden; Istanbul Technical University, Turkey) and other organizations (Andra, France; Posiva Oy, Finland).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Spatial heterogeneity analyses of pore structure and mineral composition of Barnett Shale using X-ray scattering techniques

The spatial heterogeneity of pore structure and mineral composition at mu m to mm scales in mm to cm-sized shale samples complicates the laboratory measurements of porosity & pore size distribution and consequently reservoir quality evaluation. Traditional fluid invasion characterization methods typically take hours to days to get data and can only test relatively small samples (usually 2.54 cm diameter core plugs and mm-sized rock chips). Furthermore, the Xray scattering techniques at the Advanced Photon Source of the Argonne National Laboratory have the capability to non-destructively determine the pore structure and mineral composition of mm x mm area in a short time of seconds and to hold several to hundreds of mm 2 sized sample to conduct large area heterogeneity analysis in the short duration of hours. With the use of ultra-small angle X-ray scattering (USAXS), small-angle X-ray scattering (SAXS), and wide-angle X-ray scattering (WAXS), the porosity, surface area and pore size distribution of two Barnett Shale samples have been mapped out and the mineral compositions are determined qualitatively. Overall, the porosity and pore surface area of the Barnett Shale Sample A over a 36 cm2 area ranges from 1.70 % to 8.13 % and 8.87 m 2 /g to 40.2 m 2 /g respectively. The porosity and surface area of Sample B over a 24 cm 2 area varies from 3.15 % to 11.7 % and 18.3 m 2 /g to 60.2 m 2 /g. In Sample A, the mineral composition shows a shift from carbonate-rich to siliciclastic-rich over a distance of several millimeters. For Sample B, the mineral compositions are mainly siliciclastic and do not show an obvious lithological change. The direct observations of high spatial heterogeneity of pore structure and mineral composition in shale illustrate the utility of integrated X-ray scattering techniques to provide valuable insights into shale studies and reservoir evaluation.

58 GEOSCIENCES↗
DOE OSTI2021

Predicting Fluid Flow Regime, Permeability, and Diffusivity in Mudrocks from Multiscale Pore Characterisation

In geoenergy applications, mudrocks prevent fluids to leak from temporary (H 2 , CH 4 ) or permanent (CO 2 , radioactive waste) storage/disposal sites and serve as a source and reservoir for unconventional oil and gas. Understanding transport properties integrated with dominant fluid flow mechanisms in mudrocks is essential to better predict the performance of mudrocks within these applications. In this study, small-angle neutron scattering (SANS) experiments were conducted on 71 samples from 13 different sets of mudrocks across the globe to capture the pore structure of nearly the full pore size spectrum (2 nm–5 μm). We develop fractal models to predict transport properties (permeability and diffusivity) based on the SANS-derived pore size distributions. The results indicate that transport phenomena in mudrocks are intrinsically pore size-dependent. Depending on hydrostatic pore pressures, transition flow develops in micropores, slip flow in meso- and macropores, and continuum flow in larger macropores. Fluid flow regimes progress towards larger pore sizes during reservoir depletion or smaller pore sizes during fluid storage, so when pressure is decreased or increased, respectively. Capturing the heterogeneity of mudrocks by considering fractal dimension and tortuosity fractal dimension for defined pore size ranges, fractal models integrate apparent permeability with slip flow, Darcy permeability with continuum flow, and gas diffusivity with diffusion flow in the matrix. This new model of pore size-dependent transport and integrated transport properties using fractal models yields a systematic approach that can also inform multiscale multi-physics models to better understand fluid flow and transport phenomena in mudrocks on the reservoir and basin scale.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Measuring Multicomponent Adsorption of Tracer Gases on Natural Zeolites

A natural clinoptilolite sample near the Nevada National Security Site was obtained to study adsorption and retardation on gas transport. Of interest is understanding the competition for adsorption sites that may reduce tracer gas adsorption relative to single-component measurements, which may be affected by the multi-scale pore structure of clinoptilolite. Clinoptilolite has three distinct domains of pore size distributions ranging from nanometers to micrometers: micropores with 0.4–0.7 nm diameters, measured on powders by CO2 adsorption at 273 K, representing the zeolite cages; mesopores with 4–200 nm diameters, observed using liquid nitrogen adsorption at 77 K; and macropores with 300–1000 nm diameters, measured by mercury injection on rock chips (~ 100 mesh), likely representing the microfractures. These pore size distributions are consistent with X-ray computed tomography (CT) and focused ion beam scanning electron microscope (FIB-SEM) images, which are used to construct the three-dimensional (3D) pore network to be used in future gas transport modeling. To quantify tracer gas adsorption in this multi-scale pore structure and multicomponent gas species environment, natural zeolite samples initially in equilibrium in air were exposed to a mixture of tracer gases. As the tracer gases diffuse and adsorb in the sample, the remaining tracer gases outside the sample fractionate. Using a quadrupole mass spectrometer to quantify this fractionation, the degree of adsorption of tracer gases in the multicomponent gas environment and multi-scale pore structure is assessed. The major finding is that Kr reaches equilibrium much faster than Xe in the presence of ambient air, which leads to more Kr uptake than Xe over limited exposure periods. When the clinoptilolite chips were exposed to humid air, the adsorption capability decreases significantly for both Xe and Kr with relative humidity (RH) as low as 3%. Both Xe and Kr reaches equilibrium faster at higher RH. The different, unexpected, adsorption behavior for Xe and Kr is due to their kinetic diameters similar to the micropores in clinoptilolite which makes it harder for Xe to access compared to Kr.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

A Novel Relative Permeability Model for Gas and Water Flow in Hydrate-Bearing Sediments With Laboratory and Field-Scale Application

In a producing gas hydrate reservoir the effective porosity available for fluid flow constantly changes with dissociation of gas hydrate. Therefore, accurate prediction of relative permeability using legacy models (e.g. Brooks-Corey (B-C), van Genuchten, etc.) that were developed for conventional oil and gas reservoirs would require empirical parameters to be calibrated at various S h over its range of variation, but such calibrations are precluded because of lack of experimental relative permeability data. This study proposes a new relative permeability model for gas hydrate-bearing media that is a function of maximum capillary pressure, capillary entry pressure, pore size distribution index, residual saturations, hydrate saturation, and four other constants. The three novel features of the proposed model are: (i) requires fitting its six empirical parameters only once using experimental data from any single S h , and the same set of empirical parameters predict relative permeability at all S h , (ii) includes the effect of capillarity, and (iii) includes the effect of pore-size distribution. From practical standpoint, the model can be used to simulate multiphase flow in gas hydrate-bearing sediments where the proposed relative permeability can account for the evolving hydrate saturation. The proposed model is implemented in a numerical simulator and the wall time required to perform simulations using the proposed model is shown to be similar to the time it takes to run same simulations with the B-C model. The proposed model is a step forward towards achieving the goal of physically accurate modeling of multiphase flow for gas hydrate-bearing sediments that accounts for the effect of gas hydrate saturation change on relative permeability.

54 ENVIRONMENTAL SCIENCES↗