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Final Report for DE-SC0008059

Graphene, a one-atom thick material comprising hexagonally bonded carbon atoms, is one of the strongest materials known and is impermeable to even helium gas. The potential for creation of tunable nanometer-scale pores in graphene, combined with mechanical strength, chemical resistance, and atomic thickness, make it a promising material for improving selectivity, permeability, and energy efficiency in a diverse range of membrane separations. However, fundamental understanding of creation of porous graphene, its mass transport properties, and the relationship between porosity and membrane performance is lacking. This project studied methods to create pores in graphene by ion irradiation and etching, and investigated the effect of the porosity of graphene on mass transport properties at the membrane level as well as across individual pores. Detailed characterization of pore size distributions in graphene using high-resolution scanning transmission electron microscopy was performed to elucidate the relationship between different pore creation processes and the resulting porosity. New methods to create tunable nanometer-scale pores in graphene at high density over large areas were developed. Graphene membranes were fabricated comprising single-layer porous graphene on appropriate support membranes. Mass transport of ions, molecules, water, and gases across the membranes was investigated, and predictive models were developed to relate the graphene porosity and support membrane structure to the mass transport properties of the membranes. The effect of graphene porosity on permeance of the membranes to water, salts, and small molecules was experimentally quantified. Single-pore measurements were performed and a model was developed to understand ion transport across graphene pores, which led to the experimental observation of heterogeneity in transport behaviors and spontaneous fluctuations of ion transport. Functional single-layer nanoporous graphene membranes comprising a high density of pores over macro-scale areas with molecular selectivity were demonstrated for the first time. This project led to three patent applications and 9 journal articles. The fundamental developments in understanding nanoporous graphene membranes have laid the foundations to develop energy-efficient nanoporous graphene membranes for various applications in water desalination, oil and natural gas separations, biotechnology, and chemical processing.

36 MATERIALS SCIENCE↗

Quantitative Characterization of Impacts of Coupled Geomechanics and Flow on Safe and Permanent Geological Storage of CO 2 in Fractured Aquifers

This is the final scientific report for the award DE-FE0023305, entitled “Quantitative Characterization of Impacts of Coupled Geomechanics and Flow on Safe and Permanent Geological Storage of CO 2 in Fractured Aquifers.” The work has been divided into six tasks. In Task 2, we characterized rock properties, which are important when developing a quantitative approach for understanding and predicting geomechanical effects on large-scale CO 2 injection and long-term storage in the subsurface. Rock properties of interest for this characterization include porosity, permeability, elastic constants, strength, and heat capacity. We measured rock properties for three different rock types: concrete, sandstone and shale. These properties were obtained from the acoustic measurement, permeability and porosity measurement, Brazilian test, the uniaxial compressive test, and heat capacity measurement. Then, using the Brazilian technique to fracture samples, we measured their permeability under brine injection for varying effective stresses, followed by similar measurements of permeability under sc-CO 2 injection. Permeability to brine and sc-CO 2 decreased as the effective stress increased. The apparent permeability to sc-CO 2 was an order of magnitude less than that for brine, a consequence of CO 2 being the non-wetting fluid. In Task 3, we developed understandings and correlations for CO 2 injection pressure induced fracturing. We initially fractured four eight inch cubes of concrete with brine to establish a standard test procedure. Then, additional concrete samples were fractured using brine. Confining stresses were exerted on the samples and brine was injected at a constant rate into a borehole that was previously drilled into the concrete cube. The borehole pressure was measured and fracture initiation was identified as a peak in the pressure profile. That was followed by fracture propagation, which was identified as a plateau in the pressure profile, and finally the fracture reached the sample surface. The sample surfaces were photographed before and after fracturing, which enabled determination of where the fracture reached the sample surface. Afterwards, aqueous food dye solution was injected into the fractured concrete samples to color the fracture planes. The borehole was filled with food dye solution in advance, a gas pulse was transmitted to the borehole, and the borehole was then shut in to allow the food dye to be driven into existing fractures. Then, the concrete samples were broken down by high-pressure gas injection to reveal the geometry and morphology of the hydraulic fractures. In addition, acoustic measurements were conducted on multiple locations on each face of the concrete samples before and after injection for comparison. This comparison was used to confirm changes in the internal structure of the concrete sample, namely the formation of fractures. There were six concrete samples fractured with brine. Afterwards, concrete samples were fracture using sc-CO 2 . The main change in experimental procedure was the inclusion of temperature control, since in the field, we mostly encounter temperature and pressure conditions above the supercritical point of CO 2 . The concrete samples were pre-heated in an oven to elevate their temperature, and thermal tape was used to heat the CO 2 to a temperature above its supercritical temperature. Two concrete samples were fractured using liquid CO 2 , four concrete samples were fractured using gaseous CO 2 , and twenty two concrete samples were fractured using sc-CO 2 . For the concrete samples fractured using sc-CO 2 , three had pre-existing hydraulic fractures on the surface near the wellbore, and two were water saturated (as opposed to containing only air). Two concrete samples were composite samples, with a high permeability ball in the center, in order to represent CO 2 injection into a high permeability zone surrounded by a low permeability sealing formation. Later, we fractured five shale samples, obtained from the Niobrara shale outcrop, with sc-CO 2 . The injection rate was constant, confining stresses were applied, the shale samples were pre-heated in an oven to the desired temperature, and the sample was then fractured. An analysis of the failure type was done for many of the concrete samples, based on the predicted break down pressure for tensile and shear failure, and it was found that most samples fractured due to shear failure. Also, the presence of induced fractures has little to no effect on the fracture initiation pressure, but significantly changes the fracture morphology. The CO 2 fracturing in water saturated samples behaved much similar to brine induced fracturing. There was a significant difference of breakdown pressure for injection of CO 2 and brine, where the breakdown pressure for CO 2 induced fracturing is generally around the minimum horizontal stress and that for brine is much higher. Finally, the fracture orientation for most samples with large confining stress differential was perpendicular to the minimum horizontal stress. When the stress differential, especially the difference between the two directions with the smallest stresses was small, the fracture orientation was determined not only by the minimum stress direction, but also the magnitude of the confining stress, the tensile strength of the rock, and the breakdown pressure. In Task 4, we modified our coupled flow-geomechanical models to model fracture growth and propagation in storage formations and caprocks. These flow-geomechanical models are TOUGH2-CSM and TOUGH2-FLAC. The TOUGH2-CSM fluid and heat flow formulation is based on the TOUGH2 formulation of mass and energy conservation equations that govern fluid and heat flow in general multiphase, multicomponent, multi-porosity systems. The TOUGH2-CSM simplified geomechanical formulation is based on the linear theory of elasticity applied to multi-porosity non-isothermal (thermo-multi-poroelastic) media. We previously derived, from the fundamental relations of the linear theory of elasticity, an equation relating mean stress, pore pressures, temperatures, and body force (the Mean Stress equation) that we added to the TOUGH2-CSM fluid and heat flow equations. We extended the TOUGH2-CSM simplified geomechanical formulation to calculate the entire stress tensor by deriving equations for stress tensor components from derivatives of the Cartesian thermo-multi-poroelastic Navier equation components. In addition, we derived equations for stress tensor components in rz-coordinates. We solved these geomechanical equations using the integral finite difference method. This method utilizes momentum fluxes obtained by “factoring” a divergence operator out of each geomechanical equation. In Task 5, we did a literature survey to determine suitable correlations for fracture initiation, growth, and propagation. After surveying numerous papers, we modified TOUGH2-CSM to model stress dependent fracture initiation and growth using the Mohr-Coulomb criterion for shear failure in faults and caprock and the condition of negative minimum effective stress for tensile failure. Tensile failure results in a fracture whose width depends on the difference between fracture pressure and minimum stress and whose propagation is based on the difference between the stress intensity factor at the fracture tip and the rock toughness. The TOUGH-FLAC model is based on the FLAC3D ubiquitous joint model, extended for the modeling of permeability changes induced by changes in effective normal stress across fractures as well permeability changes caused by shearing along fractures. In Task 6, we validated our coupled flow-geomechanical models using analytical solutions and problems from the literature. We validated the TOUGH2-CSM modifications using analytical solutions to the displacement from a uniform load on a semi-infinite elastic medium and the two-dimensional Mandel-Cryer effect. Those were followed by a sample problem to test our stress tensor calculations, which was for injection into a single-phase reservoir with constant properties. Comparisons of our simulator to published results were done on for the depletion of a single-phase reservoir with stress dependent porosity, two examples from the In Salah gas project, an axisymmetric baserock–reservoir–caprock system with a normal faulting stress regime that had thermally induced shear stresses, simulations of CO 2 leakage through caprock in a two-dimensional reservoir in Cartesian coordinates, and predictions of caprock failure from CO 2 injection into an axisymmetric reservoir. Finally, we simulated CO 2 injection pressure-induced fracturing from one of our laboratory studies, Sample 39, and obtained a fracture profile. We also validated the TOUGH2-FLAC model for fluid driven fracture growth against solutions based on the KGD model and a case with an inclined fracture that was loaded from the boundaries to achieve wing-crack propagation. The strain softening tensile behavior and softening of modulus considering a simple damage approach was verified by a simulation representing hydraulic fracturing stress measurement around a vertical well. Finally, the model was validated against deep fracture zone opening and surface uplift at In Salah with inverses analysis used to improve the match of simulation with field data. In Task 7, we developed a scheme based on inverse modeling that can be used to identify caprock leakage. Injection of fluid into a reservoir results in a time varying pressure profile that depends on the properties of the rock and the fluid. The presence of significant caprock leakage would effect this pressure profile and we used inverse modeling, namely the Levenberg-Marquardt method, to determine the leakage location from the pressure profile. A two-dimensional and a three-dimensional example based on published data were presented. The published simulation was run and its results were considered as “field” data. In the two-dimensional example, a simulation of CO 2 injection into a two-dimensional aquifer-caprock system, the caprock had a vertical fault through which leakage could occur. The location of this leakage was obtained from our inverse modeling scheme. In the three-dimensional example, the simulation domain had four geological layers, one of which was the injection zone that contained a horizontal injection well. We simulated fractures as high permeability gridblocks, introduced a fracture that spanned the caprock depth, and ran a simulation to obtain “field” data. Then, using our inverse modeling scheme, we obtained the location of that fracture.

58 GEOSCIENCES↗

Integrated characterization of CO 2 storage reservoirs on the Rock Springs Uplift combining geomechanics, geochemistry, and flow modeling

This project improves understanding of the effects CO 2 injection and storage on geomechanical, petrophysical, and other properties on two potential reservoirs, the Madison Limestone and Weber Sandstone, at the Rock Springs Uplift, southwest Wyoming. Rock physics studies, laboratory experiments, and computer simulations were employed. Two groups of rock samples were prepared, one aged with formation brine and the second aged with CO 2 -saturated formation brine and subsequently used for geomechanical, geochemical, and petrophysical testing. Rock physics studies provided a facies classification to discriminate among different lithologies and to investigate the feasibility of predicting petrophysical properties using seismic inversion. By applying a zone-wise regression relation established in this facies analysis, a 3D reservoir model was developed. It was determined that time-lapse seismic data are not feasible for monitoring CO 2 displacement at the Rock Springs Uplift or to mitigate leakage-risks situations because pressure and fluid saturation have small effects on elastic velocities and synthetic seismograms. The small variations that do occur are due to the low porosity of the sandstone and the high stiffness of the dolomite. In the Madison Limestone, mineral dissolution due to reaction with CO 2 -saturated brine was observed in highly permeable pathways while mineral precipitation happened in intergranular or micropores. Changes in pore size were quantified via Time-Domain Nuclear Magnetic Resonance transverse relaxation time (T 2 ) and diffusion coefficient distributions. As opposed to continuous injection of CO 2 -saturated brine, a subtle increase in porosity after static ‘soaking’ with CO 2 -saturated brine increases permeability due to the heterogeneity of changes in pore and pore throat sizes. Porosity-permeability relationships are fitted using a power-law function that can be adopted to model time-evolved porosity and permeability in a transport-limited CO 2 injection process. The effect of CO 2 -saturated brine on the linear elastic properties of Weber Sandstone and Madison Limestone cannot be generally concluded. Considering horizontal and vertical orientations and different confining pressures, no consistent relationship between stress (or strain) data and reaction with CO 2 -saturated brine was observed in the nonlinear plastic and post-failure regime. The change of elastic constants due to reaction with CO 2 -saturated brine is more significant in Madison Limestone than in Weber Sandstone; however, no consistent trend was observed. Reservoir simulations suggest that injectivity for Weber Sandstone is adversely impacted by low permeability. Changes in confining pressure do not impact injection rate and can be ignored while the effect of changes to pore pressure cannot. The effect of confining pressure and pore pressure on the size of the CO 2 plume in the Madison Limestone is negligible because of higher permeability. Geomechanical and petrophysical properties induced by CO 2 -brine-rock reactions were time-dependent. Simulations considered these time-dependent properties and indicate that injectivity, porosity distribution, pressure distribution and CO 2 saturation were affected.

58 GEOSCIENCES↗

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↗

CHIPFoam Modification to Allow for Modelling SWIFT Foams

SWIFT (Silicon-water in Familiar Template) foams are silicone foams that have a continuous porosity without having any obvious spherical or ellipsoidal pore shapes. Like other foamed rubber, SWIFT foams can experience large reversible deformations. Because of their microstructure, SWIFT foams have a stiffering behavior in compression that is very abrupt compared to most other foamed rubbers. Work by Benedikt reported by Miller showed that fitting compressive test data with the CHIPFoam model in its current form is impractical and inaccurate. This report describes an extension made to CHIPFoam to allow the modeling of SWIFT foams. While the extension allows the modeling of SWIFT foams, it also extends the range of porosity of foams that can be modelled with CHIPFoam to include very high porosity (>99%) foamed rubber. The previous model was unstable for porosities greater than 70%. The changes made to CHIPFoam include the introduction of a critical porosity at which the compressible Danielsson strain energy function that couples volumetric and deviatoric mechanical behavior begins to increase with compression. This new feature also required the introduction of a third term in the multiplicative decomposition of the relative volume, J . The organization of this report is described here. The first section, SWIFT Foam Structure and Mechanical Behavior, describes the structure of SWIFT foams as contrasted to other foamed rubbers. It also contrasts the mechanical behavior of SWIFT foams to other more traditional foamed rubbers. The second section, CHIPFoam Modifications, describes the specific modifications done to be able to modify the delayed rapid compressive stiffening seen in SWIFT foams. The third section, Results, demonstrates the use of the modified model to fit compressive loading response data from a SWIFT foam sample. The fourth section, Conclusions and Further Work, puts the work in perspective and presents likely further work.

36 MATERIALS SCIENCE↗

Compaction of crushed salt for safe containment – overview of the KOMPASS project

Abstract. In Germany, rock salt formations are possible host rock candidates for a repository for heat-emitting radioactive waste. The safety concept of a repository in salt bases on a multibarrier system consisting mainly of the geological barrier salt and geotechnical seals ensuring safe containment. Crushed salt will be used for backfilling of cavities and sealing measures in drifts and shafts due to its favourable properties and its easy availability (mined-off material). The creep of the rock salt leads to crushed salt compaction with time. Thereby, the crushed salts' porosity is reduced from the initial porosity of 30 %–40 % to a value comparable to the porosity of undisturbed rock salt (≤1 %). In such low porosity ranges, technical impermeability is assumed. The compaction behaviour of crushed salt is rather complex and involves several coupled THM processes (Kröhn et al., 2017; Hansen et al., 2014). It is influenced by internal properties like humidity and grain size distribution, as well as boundary conditions such as temperature, compaction rate or stress state. However, the current process understanding has some important gaps referring to the material behaviour, experimental database and numerical modelling. It needs to be extended and validated, especially in the low porosity range. The objective of the KOMPASS project was development of methods and strategies for the reduction of deficits in the prediction of crushed salt compaction leading to an improvement of the prognosis quality. Key results are as follows (KOMPASS Phase 1, 2020): selection of an easily available and permanently producible synthetic crushed salt mixture, acting as a reference material for generic investigations; development and proof of different techniques for producing pre-compacted samples for further investigations; establishment of a tool of microstructure investigation methods to demonstrate the comparability of grain structures of pre-compacted samples with in-situ compacted material for future investigations; execution of various laboratory experiments using pre-compacted samples, e.g. long-term creep tests which deliver reliable information about time- and stress-dependent compaction behaviour; development of a complex experimental investigation strategy to derive necessary model parameters considering individual functional dependencies. Its technical feasibility was successfully verified; benchmarking with various existing numerical models using datasets from three different triaxial long-term tests. The result was not entirely satisfactory; however, the number of influencing factors is small and further validation work has to be done. Overall, the KOMPASS project has made significant progress in the approaches to solving the outstanding question, building the basis for further investigations.

Friedenberg, Larissa↗

Experimental investigation of wall shock cancellation and reduction of wall interference in transonic testing

A series of experiments were performed to evaluate the effectiveness of a three-dimensional land and groove wall geometry and a variable permeability distribution to reduce the interference produced by the porous walls of a supercritical transonic test section. The three-dimensional wall geometry was found to diffuse the pressure perturbations caused by small local mismatches in wall porosity permitting the use of a relatively coarse wall porosity control to reduce or eliminate wall interference effects. The wall porosity distribution required was found to be a sensitive function of Mach number requiring that the Mach number repeatability characteristics of the test apparatus be quite good. The effectiveness of a variable porosity wall is greatest in the upstream region of the test section where the pressure differences across the wall are largest. An effective variable porosity wall in the down stream region of the test section requires the use of a slightly convergent test section geometry.

Ferri, A.↗

Investigation to optimize the passive shock wave-boundary layer control for supercritical airfoil drag reduction

The optimization of passive shock wave/boundary layer control for supercritical airfoil drag reduction was investigated in a 3 in. x 15.4 in. Transonic Blowdown Wind Tunnel. A 14% thick supercritical airfoil was tested with 0%, 1.42% and 2.8% porosities at Mach numbers of .70 to .83. The 1.42% case incorporated a linear increase in porosity with the flow direction while the 2.8% case was uniform porosity. The static pressure distributions over the airfoil, the wake impact pressure data for determining the profile drag, and the Schlieren photographs for porous surface airfoils are presented and compared with the results for solid-surface airfoils. While the results show that linear 1.42% porosity actually led to a slight increase in drag it was found that the uniform 2.8% porosity can lead to a drag reduction of 46% at M = .81.

Nagamatsu, H. T.↗

Gravitational Effects on Distortion in Sintering

During sintering a powder compact gains strength through low-temperature interparticle bonding, usually induced by solid-state surface diffusion, followed by further strength contributions from high-temperature densification. In cases where a liquid phase forms, sintering densification is accelerated and shape retention is sustained while open pores remain and contribute capillary forces. Unfortunately, sintering densification requires the compact become thermally softened to a point where creep strain rates reach levels near 10(exp -2)/s when the liquid forms. On the other hand, thermal softening of the powder compact substantially reduces the strength at high temperatures. Therefore, the in situ strength evolution during sintering is a primary focus to separate compact densification (as required for high performance) with minimized distortion (as required for net-shaping). With respect to gravitation effects on distortion during sintering there are two points of substantial weakness - prior to significant interparticle bonding and during final pore closure. This research is focused on understanding the competition among interparticle neck growth, densification, thermal softening, grain boundary wetting, capillary effects associated with liquid wetting and residual porosity, and gravity. Most surprising is the apparent role of gravity, where the deviatoric stress acting on the powder structure induces skeletal formation that reduces distortion. In contrast with theory, microgravity samples exhibit more distortion yet fail to fully densify. Results are presented on the experimental concepts supporting an emerging model of sintering strength evolution that enables understanding of both distortion and densification. The experiments have relied on tungsten heavy alloys, various combinations of dihedral angle, pore size, initial porosity, liquid:solid ratio, and heating rates. On Earth, the dominant factor with respect to distortion is the starting body heterogeneity. Current modeling efforts are seeking some means to uniformly predict the distortion based on a starting pore structure heterogeneity parameter. Densification is largely unaffected by the initial pore structure, but distortion is highly variable, suggesting that nonuniform pore closure might be a significant parameter during sintering. With respect to flight experiments, plans include removal of the solid body forces acting on the solid grains, allowing stabilization of the pore structure and examination of the buoyancy effects with regard to distortion. In microgravity there is the surprising result that compacts do not densify, yet distort a factor that is contrary to all current sintering models. Densification without distortion during liquid phase sintering was achieved by manipulating microstructure and its evolution during sintering. Microstructure parameters such as the solid volume fraction, dihedral angle, initial porosity, and pore size were varied to measure densification and distortion behavior during LPS using W-Ni-Cu alloys. Green compacts were formed using ethylene-bis-stearamide as a pore-forming agent with the amount of polymer controlling the initial porosity. Different initial pore sizes were generated by varying the polymer particle size. Dihedral angle was varied by changing the Ni:Cu ratio in the alloys. Finally, the solid volume fraction was adjusted via the tungsten content. Distortion was quantified using profiles determined with a coordinate measuring machine to calculate a distortion parameter. Sintering results showed that solid volume fraction and dihedral angle are the dominant factors on densification and distortion during liquid phase sintering. Distortion decreases with increasing solid volume fraction and dihedral angle, while initial porosity and pore size have no observable effect on distortion at nearly full densification. Various strategies emerge to improve distortion control in liquid phase sintering.

German, Randall M.↗

Estimation of Length-Scales in Soils by MRI

Soil can be best described as an unconsolidated granular media that forms porous structure. The present macroscopic theory of water transport in porous media rests upon the continuum hypothesis that the physical properties of porous media can be associated with continuous, twice-differentiable field variables whose spatial domain is a set of centroids of Representative Elementary Volume (REV) elements. MRI is an ideal technique to estimate various length-scales in porous media. A 0.267 T permanent magnet at NASA GRC was used for this study. A 2D or 3D spatially-resolved porosity distribution were obtained from the NMR signal strength from each voxel and the spin-lattice relaxation time. A classical spin-warp imaging with Multiple Spin Echos (MSE) was used to evaluate proton density in each voxel. Initial resolution of 256 x 256 was subsequently reduced by averaging neighboring voxels and the porosity convergence was observed. A number of engineered "space candidate" soils such as Isolite(trademark), Zeoponics(trademark), Turface(trademark), and Profile(trademark) were used. Glass beads in the size range between 50 microns to 2 mm were used as well. Initial results with saturated porous samples have shown a good estimate of the average porosity consistent with the gravimetric porosity measurement results. For Profile(trademark) samples with particle sizes ranging between 0.25 to 1 mm and characteristic interparticle pore size of 100 microns the characteristic Darcy scale was estimated to be about delta(sub REV) = 10 mm. Glass beads porosity show clear convergence toward a definite REV which stays constant throughout homogeneous sample. Additional information is included in the original extended abstract.

N E Daidzic↗

Aerodynamic Characterization of New Parachute Configurations for Low-Density Deceleration

The Low Density Supersonic Decelerator project performed a wind tunnel experiment on the structural design and geometric porosity of various sub-scale parachutes in order to inform the design of the 110ft nominal diameter flight test canopy. Thirteen different parachute configurations, including disk-gap-band, ring sail, disk sail, and star sail canopies, were tested at the National Full-scale Aerodynamics Complex 80- by 120-foot Wind Tunnel at NASA Ames Research Center. Canopy drag load, dynamic pressure, and canopy position data were recorded in order to quantify there lative drag performance and stability of the various canopies. Desirable designs would yield increased drag above the disk-gap-band with similar, or improved, stability characteristics. Ring sail parachutes were tested at geometric porosities ranging from 10% to 22% with most of the porosity taken from the shoulder region near the canopy skirt. The disk sail canopy replaced the rings lot portion of the ring sail canopy with a flat circular disk and wastested at geometric porosities ranging from 9% to 19%. The star sail canopy replaced several ringsail gores with solid gores and was tested at 13% geometric porosity. Two disk sail configurations exhibited desirable properties such as an increase of 6-14% in the tangential force coefficient above the DGB with essentially equivalent stability. However, these data are presented with caveats including the inherent differences between wind tunnel and flight behavior and qualitative uncertainty in the aerodynamic coefficients.

parachute↗

Effects of Layer Spacing for a Multilayered Facesheet Acoustic Liner

A single degree-of-freedom acoustic liner, a perforate facesheet over honeycomb core, is modified to have a facesheet comprised of three layers. The top and bottom perforate layers have the same dimensions with aligned perforations while the middle layer perforate can be longitudinally shifted up to 0.075 inches to change the effective porosity of the facesheet. These configurations range in porosity from 100% open down to 10% open in addition to two closed configurations (0% porosity). Gaps are introduced between the facesheet layers ranging from no gap to 0.016 inches. These configurations are tested in the NASA Langley Grazing Flow Impedance Tube to determine their acoustic impedance spectra. Introduction of a gap affects the acoustic impedance of the liner where the resonant frequency of the liners decreases with increased gap thickness for liners with an open area ratio above 25% but increases with gap thickness for liners with an open area ratio below 25%. Additionally, it is observed that increasing the gap height results in a reduction of the effect of porosity on acoustic impedance. The results show that the presence of such gaps can have a significant effect on liner impedance especially as porosity decreases.

acoustic liners↗

Utilization of the St. Peter Sandstone in the Illinois Basin for CO2 Sequestration

This project is part of a larger project co-funded by the United States Department of Energy (US DOE) under cooperative agreement DE-FE0002068 from 12/08/2009 through 9/31/2014. The study is to evaluate the potential of formations within the Cambro-Ordovician strata above the Mt. Simon Sandstone as potential targets for carbon dioxide (CO2) sequestration in the Illinois and Michigan Basins. This report evaluates the potential injectivity of the Ordovician St. Peter Sandstone. The evaluation of this formation was accomplished using wireline data, core data, pressure data, and seismic data acquired through funding in this project as well as existing data from two additional, separately funded projects: the US DOE funded Illinois Basin – Decatur Project (IBDP) being conducted by the Midwest Geological Sequestration Consortium (MGSC) in Macon County, Illinois, and the Illinois Industrial Carbon Capture and Sequestration (ICCS) Project funded through the American Recovery and Reinvestment Act (ARRA), which received a phase two award from DOE. This study addresses the question of whether or not the St. Peter Sandstone may serve as a suitable target for CO2 sequestration at locations within the Illinois Basin where it lies at greater depths (below the underground source of drinking water (USDW)) than at the IBDP site. The work performed included numerous improvements to the existing St. Peter reservoir model created in 2010. Model size and spatial resolution were increased resulting in a 3 fold increase in the number of model cells. Seismic data was utilized to inform spatial porosity distribution and an extensive core database was used to develop porosity-permeability relationships. The analysis involved a Base Model representative of the St. Peter at “in-situ” conditions, followed by the creation of two hypothetical models at in-situ + 1,000 feet (ft.) (300 m) and in-situ + 2,000 ft. (600 m) depths through systematic depthdependent adjustment of the Base Model parameters. Properties for the depth shifted models were based on porosity versus depth relationship extracted from the core database followed by application of the porosity-permeability relationship. Each of the three resulting models were used as input to dynamic simulations with the single well injection target of 3.2 million tons per annum (MTPA) for 30 years using an appropriate fracture gradient based bottom hole pressure limit for each injection level. Modeling results are presented in terms of well bottomhole pressure (BHP), injection rate profiles, and three-dimensional (3D) saturation and differential pressure volumes at selected simulation times. Results suggest that the target CO2 injection rate of 3.2 MTPA may be achieved in the St. Peter Sandstone at in-situ conditions and at the in-situ +1,000 ft. (300 m) depth using a single injector well. In the latter case the target injection rate is achieved after a ramp up period which is caused by multi-phase flow effects and thus subject to increased modeling uncertainty. Results confirm that the target rate may not be achieved at the in-situ +2,000 ft. (600 m) level even with multiple wells. These new modeling results for the in-situ case are more optimistic than previous modeling results. This difference is attributed to the difference in methods and data used to develop model permeability distributions. Recommendations for further work include restriction of modeling activity to the in-situ +1,000 ft. (300 m) and shallower depth interval, sensitivity and uncertainty analysis, and refinement of porosity and permeability estimates through depth and area selective querying of the available core database. It is also suggested that further modeling efforts include scope for evaluating project performance in terms of metrics directly related to the Environmental Protection Agency (EPA) Class VI permit requirements for the area of review (AoR) definition and post injection site closure monitoring.

Will, Robert↗

The Potosi Reservoir Model 2013c, Property Modeling Update

As part of a larger project co-funded by the United States Department of Energy (US DOE) to evaluate the potential of formations within the Cambro-Ordovician strata above the Mt. Simon as potential targets for carbon sequestration in the Illinois and Michigan Basins, the Illinois Clean Coal Institute (ICCI) requested Schlumberger to evaluate the potential injectivity and carbon dioxide (CO2) plume size of the Cambrian Potosi Formation. The evaluation of this formation was accomplished using wireline data, core data, pressure data, and seismic data from this project as well as two other separately funded projects: the US DOE-funded Illinois Basin–Decatur Project (IBDP) being conducted by the Midwest Geological Sequestration Consortium (MGSC) in Macon County, Illinois, and the Illinois Industrial Carbon Capture and Sequestration (ICCS) project funded through the American Recovery and Reinvestment Act. In 2010, technical performance evaluations on the Cambrian Potosi Formation were performed through reservoir modeling. The data included formation tops from mud logs, well logs from the Verification Well #1 (VW1) and the Injection Well (CCS1), structural and stratigraphic formation from three dimensional (3D) seismic data, and field data from several waste water injection wells for Potosi Formation. The intention was for 2.2 million tons per annum (2 million tonnes per annum [MTPA]) of CO2 to be injected for 20 years. In the Task Error! Reference source not found., the 2010 Potosi heterogeneous model (referred to as the "Potosi Dynamic Model 2010") was re-run using a new injection scenario of 3.5 million tons per annum (3.2 MTPA) for 30 years. The extent of the Potosi Dynamic Model 2010, however, appeared too small for the new injection target. The models size was insufficient to accommodate the evolution of the plume. The new model, Potosi Dynamic Model 2013a, was built by extending the Potosi Dynamic Model 2010 grid to 30 by 30 mi (48 by 48 km), while preserving all property modeling workflows and layering. This model was retained as the base case. In the preceding Task [1], the Potosi reservoir model was updated to take into account the new data from the Verification Well #2 (VW2) which was drilled in 2012. The porosity and permeability modeling was revised to take into account the log data from the new well. Revisions of the 2010 modeling assumptions were also done on relative permeability, capillary pressures, formation water salinity, and the maximum allowable well bottomhole pressure. Dynamic simulations were run using the injection target of 3.5 million tons per annum (3.2 MTPA) for 30 years. This dynamic model was named Potosi Dynamic Model 2013b. In this Task, a new property modeling workflow was applied, where seismic inversion data guided the porosity mapping and geobody extraction. The static reservoir model was fully guided by PorosityCube interpretations and derivations coupled with petrophysical logs from three wells. The two main assumptions are: porosity features in the PorosityCube that correlate with lost circulation zones represent vugular zones, and that these vugular zones are laterally continuous. Extrapolation was done carefully to populate the vugular facies and their corresponding properties outside the seismic footprint up to the boundary of the 30 by 30 mi (48 by 48 km) model. Dynamic simulations were also run using the injection target of 3.5 million tons per annum (3.2 MTPA) for 30 years. This new dynamic model was named Potosi Dynamic Model 2013c. Reservoir simulation with the latest model gives a cumulative injection of 43 million tons (39 MT) in 30 years with a single well, which corresponds to 40% of the injection target. The injection rate is approx. 3.2 MTPA in the first six months as the well is injecting into the surrounding vugs, and declines rapidly to 1.8 million tons per annum (1.6 MTPA) in year 3 once the surrounding vugs are full and the CO2 start to reach the matrix. After, the injection rate declines gradually to 1.2 million tons per annum (1.1 MTPA) in year 18 and stays constant. This implies that a minimum of three (3) wells could be required in the Potosi to reach the injection target. The injectivity evaluated in this Task was higher compared to the preceding Task, since the current facies modeling (guided by the porosity map from the seismic inversion) indicated a higher density of vugs within the vugular zones. 5 As the CO2 follows the paths where vugs interconnection exists, a reasonably large and irregular plume extent was created. After 30 years of injection, the plume extends 13.7 mi (22 km) in E-W and 9.7 mi (16 km) in N-S directions. After injection finishes, the plume continues to migrate laterally, mainly driven by the remaining pressure gradient. After 60 years post-injection, the plume extends 14.2 mi (22.8 km) in E-W and 10 mi (16 km) in N-S directions, and remains constant as the remaining pressure gradient has become very low. Should the targeted cumulative injection of 106 million tons (96 MT) be achieved; a much larger plume extent could be expected. The increase of reservoir pressure at the end of injection is approximately 1,200 psia (8,274 kPa) around the injector and gradually decreases away from the well. The reservoir pressure increase is less than 10 psia (69 kPa) beyond 14 mi (23 km) away from injector. Should the targeted cumulative injection of 106 million tons (96 MT) be achieved; a much larger areal pressure increase could be expected. The reservoir pressure declines rapidly during the first 30 years post injection and the initial reservoir pressure is nearly restored after 100 years post-injection. The present evaluation is mainly associated with uncertainty on the vugs permeability and interconnectivity. The use of porosity mapping from seismic inversion might have reduced the uncertainty on the lateral vugs body distributions. However, major uncertainties on the Potosi vugs permeability remains. Therefore, injection test and pressure interference test among the wells could be considered to evaluate the local vugs permeability, extent, and interconnectivity. Facies modeling within the Potosi has yet to be thoroughly addressed. The carbonates during the time of deposition are believed to be regionally extensive. However, it may be worth delineating the reservoir with other regional wells or modern day analogues to understand the extent of the Potosi. More specifically, the model could incorporate lateral changes or trends if deemed necessary to represent facies transition. Data acquisitions to characterize the fracture pressure gradient, the formation water properties, the relative permeability, and the capillary pressure could also be considered in order to allow a more rigorous evaluation of the Potosi storage performance. A simulation using several injectors could also be considered to determine the required number of wells and appropriate spacing to achieve the injection target while taking into account the pressure interference.

Adushita, Yasmin↗

Multivariate Analysis of the Influence of Process Parameters on Suspension Plasma-Sprayed Coatings

Suspension plasma spray (SPS) is far more complicated than conventional plasma spray and requires a deep knowledge about the influence of process parameters and their correlations. In this study, YSZ coatings were manufactured by SPS with six different process parameters such as plasma power, suspension mass load, original powder size, substrate surface topology, spray distance, and spray step. Afterwards, the porosity of as-prepared coatings was investigated by image method and X-ray transmission technique. A multivariate analysis on the collected experimental data was carried out by employing mathematical statistics methods. The results showed that: 1) Coating porosity has a negative correlation with plasma power and suspension mass load and a positive correlation with the original powder size, spray distance, spray step, and substrate roughness; 2) Spraying distance is the main factor affecting to coating porosity, followed by suspension mass load and substrate surface roughness, respectively. A linear model for porosity prediction was developed and was verified by experiments. The mechanism by which process parameters influence coating porosity is also discussed.

Zhao, Yongli↗

Hierarchical printed product and composition and method for making the same

Disclosed herein are embodiments of a printable composition that can be used to make printed products of a chosen material chemistry that have different levels of porosity within the printed product's structure Also disclosed herein are embodiments of a printed product that has multiple levels of porosity throughout its structure, which can include a macroscale level of porosity, a microscale level of porosity, a nanoscale level of porosity and any combination thereof. These printed products can be made using a 3-D printer and can be made from a single printable composition without the need to add different structural components during the production process. Also disclosed herein are embodiments of a method for making and using a printed product.

Lee, Matthew N.↗

Reaction-Induced Fracturing of Porous Carbonate Rocks during Volume-Increasing Replacement by Witherite

Volume-increasing replacement reactions can lead either to fracturing of the parent phase or to the formation of cohesive layers that passivate further reaction, but the factors that drive one outcome or the other are not understood. In this experimental study, we investigated the volume-increasing replacement of carbonate rocks (consisting of CaCO 3 and CaMg(CO 3 ) 2 ) of different porosity by witherite (BaCO 3 ). Samples were characterized using scanning electron microscopy, Raman spectroscopy, small-angle neutron/X-ray scattering, X-ray tomography, and scanning transmission electron microscopy. We observed the formation of a witherite reaction layer and witherite formation within pores and along grain boundaries. Despite this being a volume-increasing replacement reaction, newly formed witherite was porous, potentially allowing further replacement. Filled fractures were observed in the low-porosity carbonates, whereas witherite formed within pores in high-porosity carbonates. We conclude that fracturing of the parent phase versus passivation is contingent on the initial microstructure of the parent with an optimal degree of porosity required for fracturing.

Calcite↗

Mechanism of formation of wiggly compaction bands in porous sandstone: 1. Observations and conceptual model

Field observations are combined with microscopic analyses to investigate the mechanism of formation of wiggly compaction bands (CBs) in the porous Jurassic aeolian Aztec Sandstone exposed at Valley of Fire State Park, Nevada. Among the three types of CBs (T1, T2, and T3), we focused on the wiggly CBs (T3), which show a chevron (T3 1 ) or wavy (T3 2 ) pattern with typical corner angles of approximately 90° or 130°, respectively. Where corner angles of wiggly CBs increase to 180°, they become straight CBs (T3 3 ). Image analyses of thin sections using an optical microscope show host rock porosity increases downslope in this dune, and the predominant type of wiggly CBs also varies from chevron to straight CBs. Specifically, band type varies continuously from chevron to wavy to straight where the porosity and grain sorting of the host rock increase systematically. Based on the crack and anticrack models, we infer that the change from chevron to straight CBs is due to increasing failure angle of the sandstone and this may correlate with increasing grain sorting. Wavy CBs with intermediate failure angle and host rock porosity are an intermediate stage between chevron and straight CBs. Previous sedimentological studies also have suggested that grain size and sorting degree increase downslope on the downwind side of sand dunes due to a sieving process of the wind-blown grains. Furthermore, the transition of wiggly CB types in this regard correlates with increasing sorting and perhaps with increasing porosity downslope.

58 GEOSCIENCES↗