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At least 397 records · Page 22
All sourcesNASA NTRSDOE OSTI
NASA NTRS2002

Preparation and Characterization of Polyimide Nanocomposites

Many properties of polymeric materials can be enhanced by dispersing small quantities of clay nanocomposites throughout the polymer. Among the enhancements are increases in modulus and resistance to erosion by atomic oxygen and reductions in thermal expansivity, gas permeability, and flammability. To achieve the full extent of enhancement with these polymer-clay nanocomposites, the clay nanoparticles, which have thicknesses of only one-to-several nanometers and lengths and widths of hundreds of nanometers to micrometers, must be exfoliated one from another and then individually dispersed throughout the polymer. This dispersion is achieved only after alkali metal cations (usually Na(+)) that reside on the surfaces of the nanoparticles have been replaced by organocations (typically a quaternary amine cation). This renders the surface of the nanoparticle a more hospitable interface for the organic polymer matrix. Following the cation exchange, the organic clay is either mixed directly into the polymer or is dispersed in monomer which is later polymerized around the nanoparticle.

Orwoll, Robert A.↗
NASA NTRS1991

Air oxidation of hydrazine. 1. Reaction kinetics on natural kaolinites, halloysites, and model substituent layers with varying iron and titanium oxide and O- center contents

Air oxidation of hydrazine was studied by using a group of kaolinites, halloysites, and substituent oxides as models for the tetrahedral and octahedral sheets. The rate was found to be linear with oxygen. The stoichiometry showed that oxygen was the primary oxidant and that dinitrogen was the only important nitrogen-containing product. The rates on kaolinites were strongly inhibited by water. Those on three-dimensional silica and gibbsite appeared not to be. That on a supposedly layered silica formed from a natural kaolinite by acid leaching showed transitional behavior--slowed relative to that expected from a second-order reaction relative to that on the gibbsite and silica but faster than those on the kaolinites. The most striking result of the reaction was the marked increase in the rate of reaction of a constant amount of hydrazine as the amount of clay was increased. The increase was apparent (in spite of the water inhibition at high conversions) over a 2 order of magnitude variation of the clay weight. The weight dependence was taken to indicate that the role of the clay is very important, that the number of reactive centers is very small, or that they may be deactivated over the course of the reaction. In contrast to the strong dependence on overall amount of clay, the variation of amounts of putative oxidizing centers, such as structural Fe(III), admixed TiO2 or Fe2O3, or O- centers, did not result in alteration of the rate commensurate with the degree of variation of the entity in question. Surface iron does play some role, however, as samples that were pretreated with a reducing agent were less active as catalysts than the parent material. These results were taken to indicate either that the various centers interact to such a degree that they cannot be considered independently or that the reaction might proceed by way of surface complexation, rather than single electron transfers.

NASA Discipline Number 52-20↗
NASA NTRS2003

Organic/Inorganic Hybrid Polymer/Clay Nanocomposites

A novel class of polymer/clay nanocomposites has been invented in an attempt to develop transparent, lightweight, durable materials for a variety of aerospace applications. As their name suggests, polymer/ clay nanocomposites comprise organic/ inorganic hybrid polymer matrices containing platelet-shaped clay particles that have sizes of the order of a few nanometers thick and several hundred nanometers long. Partly because of their high aspect ratios and high surface areas, the clay particles, if properly dispersed in the polymer matrix at a loading level of 1 to 5 weight percent, impart unique combinations of physical and chemical properties that make these nanocomposites attractive for making films and coatings for a variety of industrial applications. Relative to the unmodified polymer, the polymer/ clay nanocomposites may exhibit improvements in strength, modulus, and toughness; tear, radiation, and fire resistance; and lower thermal expansion and permeability to gases while retaining a high degree of optical transparency.

Park, Cheol↗
DOE OSTI2020

Layer size polydispersity in hydrated montmorillonite creates multiscale porosity networks

The aluminosilicate layers of the swelling clay mineral montmorillonite, and the saturated pores they delineate, control the mechanical properties and the transport of solutes in many natural and engineered environments. However, the structural basis of montmorillonite porosity remains poorly characterized due to the difficulty in visualizing hydrated samples in their native state. Here in this paper, we used cryogenic transmission electron microscopy (cryo-TEM) and cryo electron tomography (cryo-ET) to show that stacking defects within minimally altered, fully hydrated montmorillonite particles define multiscale porosity networks. Variations in layer lateral dimensions over tens to thousands of nanometers cause a range of topological and dynamic defects that generate pervasive curvature and introduce previously uncharacterized solute transport pathways. Observations of long-range rotational order between neighboring layers indicate that the layer-layer interactions that govern clay swelling involve three dimensional orienting forces that operate across nanoscale pores. These direct observations of the hierarchical structure of hydrated montmorillonite pore networks with nanoscale resolution reveal potentially general aspects of colloidal interactions in fluid-saturated clay minerals.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Illitization in the Mt. Simon Sandstone, Illinois Basin, USA: Implications for carbon dioxide storage

Clay mineral cementation is one of the most important controls on sandstone reservoir properties. Here, in this paper, the diagenetic history of the Mt. Simon reservoir complex is studied to reveal the origin, timing, and controls of illitization. Samples of sandstone and shale from Mt. Simon reservoir complex were acquired from the Illinois Basin–Decatur Project (IBDP), a CO 2 storage demonstration project in the central Illinois Basin. Petrographic, SEM, TEM, XRD analyses and K/Ar age dating were completed to identify the major detrital and diagenetic components of the samples and reveal illite to be the major clay component in all samples. Illitic clay coatings in the lower Mt. Simon reservoir are identified as a major control on reservoir properties by inhibiting major precipitation of authigenic quartz during illitization, resulting in highly permeable sandstone, essential for CO 2 storage. The coating box-work morphology and mineralogy are indicative of a detrital smectite origin with subsequent illite growth associated with feldspar dissolution and kaolinite alteration. The mineralogy of bulk material and separate grain size fractions (2–0.6 μm; 0.6–0.2 μm; < 0.2 μm) with illite polytypes 2M 1 , 1M, and 1M d were quantified and age dated via 40 K- 40 Ar methods. The shales or reservoir seals contain the highest proportions of detrital illite with illite in the lower Mt. Simon Sandstone reservoir identified as solely diagenetic. Two major events of illitization are identified throughout the Mt. Simon with more porous reservoir rock exhibiting the older event from approximately 360 to 315 Ma and tighter sandstone units with reservoir properties too low to be considered reservoir exhibiting illite dates from 250 to 220 Ma. This partitioning of illitization is attributed to varied mineralogy controlled by depositional changes and evolution of the greater basin.

58 GEOSCIENCES↗
DOE OSTI2021

Molecular Determination of Organic Adsorption Sites on Smectite during Fe Redox Processes Using ToF-SIMS Analysis

Turnover of soil organic carbon (SOC) is strongly affected by a balance between mineral protection and microbial degradation. However, the mechanisms controlling the heterogeneous and preferential adsorption of different types of SOC remain elusive, especially for humic substrates (HSs) and microbial carbon (MC), two hotly-debated forms of SOC prevalent in soils. In this work, the heterogeneous adsorption of HSs and MC on a clay mineral (nontronite NAu-2) during microbial-mediated Fe redox cycling was determined with the use of time-of-flight secondary ion mass spectrometry (ToF-SIMS). The results revealed that HSs pre-adsorbed on NAu-2 would partially inhibit the microbial Fe(III) reduction and structural modification of NAu-2, thus retarding the subsequent adsorption of MC. In contrast, NAu-2 without pre-coated HSs was adsorbed by a significant amount of MC from microbial polysaccharides as a result of Fe(III) reduction. This was attributed to the deposition of a thin Al-rich layer on clay surface, which provided active sites for MC adsorption. This study provides direct and detailed molecular evidence for the first time to explain the preferential adsorption of MC over HSs on the surface of clay minerals in the iron redox processes, which could be critical for the preservation of MC in soil. The results also indicate that ToF-SIMS is a unique tool for understanding complex organic-mineral-microbe interactions.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2026

Dynamic Evaluation of the Upper Tyler Formation and Well Stimulation Fluid Interactions Using Micro-CT Imaging

Abundant concentrations of swelling clays in the oil-bearing upper Tyler Formation inhibit unconventional well stimulation techniques and associated long-term oil and gas production success. Laboratory evaluation of the geochemical interactions between the formation material and various stimulation fluids may help identify innovative approaches that provide a solution to successful well stimulation and subsequent oil production. The objective of this research was to understand the complexities of well stimulation fluid and clay mineral interactions within the Tyler Formation and identify potential fracturing fluid formulations that mitigate swelling properties of the clays in the reservoir to enhance stimulation success and promote long-term oil and gas production. Collaboration with the National Energy Technology Laboratory (NETL), utilizing their Tescan DynaTOM micro-CT analysis instrumentation, provided an innovative approach to understand real-time, dynamic interactions of the formation material and various potential stimulation fluids. Results are anticipated to identify key mechanisms occurring at the micro-scale level and provide insight into modified stimulation techniques uniquely suited for successful production applications.

enhanced oil recovery↗
DOE OSTI2020

An anisotropic viscoplasticity model for shale based on layered microstructure homogenization

Viscoplastic deformation of shale is frequently observed in many subsurface applications. Many studies have suggested that this viscoplastic behavior is anisotropic—specifically, transversely isotropic—and closely linked to the layered composite structure at the microscale. In this work, we develop a two-scale constitutive model for shale in which anisotropic viscoplastic behavior naturally emerges from semianalytical homogenization of a bilayer microstructure. The microstructure is modeled as a composite of soft layers, representing a ductile matrix formed by clay and organics, and hard layers, corresponding to a brittle matrix composed of stiff minerals. This layered microstructure renders the macroscopic behavior anisotropic, even when the individual layers are modeled with isotropic constitutive laws. Using a common correlation between clay and organic content and magnitude of creep, we apply a viscoplastic modified Cam-Clay plasticity model to the soft layers, while treating the hard layers as a linear elastic material to minimize the number of calibration parameters. We then describe the implementation of the proposed model in a standard material update subroutine. The model is validated with laboratory creep data on samples from three gas shale formations. We also demonstrate the computational behavior of the proposed model through simulation of time-dependent borehole closure in a shale formation with different bedding plane directions.

58 GEOSCIENCES↗
DOE OSTI2023

The role of oak species in long-term soil P loss in a humid river bottomland

There is a gap in our understanding of if and how bottomland forest type will affect long-term nutrient cycling and loss. This study aims to determine how different forests affect soil hydrologic variability and whole-soil P loss in a humid-subtropical setting. Here, we used replicate-sampling and measured soil physical, chemical, and mineralogical properties at 12 sites in two forest ecosystems, post oak (Quercus stellata) and cherry bark oak (Quercus pagoda) in Clarks River National Wildlife Refuge in Western Kentucky. We hypothesize that wetting–drying events in redox soils of forested bottomlands can cause positive feedback in whole-soil P loss. Trees with greater P demand (e.g., post oak) take up more water creating more frequent and pronounced episodes in swelling and shrinking of expandable clays. Repeated swelling and shrinking of clays occlude the surface of Fe-Mn oxides from further adsorption of P in acidic soil. This can lead to greater loss or plant uptake of available P. Our results show (i) a significant difference in mean whole-soil P loss between the oak species with more loss in soils underlying the post oak forest, and (ii) a difference in the total P found in the sap- and heartwood of the two oak species. Soil analysis reveals that the clay mineralogy of the post and cherry bark oak sites are similar, and thus, may only play a minor role in governing the whole-soil P loss difference. However, the leaf data analysis suggests that the post oak site could be P and nitrogen-limited, while the cherry bark is only nitrogen limited. Our study shows that differences in the oak forest ecosystem may affect the long-term balance in water and nutrient uptake and may alter the redistribution of nutrients in the canopy and the underlying soils.

58 GEOSCIENCES↗
DOE OSTI2023

New coal char-based bricks: Effects of curing temperature, humidity, pressing pressure, and addition of superplasticizer on the physical, mechanical, and thermal properties

Coal char, as a sustainable and eco-friendly material, holds significant potential for use in new construction materials, specifically, coal char-based bricks. This study employed the pre-pressing method to create char bricks containing high char content of 70%. The impact of various curing temperatures (20, 40, 60 °C), humidity levels (15% and 90%), and pressing pressures (3.5, 7, and 10 MPa) on the density, X-ray diffraction, compressive strength, and thermal conductivity of char-based samples were examined. The addition of superplasticizer and the performance of char bricks were assessed by comparing them to traditional clay bricks and corresponding standards. The study discovers that the temperature of 40 °C enhances the early 7-day strength of char brick samples, while the highest 28-day strength is observed in char bricks at a temperature of 20 °C and humidity of 90%. Compared to conventional clay bricks (with density of 1.9 g/cm3, thermal conductivity of 0.39-0.63 W/mK, compressive strength of 10-20 MPa), the proposed char bricks exhibit lower density (~0.8 g/cm 3 ), lower thermal conductivity (0.26-0.35 W/mK), and good performance in compressive strength (up to 15 MPa). Lastly, coal char-based bricks with high char content demonstrate significant advantages over traditional clay bricks, making them a sustainable and environmentally friendly building material option.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Dissolution and reprecipitation of amorphous silica in silica Rich shales induces Non-Monotonic evolution of porosity in acidic reactive environments

Advances in sustainable subsurface energy technologies are crucial for meeting our energy and resource needs for a climate-resilient future. Novel strategies to harness subsurface shale reservoirs for recovering valuable metals and for enabling CO 2 storage are influenced by the morphological and mineralogical heterogeneities of these materials. In this context, delineating the interactions of highly acidic solutions such as wet supercritical CO 2 on shales with varying mineralogy is crucial to inform the stability of caprock seal for CO 2 storage and enhancements in permeability for fluid transport, reactivity, and storage. The feedback chemical effects associated with the interactions of acidic solutions on the morphologies and mineralogies of shales have not been extensively investigated. These insights are crucial for assessing temporal changes in the reactivity and the fate of the fluids in subsurface environments. In this study, we investigate the effect of 1M HCl solution on the chemistry and morphology of three different shale samples with varying carbonate, clay and silica contents. An increase in the amorphous content, from 37% to 41.3%, of silica-rich and carbonate/clay lean shale is noted due to reactions with an acidic solution which is attributed to the dissolution of Si-bearing phases such as clays, accompanied by SiO 2 precipitation. In shales bearing high content of clays and carbonates, significant increase in the pore volumes and surface areas are noted. Non-monotonic changes in the micron-scale porosity of silica rich–carbonate/clay lean (e.g., Mowry shale) are noted using in-situ X-ray microtomography experiments. Due to the initial mobilization of silica and dissolution of carbonate/clay phases, the total porosity slightly increases from 6.7% to 10.7% followed by a decrease to similar to 4% caused by SiO 2 reprecipitation. In conclusion, these findings suggest that even though silica is less reactive in acidic environments, the changes in the amorphous and crystalline content due to dissolution and reprecipitation alter the porosity and fluid flow paths.

04 OIL SHALES AND TAR SANDS↗
DOE OSTI2025

Unravelling the origins of shale nanoporosity using small-angle neutron scattering (SANS)

Hydrocarbon production from tight rocks is constrained by slow diffusion within the shale matrix, limited by small pore sizes and low permeability. The nanopore proportion and size distribution significantly influence matrix permeability, a key property for optimizing hydrocarbon recovery and supporting hydrogen production while minimizing environmental impacts. Small-angle neutron scattering (SANS) has been an important tool for exploring the characteristics and structure of shale nanopores. This study used SANS to analyze nanoporosity and pore size distribution (<100 nm) in tight rocks with varying compositions to determine the influence of rock heterogeneity on SANS measurements. Results showed that nanoporosity correlates with clay content, with the highest clay-rich shale (52.48 wt% clay) exhibiting 8.8 % nanoporosity. SANS also revealed more nanopores than traditional nitrogen adsorption measurements, affirming its ability to reflect bulk mineralogy and upholding the relevance of experimental findings using this technique to optimize field operational approaches.

03 NATURAL GAS↗
DOE OSTI2023

Oxidation rates and redox stabilization of ferrous iron in trioctahedral smectites

Iron(II)-bearing trioctahedral smectites (saponites) form during anoxic alteration of basaltic rock. They are predicted to have been widespread on the early Earth and are observed in the oceanic subsurface today. Smectite structures, including the occupancy of sites in the octahedral sheet, affect iron redox behavior but the rates and products of trioctahedral smectite oxidation have been largely unexplored to date. In this study we synthesized two Fe(II)-bearing trioctahedral smectites, one moderate (22 wt% Fe) and one high (27 wt% Fe) in iron content. We then examined the rate, extent, and products of their oxidation by dissolved oxygen, nitrite, and hydrogen peroxide. Dissolved oxygen caused partial oxidation of Fe(II) in the smectites with 14 to 43% of Fe(II) unoxidized after 20 to 30 days of exposure. The rate and extent of oxidation correlated with the dissolved oxygen concentration and the Fe(II) content of the clay. The incomplete oxidation in these experiments is consistent with the mixed-valent trioctahedral smectites observed in oxidized natural samples but contrasts with the complete reoxidation by oxygen shown by chemically- or microbially-reduced dioctahedral smectites. Oxidation of structural Fe(II) by 5 mmol L -1 nitrite was negligible for the moderate-iron smectite and yielded only ~17% oxidation after 54 days of reaction for the high-iron smectite. Hydrogen peroxide caused rapid and near-complete oxidation of both clays. Powder X-ray diffraction, variable-temperature Mössbauer spectroscopy, and extended X-ray absorption fine structure spectroscopy together detected no crystalline or short-range-ordered secondary phases and show that oxidized iron remained in the trioctahedral smectite structure. The recalcitrant Fe(II) pool in oxidized trioctahedral smectites exists in less distorted sites than Fe(II) in the initial clays. Its unreactive nature at prolonged reaction times indicates an elevated redox potential generated by the local coordination environment. Slower oxidation rates create a larger recalcitrant Fe(II) pool, suggesting kinetic competition between oxidation and a process involved in redox stabilization, such as electron exchange between octahedral iron sites or deprotonation of hydroxyl groups in the structure. The resistance to complete oxidation of trioctahedral ferrous smectites and their full retention of iron demonstrates that transitions from anoxic to oxic conditions generate mixed-valence smectites rather than a mixture of new phases. Identifying the diagenetic products of mixed-valent trioctahedral smectites may provide an indicator in the rock record of past redox cycling. In conclusion, substantial portions of structural Fe(II) in trioctahedral smectites display slow abiotic oxidation kinetics and represent potential electron donors for both microaerophilic iron oxidizing and nitrate-reducing, iron-oxidizing microorganisms in altered mafic rocks and related settings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Effect of pore fluid chemistry on the mechanical behavior of a divalent compacted bentonite, an experimental and constitutive study

Ongoing research in isolating high-level nuclear waste and spent fuel has highlighted compacted bentonite as a suitable material for engineered barrier systems in deep geological repositories due to its extraordinary swelling and retention properties. This research focuses on the chemo-mechanical behavior of compacted bentonite exposed to different pore fluids with different concentrations and loading conditions. The study involves swelling pressure and compressibility experiments along with mineralogy analysis employing X-ray diffraction (XRD) and Cation exchange. The tests were conducted on BCV (a Mg/Ca- bentonite) compacted at a dry density of 1.48 ± .02 Mg/m 3 . An advanced chemical-mechanical constitutive model for unsaturated highly expansive clays was adopted to simulate the material response and better understand its behavior. The model is able to account for the main phenomena at both macro and microstructural levels and the interactions between them. The model successfully replicated experimental observations. The XRD analyses support the macroscopic observation, indicating that salinity impacts crystalline swelling as demonstrated by the reduction of basal spacing from 19.27 Å to 15.68 Å when the osmotic suction increases from 0 MPa to 33 MPa. The results suggested that the osmotic pressure generated by the concentration in the pore fluids promotes a reduction in swelling pressures, swelling strains, and crystalline swelling of clay minerals. Also, it affects the pre-consolidation stress and the compressibility of the compacted samples. In conclusion, it was also observed that both solution type and solution concentration impact the clay swelling pressure.

Chemo-mechanical constitutive model↗
DOE OSTI2023

Measured CO 2 sorption isotherms with 25 Bakken Petroleum System rock samples from the Lower and Upper Shales, Middle Bakken, and Three Forks formations

Isotherms were measured with 25 Bakken Petroleum System (BPS) rock samples using a magnetic suspension balance at reservoir conditions of 110 °C and pressures up to 345 bar. Samples from four wells represented the Middle Bakken (MB) and Three Forks (TF) production zones, and the Upper Bakken Shale (UBS) and Lower Bakken Shale (LBS) source shales. UBS and LBS CO 2 sorption capacities at 345 bar averaged 12–14 g/kg rock compared to 1.3 to 2.5 g/kg rock for MB and TF. Increasing pressure from 150 to 345 bar resulted in only small increases in CO 2 sorption for all lithofacies. For the UBS and LBS source shales, the higher average total organic carbon (TOC) values (14.7 and 11.4 wt.%) and clay values (25 and 28 wt.%) corresponded to their higher CO 2 sorption values while for the MB and TF samples, lower TOCs (0.3 and 0.5 wt.%) and clay values (8.2 and 18.2 wt.%) corresponded to lower CO 2 sorption values. Here, when all 25 samples (from all lithofacies) were evaluated as a group, sorption capacities were highly correlated with TOC (Spearman's rho values +0.84 to +0.85), with rock density (rho values -0.75 to -0.76), and clay content (rho values +0.66). However, correlations with porosity and thermal maturity (Tmax) were weak. Measured sorption capacities and rock porosities showed that sorption accounted for about 10-times as much CO 2 storage as the available pore space for the UBS and LBS lithofacies. In contrast, the pore space dominated the storage resource of the TF and MB lithofacies.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Predicting zeolites’ stability during the corrosion of nuclear waste immobilization glasses: Comparison with glass corrosion experiments

During the long-term corrosion of nuclear waste glasses under nuclear waste disposal conditions, the precipitation of zeolitic phases has been linked to a delayed acceleration in glass corrosion (known as “Stage III”). Hence, predicting the thermodynamic propensity for zeolites to form upon the dissolution of nuclear waste glasses is key to ensure their long-term performance. Here, we compile a unified, internally-consistent thermodynamic database “clay20” to estimate the stability of clay and feldspar phases relevant to nuclear waste immobilization glasses, including beidellite(Mg, Ca, Na, K), kaolinite, montmorillonite(Mg, Ca, Na, K), nontronite(Mg, Ca, Na, K), saponite(Ca, Na, K), and albite. Based on this, we report a geochemical modeling method allowing us to predict the stability of secondary phases (including zeolites, calcium–silicate–hydrate gels, and clays) upon the dissolution of nuclear waste immobilization glasses. We show that this approach offers a realistic description of the stability of the secondary phases forming during the dissolution of two archetypical model nuclear glasses (namely, the International Simple Glass, ISG, and WVUTh-203) under conditions relevant to nuclear waste disposal (T = 90°C, p = 1 bar) as a function of pH. We find that the formation of silica and clay secondary phases is thermodynamically favored at low pH (pH < 10), whereas, in contrast, zeolite (analcime) and calcium–silicate–hydrate phases are favored at high pH (pH > 10.5). This suggests that thermodynamics (i.e., not solely kinetics) plays a key role in determining the range of solution pH wherein stage III corrosion may occur, i.e., when zeolite formation is favored.

Zhen-Wu, Bi Yun↗
DOE OSTI2022

Integrated Experimental and Modeling Study of Geochemical Reactions of Simple Fracturing Fluids with Caney Shale

Interactions between rock minerals and hydraulic fluids directly impact the geochemical and geomechanical properties of shale formations. However, the mechanisms of geochemical reactions in shale unconventional reservoirs remain poorly understood. Here, to investigate the geochemical reactions between shale and hydraulic fracturing fluids, a series of batch reactor experiments were undertaken. Three rock samples with different mineralogical compositions and three fluid samples of different compositions (deionized water, deionized water + 2% potassium chloride (KCl), and deionized water + 0.5% choline chloride (C 5 H 14 ClNO) were used. Experiments were undertaken at reservoir temperature and atmospheric pressure. Elemental compositions of effluents after 1, 3, 7, 14, 28 days were analyzed using Inductively Couple Plasma Mass Spectrometry (ICP-MS). Medical Computed Tomography (CT) scan and X-ray Fluorescence (XRF) were conducted on the entire core run to help upscale results obtained from rock-fluid interaction experiments. Geochemical modeling using a reactive simulator, TOUGHREACT, was undertaken to corroborate experimental results. Results show that lower pH triggered high dissolution rates in the rock samples, especially the carbonate components. As pH increased, the rate of dissolution declined significantly, though for most cases dissolution still continued. Observed dissolved silica concentrations were much higher than the quartz solubility, suggesting that much of the silica originates from more soluble silica polymorphs and possibly desorption from clay mineral exchange sites. Concentration of most elemental species in solution increased but aluminium and magnesium concentrations declined rapidly following initial entry into solution. Geochemical modeling corroborated the conclusions regarding mineral dissolution and precipitation observed from experiments, notably; the dissolution of calcite and oxidation of pyrite in reacted shale samples, the likely presence of silica polymorphs such as opal, chalcedony or amorphous silica in these samples, and the reduction of Al and Mg concentrations in solution by precipitation of secondary aluminosilicate phases. The de-flocculation of clay minerals during reaction implies fines migration after hydraulic fracturing. This is detrimental to reservoir productivity as clay fines are displaces and lodged within the micro and nano-fractures created during fracturing. The immediate consumption of aluminium and magnesium also has implications on blockage of hydrocarbon pathways due to precipitation of new minerals in these locations.

04 OIL SHALES AND TAR SANDS↗
DOE OSTI2021

Role of Mineralogy in Controlling Fracture Formation

The presence of fractures in caprocks can pose increased risks in subsurface energy systems and processes like CO 2 sequestration by introducing high-permeability leakage paths. Fracture apertures and permeability can be altered through mineral dissolution and precipitation reactions, but the reactive evolution of fractures is not well understood. In fractures, minerals that are otherwise inaccessible to reactive fluids can become exposed, resulting in mineral reactions unpredicted by bulk formation data. This work seeks to understand the relationship between mineralogy and fracture formation to enhance our understanding of reactive fracture evolution and CO 2 leakage potential. Here, the mineral compositions of mechanically induced fracture surfaces in samples of the Mancos and Marcellus shales have been quantified and compared to those of the near-fracture matrices using imaging and bulk X-ray diffraction (XRD) data. In the Mancos shale, the concentrations of clay minerals are enhanced along fracture surfaces with respect to the bulk, and the fracture is most likely to form at kaolinite–kaolinite interfaces. Further, evaluation of the mineralogical spatial variability through cross-correlation analysis of the surrounding matrix in images of samples cut perpendicular to the fracture shows that clay is 16.7 times more likely to be present than carbonate minerals near the fracture surface. The high correlation persists roughly 200 μm into the surrounding matrix for the Mancos sample and implies that the fracture formed within a defined clay-rich lithofacies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗