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At least 91 records · Page 5

Improved BN Coatings on SiC Fibers in SiC Matrices

Modifications of BN-based coatings that are used as interfacial layers between the fibers and matrices of SiCfiber/SiC-matrix composite materials have been investigated to improve the thermomechanical properties of these materials. Such interfacial coating layers, which are also known as interphases (not to be confused with interphase in the biological sense), contribute to strength and fracture toughness of a fiber/matrix composite material by providing for limited amounts of fiber/matrix debonding and sliding to absorb some of the energy that would otherwise contribute to the propagation of cracks. Heretofore, the debonding and sliding have been of a type called inside debonding because they have taken place predominantly on the inside surfaces of the BN layers that is, at the interfaces between the SiC fibers and the interphases. The modifications cause the debonding and sliding to include more of a type, called outside debonding, that takes place at the outside surfaces of the BN layers that is, at the interfaces between the interphases and the matrix (see figure). One of the expected advantages of outside debonding is that unlike in inside debonding, the interphases would remain on the crack-bridging fibers. The interphases thus remaining should afford additional protection against oxidation at high temperature and should delay undesired fiber/fiber fusion and embrittlement of the composite material. A secondary benefit of outside debonding is that the interphase/matrix interfaces could be made more compliant than are the fiber/interphase interfaces, which necessarily incorporate the roughness of the SiC fibers. By properly engineering BN interphase layers to favor outside debonding, it should be possible, not only to delay embrittlement at intermediate temperatures, but also to reduce the effective interfacial shear strength and increase the failure strain and toughness of the composite material. Two techniques have been proposed and partially experimentally verified as candidate means to promote outside debonding in state-of-the-art SiC/SiC composites.

Morscher, Gregory N.↗

The Ductility of 49Fe-49Co-2V Soft Magnetic Alloy Bar: Surface Effects and Test Methods

The tensile ductility of 49Fe-49Co-2V (Hiperco® 50A) bar was investigated in both as-received and heat-treated conditions. The as-received/machined specimens exhibit very low ductility compared to samples where heat treatment was the final step prior to testing. Microstructural characterization showed that internal residual strain from bar processing and, most importantly, surface machining damage, cause lower elongation in the as-received material. Because fracture of this intermetallic alloy initiates at the surface, it is particularly susceptible to surface machining damage, i.e., the near-surface region has already exhausted most of its ability to accumulate tensile strain. During heat treatment, the internal residual strain and near-surface machining damage are eliminated and ductility is improved, despite a higher degree of crystallographic ordering in the heat-treated condition (which typically lowers ductility). Furthermore, if machining is again performed after heat treatment, the material again exhibits brittle behavior, even with only light touch-up machining passes. Here, in this work, methods of tensile strain measurement were investigated, namely conventional knife-edge extensometry and noncontact digital image correlation (DIC) on heat-treated material. For clip-on knife-edge extensometry, the range of failure strain was 2.5-5.5% for heat-treated Hiperco. For noncontact methods, ductility up to 7% was observed. The results highlight the tendency for the alloy to fail at surface imperfections, even those produced by application of the extensometer itself. Noncontact laser extensometry is recommended for determining the intrinsic ductility of the alloy. A method of laser surface modification was developed which increased ductility by ~ 100% compared to unmodified samples. The high cooling rates achieved during laser surface processing can bypass the ordering reaction and produce a ductile disordered structure at the surface that exhibits ductile fracture characteristics.

EBSD↗

Hi-Nicalon Fiber-Reinforced Celsian Matrix Composites: Influence of Interface Modification

Unidirectional celsian matrix composites having 42-45 vol % of uncoated or BN-SIC coated Hi-Nicalon fibers were tested in three-point bend at room temperature. The uncoated fiber-reinforced composites showed catastrophic failure with strength of 210 35 MPa and a flat fracture surface. In contrast, composites reinforced with coated fibers exhibited graceful failure with extensive fiber pullout. Values of first matrix cracking stress and strain were 435 +/- 35 MPa and 0.27 +/- 0.01%, respectively, with ultimate strength as high as 960 MPa. The elastic Young modulus of the uncoated and coated fiber-reinforced composites were 184 +/- 4 GPa and 165 +/- 5 GPa, respectively. Fiber push-through tests and microscopic examination indicated no chemical reaction at the uncoated or coated fiber-matrix interface. The low strength of composite with uncoated fibers is due to degradation of the fiber strength from mechanical damage during processing. Because both the coated- and uncoated-fiber-reinforced composites exhibited weak interfaces, the beneficial effect of the BN-SIC dual layer is primarily the protection of fibers from mechanical damage during processing.

Bansal, Narottam P.↗

Parametric Optimization of Nanostructured Alumina Forming Austenitic Alloys

Alumina-forming austenitic (AFA) alloys provide excellent oxidation resistance through the formation of a stable alumina scale, but their relatively high Ni content might limit application in core structural components because of helium generation and swelling under irradiation. Increasing the density of nanoscale features in the microstructure is a promising route to improve sink strength and mitigate these effects. Conventional oxide dispersion–strengthened (ODS) steels achieve this through mechanical alloying (MA), but the approach is costly and difficult to scale. In this milestone, additive manufacturing was applied as an alternative pathway to fabricate nanostructured AFA (NAFA) alloys with dual precipitation of oxides and nitrides enabled by reactive atmosphere processing. In FY25, two compositions, NAFA-1 (AFA-05) and NAFA-2, were produced and compared. Both alloys achieved densities above 99% of theoretical values, but NAFA-2 exhibited microcracking associated with Nb-rich intermetallic formation, indicating the need for further chemistry optimization. Nitrogen and oxygen uptake was confirmed on selected builds, demonstrating the intended dual-precipitate dispersion. Mechanical testing showed that AM-processed NAFA alloys exceed conventionally produced ODS steels in high-temperature tensile strength and fracture toughness. Preliminary Cu ion irradiation results further suggest improved resistance compared to wrought austenitic alloys. While the current alloys are promising for their compatibility in high-temperature air or liquid Pb environments, modifications to composition will be required for long-term operation in high-temperature impure sodium systems. Future work will focus on refining alloy chemistry to suppress laser powder bed fusion–induced cracking and scaling production to reactor-relevant dimensions using directed energy deposition as a pathway toward net-shape cladding fabrication.

36 MATERIALS SCIENCE↗

Microstructure and fracture in SiC whisker reinforced 2124 aluminum composite

The microstructures of extruded and hot-rolled 2124 Al-15 percent (by weight) SiC whisker composites have been investigated, experimentally. Among the specific factors studied were: the strength of the whisker-matrix interfaces; (2) the presence of oxides; (3) the presence of defective whiskers; (4) and the presence of distribution of intermetallic compounds, impurities in the SiC(w) powder, and microstructural inhomogeneities. Modifications in the microstructure of the SiC/AL composites due to hot rolling and extrusion are illustrated in a series of microphotographs. It was found that hot rolling along the axis of extrusion was associated with some types of whisker damage, while the whiskers still retain their original orientation. Hot-rolling perpendicular to the axis of extrusion, however, tended to rotate the whiskers and produced a nearly isotropic material. Whisker free zones were virtually eliminated or reduced in size by hot rolling. In situ Auger fractography of the composite showed that the interfacial bonding between the SiC and the Al matrix was good and that Al2O2 had no significant influence on the fracture mechanics of the composite.

Nieh, T. G.↗

Implementation and testing of physics-based pulverization model in BISON

This report summarizes lower length scale computational research conducted to improve the pulverization criterion for high-burnup UO 2 fuel in the BISON fuel performance code. This research was sponsored by the NEAMS program during FY22. Efforts to improve the model primarily focus on calculating the current pressure of bubbles in the high-burnup structure (HBS) region, as well as the critical bubble pressure at which pulverization occurs in the HBS. The phase-field model for predicting initial bubble pressure in the HBS was improved by implementing a more realistic model for defect production, and by coupling the phase-field model for inter-granular bubble evolution with the spatially-resolved cluster dynamics code Xolotl to simulate intra-granular fission gas evolution. An evolution equation for current bubble pressure was added to BISON, an improvement over the previous model that assumed that bubble pressure was static following HBS formation. To improve calculations of critical bubble pressure for pulverization, 3-D phase-field fracture simulations were performed, and a function for critical bubble pressure was fit—based on the simulation results—to replace the previous function, which had been determined using 2-D simulations. The impacts of these modifications to the existing pulverization assessment cases will be reported in the forthcoming engineering scale milestone on high-burnup UO 2 pulverization. A poromechanics-based approach was used to include the effect of bubble over pressurization on the stress state of the pellet at the engineering scale, and the initial strategy for integration of the pulverization criterion with pellet-scale mechanical degradation using a smeared cracking model was developed. This report also describes the initial research that was conducted to inform a forthcoming transient fission gas release (tFGR) model in BISON. Focusing on the fission gas release caused by pulverization of the outer pellet rim, a model for the amount of fission gas release was developed as a function of fuel porosity, bubble size, and fragment size. Implementation of this model in BISON and its impact of engineering-scale predictions will also be described in the aforementioned engineering-scale milestone on high-burnup UO 2 pulverization.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Floor-fractured craters on the moon and Mars

Impact craters on the moon provided primary pathways for volcanic eruptions through shock-induced fractures that immediately or subsequently tap magma reservoirs. Evidence for this process includes unbreached lava-filled craters and fractured crater floors with associated eruptives. Over 200 craters with floor fractures have been identified on the moon. They commonly occur along the margins of irregular maria, thereby suggesting a link to this important phase of lunar volcanism. Topographic data reveal small elevation differences between the summit of the remnant central peaks and crater rim, and in many cases suggest that floor fracturing resulted from a tabular intrusion localized beneath the crater with uplift of the crater floor. A comparison of lunar and Martian crater photographs shows that some Martian craters also exhibit similar highly localized endogenic modifications.

Schultz, P. H.↗

A Novel Hybrid Ultramicrotomy/FIB-SEM Technique: Preparation of Serial Electron-Transparent Thin Sections of a Hayabusa Grain

The Japanese space agency's (JAXA) Hayabusa mission returned the first particulate samples (typically <100micron) from the surface of an asteroid (25143 Itokawa). These precious samples provide important insights into early Solar System processes, but their sizes pose tremendous challenges to coordinated analysis using a variety of nano- and micro-beam techniques. The ability to glean maximal information from individual particles has become increasingly important and depends critically on sample preparation. We developed a hybrid technique combining traditional ultramicrotomy with focused ion beam (FIB) techniques, allowing for more thorough in situ investigations of grain surfaces and interiors. Using this method, we increase the number of FIB-prepared sections that can be recovered from a particle with dimensions on the order of tens of microns. These sections can be subsequently analyzed using a variety of analytical techniques. Particle RA-QD02-0211 is a approx. 40×40×20 micron particle from Itokawa containing olivine and Fe sulfides. It was embedded in low viscosity epoxy and partly sectioned to a depth of approx 10 micron; sections are placed on Cu grids with thin amorphous films for transmission electron microscope (TEM) analyses. With the sample surface partly exposed, the epoxy bullet is trimmed to a height of approx. 5mm to accommodate the allowable dimensions for FIB work (FEI Quanta 600 3D dual beam FIB-SEM). Using a diamond trim knife, the epoxy surrounding the grain is removed on 3 sides (to within a few microns of the grain); the depth of material removed extends well below the bottom of the particle. The sample is attached to an SEM pin mount, the epoxy coated with conductive paint, and the entire assembly coated with approx. 40nm of carbon to eliminate sample charging during FIB work. A protective carbon cap is placed according to the plan for the 15 FIB sections. The central 'spine' of the cap runs perpendicular to the front of the sample, and the 'ribs' protruding from either side run parallel. Each rib indicates the location of a planned FIB section, and the spine contains the final two planned sections. We use a cap with a 4 micron-wide spine and 2micron-wide ribs that have ≳3.5 micron of space between them (narrower cuts result in too much re-deposition of material inside the trenches). Using a 30kV, 3nA ion-beam we expose the front surface of the grain and commence milling trenches between sections. Rather than using the typical C-cut to prepare the sample for lift-out, an L-cut is used instead, leaving the sample connected by an interior tab. tab. Sections are lifted out, attached to TEM grids and thinned to electron transparency. TEM analyses show that our hybrid technique preserves both interior and edge features, including surface modifications from exposure to the space environment, such as damaged rims that form in response to solar wind implantation effects and adhering grains. In addition, the FIB sections provide larger areas that are free of fractures and chatter effects in comparison to the microtome thin sections, thus enabling more accurate measurements of solar flare particle track densities that are used to determine the surface exposure age of the particles.

Berger, Eve L.↗

Ages of fracturing and resurfacing in the Amenthes region, Mars

An attempt is made to determine whether there is any tectonic evidence in the relatively recent history of the boundary zone that will place contraints on the origin of the Martian dichotomy. It is found that the timing of resurfacing events and structural modification of outlier plateaus and mesas in the Martian eastern hemisphere provides a contraint on the history of tectonic events along the cratered terrain-northern plains boundary. The circumferential grabens surrounding the Isidis basin ceased forming before the final emplacement of ridged plains on the adjacent northern lowlands. The cratered plateau east of the Isidis basin includes two crater populations; stripping of the rims of craters was complete before downfalling of the transition zone between the cratered terrain and the northern plains, and a young population of craters on the plateau records the same age as the ridged plains units north of the boundary.

Maxwell, Ted A.↗

Durability and Damage Tolerance of High Temperature Polymeric Composites

Modern durability and damage tolerance predictions for composite material systems rely on accurate estimates of the local stress and material states for each of the constituents, as well as the manner in which the constituents interact. In this work, an number of approaches to estimating the stress states and interactions are developed. First, an elasticity solution is presented for the problem of a penny-shaped crack in an N-phase composite material system opened by a prescribed normal pressure. The stress state around such a crack is then used to estimate the stress concentrations due to adjacent fiber fractures in composite materials. The resulting stress concentrations are then used to estimate the tensile strength of the composite. The predicted results are compared with experimental values. In addition, a cumulative damage model for fatigue is presented. Modifications to the model are made to include the effects of variable amplitude loading. These modifications are based upon the use of remaining strength as a damage metric and the definition of an equivalent generalized time. The model is initially validated using results from the literature. Also, experimental data from APC-2 laminates and IM7/K3B laminates are used in the model. The use of such data for notched laminates requires the use of an effective hole size, which is calculated based upon strain distribution measurements. Measured remaining strengths after fatigue loading are compared with the predicted values for specimens fatigued at room temperature and 350 F (177 C).

Case, Scott W.↗

Modeling of Response of Thermoplastic Composites Under High Energy Impact

This work investigates the response of a thermoplastic panel under high energy ballistic impact. The composite material system is a carbon fiber reinforced low melt semi-crystalline resin TC1225 LMPAEK T700G (T700/LMPAEK3). Several high energy dynamic impact tests were performed where an aluminum projectile impacted various panels at different impact velocities. For this work, the test performed at an impact velocity of 73.2 m/s was investigated. The projectile rebounded upon impact, and the damage to the panel was characterized through ultrasonic and CT-scanning. Response of the panel under impact and the associated damage is discussed. Numerical simulation of the impact process was performed using the LS-DYNA® computer code [1] with a new material model MAT_COMPOSITE_DAMAGE_DGD (MAT 299), a modification over MAT 261 material model in terms of an improved representation of damage coupling and additional capability for strain rate effects. Delaminations were modeled using cohesive zone contact formulation in LS-DYNA®, wherein the mixed-mode fracture is captured via the Benzegaggh-Kenane (B-K) mode-dependent fracture energy interpolation law. Simulation of this impact test demonstrates a good match of results in terms of panel deflection and panel-projectile interactions. The overall extent of delaminations was under-predicted by the simulation. This work forms the basis to model tests performed at higher velocities, involving projectile penetration of panel.

Composite Materials↗

Changes in environmental and engineered conditions alter the plasma membrane lipidome of fractured shale bacteria

ABSTRACT Microorganisms that persist in fractured shale reservoirs cause several problems including secreting foul gases and forming biofilms. Current biocontrol measures often fail due to limited knowledge of their in situ activities. The plasma membrane protects the cell, mediates many of its critical functions, and responds to intracellular cues and ecological perturbations through physicochemical modifications. As such, it provides valuable insight into the physiological adaptation of microorganisms in disturbed environmental systems. Here, we (i) demonstrate how changes in salinity and hydraulic retention time (HRT) influence the plasma membrane intact polar lipid (IPL) chemistry of model bacterium, Halanaerobium congolense WG10, and mixed microbial consortia enriched from shale-produced fluids and (ii) elucidate adjustments in membrane IPL chemistry during biofilm growth relative to planktonic cells. We incubated H. congolense WG10 in chemostats under three salinities (7%, 13%, and 20% NaCl), operated under three HRTs (19.2, 24, and 48 h), and in drip flow biofilm reactors under the same salinity gradients. Also, mixed microbial consortia in produced fluids were enriched in triplicate chemostat vessels under three HRTs (19.2, 24, and 72 h) and biofilm reactors. Lipids were analyzed by ultra high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Our results show that phosphatidylglycerols, cardiolipins, and phosphatidylethanolamines were predominantly enriched in planktonic H. congolense WG10 cells grown at hypersalinity (20%) compared to optimum (13%). In addition, several zwitterionic phosphatidylcholines and phosphatidylethanolamines were higher in abundance during biofilm growth. These observations suggest that microbial adaptation and biofilm formation in fractured shale are enabled by strategic plasma membrane IPL chemistry adjustments. IMPORTANCE Microorganisms inadvertently introduced into the shale reservoir during fracturing face multiple stressors including brine-level salinities and starvation. However, some anaerobic halotolerant bacteria adapt and persist for long periods of time. They produce hydrogen sulfide, which sours the reservoir and corrodes engineering infrastructure. In addition, they form biofilms on rock matrices, which decrease shale permeability and clog fracture networks. These reduce well productivity and increase extraction costs. Under stress, microbes remodel their plasma membrane to optimize its roles in protection and mediating cellular processes such as signaling, transport, and energy metabolism. Hence, by observing changes in the membrane lipidome of model shale bacteria, Halanaerobium congolense WG10, and mixed consortia enriched from produced fluids under varying subsurface conditions and growth modes, we provide insight that advances our knowledge of the fractured shale biosystem. We also offer data-driven recommendations for improving biocontrol efficacy and the efficiency of energy recovery from unconventional formations.

03 NATURAL GAS↗

Methods for improving reliability in ceramic turbine rotors

Evaluation of Carborundum (CBO) injection-molded sintered alpha silicon carbide (SiC) AGT 100 gasifier turbine rotors by spin testing established a baseline for material strength characteristics. Spin test results of a subsequent group of rotors demonstrated a reduction in average failure speed. Post-test fracture analysis identified surface and near-surface flaws in the back face region to be the typical failure origins. Corrective actions were initiated to address the elimination of the strength controlling flaws. Initial evaluation of rotors fabricated to these process modifications indicates improvements in overall surface quality and average burst speed.

Turner, D. A.↗

Effects of Interface Modification on Mechanical Behavior of Hi-Nicalon Fiber-Reinforced Celsian Matrix Composites

Unidirectional celsian matrix composites having approx. 42 volume percent of uncoated or BN/SiC-coated Hi-Nicalon fibers were tested in three-point bend at room temperature. The uncoated fiber-reinforced composites showed catastrophic failure with strength of 210 +/- 35 MPa and a flat fracture surface. In contrast, composites reinforced with BN/SiC-coated fibers exhibited graceful failure with extensive fiber pullout. Values of first matrix cracking stress and strain were 435 +/- 35 MPa and 0.27 +/- 0.01 %, respectively, with ultimate strength as high as 960 MPa. The elastic Young's modulus of the uncoated and BN/SiC-coated fiber-reinforced composites were measured as 184 q 4 GPa and 165 +/- 5 GPa, respectively. Fiber push-through tests and microscopic examination indicated no chemical reaction at the uncoated or coated fiber-matrix interface. The low strength of the uncoated fiber-reinforced composite is probably due to degradation of the fibers from mechanical surface damage during processing. Because both the coated and uncoated fiber reinforced composites exhibited weak interfaces, the beneficial effect of the BN-SiC dual layer is primarily the protection of fibers from mechanical damage during processing.

Bansal, Narottam P.↗

Artificial Gravity: Will it Preserve Bone Health on Long-Duration Missions?

Prolonged microgravity exposure disrupts bone, muscle, and cardiovascular homeostasis, sensory-motor coordination, immune function, and behavioral performance. Bone loss, in particular, remains a serious impediment to the success of exploration-class missions by increasing the risks of bone fracture and renal stone formation for crew members. Current countermeasures, consisting primarily of resistive and aerobic exercise, have not yet proven fully successful for preventing bone loss during long-duration spaceflight. While other bone-specific countermeasures, such as pharmacological therapy and dietary modifications, are under consideration, countermeasure approaches that simultaneously address multiple physiologic systems may be more desirable for exploration-class missions, particularly if they can provide effective protection at reduced mission resource requirements (up-mass, power, crew time, etc). The most robust of the multi-system approaches under consideration, artificial gravity (AG), could prevent all of the microgravity-related physiological changes from occurring. The potential methods for realizing an artificial gravity countermeasure are reviewed, as well as selected animal and human studies evaluating the effects of artificial gravity on bone function. Future plans for the study of the multi-system effects of artificial gravity include a joint, cooperative international effort that will systematically seek an optimal prescription for intermittent AG to preserve bone, muscle, and cardiovascular function in human subjects deconditioned by 6 degree head-down-tilt-bed rest. It is concluded that AG has great promise as a multi-system countermeasure, but that further research is required to determine the appropriate parameters for implementation of such a countermeasure for exploration-class missions.

Davis-Street, Janis↗

Investigating Material Properties of Subsurface Rock Formations Modified by Engineering Mineral Precipitation (Final Scientific and Technical Report)

Montana State University’s (MSU) Energy Research Institute (ERI), in collaboration with the Center for Biofilm Engineering (CBE) and the Department of Civil Engineering (CE), has conducted a long‐term research program aimed at developing a novel cementing agent to address wellbore integrity and reduce the unwanted upward migration of fluids and greenhouse gases from the subsurface. The primary technology developed through this research program is known as ureolysis‐induced calcite precipitation (UICP), which harnesses bio‐chemical processes to precipitate calcium carbonate (CaCO 3 ). The same general process can also be called microbially-induced calcium carbonate precipitation (MICP) when microbes provide the process-catalyzing urease enzyme. Both terms are used in this report. Results have conclusively demonstrated that, if properly controlled, UICP can successfully seal fractures, high permeability zones, and compromised cement in the vicinity of wellbores and in nearby caprock. This technology has been successfully deployed to mitigate annular leakage in two test wells and over sixty commercial wells with a 100% success rate. This success in downhole deployment generates consideration of other subsurface applications where UICP could provide benefit to the energy sector, such as shale property modification for unconventional oil and gas recovery. The focus of this research project was to investigate fundamental material and mechanical properties of select shale cores and analyze how these properties change due to engineered mineral precipitation with the intent to control these properties to achieve a range of engineering objectives. Ultimately, the project aim was to identify valuable new areas where application of UICP might contribute to national energy security and environmental protection. The research workplan coupled UICP treatment of core samples, nuclear magnetic resonance (NMR) characterization, and mechanical strength testing at MSU with advanced X‐Ray micro-computed tomography (μCT) imaging and numerical modeling performed by collaborators at two national laboratories, the National Energy Technology Laboratory (NETL) and Lawrence Berkeley National Laboratory (LBNL). Experimental results are useful to inform geo-mechanical models which could be applied to predict mineralized rock formation behavior at field scale. Our findings suggest that NMR and μCT methods to detect and quantify biomineral formation in shale fractures are complementary and consistent with each other. Either could be used to estimate the volume of new mineral formed by UICP in shale fractures. The use of surfactants and guar gum to enhance biomineral precipitation in shale fractures merits further research. UICP can, under some conditions, increase the tensile strength of sealed shale fractures beyond that of the intact shale. These findings demonstrate that continued research in this area may be valuable to understanding and improving shale resource recovery techniques.

58 GEOSCIENCES↗

Dynamic development of geochemical reaction fronts during hydraulic stimulation of shale

Injection of acidic hydraulic fracture fluid (HFF) into shale formations for unconventional oil/gas production results in chemical reactions in the shale matrix that can alter fluid transport. Here, we report the results of set of experiments designed to evaluate the impact of calcite dissolution as a function of carbonate mineral content on matrix chemical reactivity and pore-space modification concomitant with imbibition. In this study, we tracked acidic HFF transport in four samples of Wolfcamp shale with calcite contents varying from 4% to 59% by monitoring the rate and spatial extent of bromide tracer transport using synchrotron-based X-ray fluorescence microprobe (XFM) imaging. Concurrently, we also carried out XFM imaging of the spatial distribution of Ca in the Wolfcamp shale cores (as a proxy of calcite distribution). Our approach thus yields a direct record of time-resolved selective ion transport resulting from the penetration of acidic HFF and the associated mineral transformations in the shale cores. We show that the variability in calcite content of Wolfcamp shale samples can directly affect the rate and spatial extent of imbibition. Although reaction of the acidic HFF with carbonates in shales enhances calcite dissolution and increases porosity, the spatial extent of calcite dissolution in the shale matrix is limited due to a rapid neutralization of pH. The relative abundance and spatial distribution of calcite control the chemical saturation state of the HFF progressing into the matrix. As a result, calcite has a major impact on the spatial extent and rate of matrix alteration and thus on HFF transport during subsurface reservoir stimulation. Consequently, increased calcite content in the shale matrix inhibits the spatial extent of the pore-volume increase and, by extension, the spatial extent and rate of imbibition. Our results thus show that the overall rates of calcite dissolution approach the rates of acidic HFF transport (i.e., Damköhler number ~1), which could contribute to the efficiency of subsurface reservoir stimulation. A better understanding of HFF-calcite reaction rates is crucial for improving the prediction and optimization of fluid transport across HFF-shale interfaces during hydraulic fracturing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Kasei Vallis of Mars: Dating the Interplay of Tectonics and Geomorphology

Crater density age dates on more than 250 small geomorphic surfaces in the Kasei Region of Mars show clusterings indicative of times of peak geomorphic and tectonic activity. Kasei Vallis is part of a 300 km wide channel system breaching a N-S trending ancient basement high (+50,000 crater age) separating the Chryse Basin from the Tharsis Volcanic Province of Mars. The basement high was covered by a least 3 groups of probable volcanic deposits. Major regional fracturing took place at age 4,000 to 5,000 and was immediately followed by deposition of regional volcanics of the Fesenkov Plains (age 3,000 to 4,200). Younger clusterings of dates in the 900 to 1,500 and 500 to 700 range represent only minor modification of the basic tectonic geomorphic landform. The data suggest that Kasei gap is a structurally controlled breach of a buried ridge by a rather brief episode of fluvial activity.

Wise, D. U.↗