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All sourcesNASA NTRSDOE OSTI
NASA NTRS2018

Coupled Thermomechanical Micromechanics Modeling of the Influence of Thermally Grown Oxide Layer in an Environmental Barrier Coating System

Environmental Barrier Coatings (EBCs) have emerged as a promising means of protecting critical components for high temperature applications (e.g., aircraft engines). EBCs are often used to protect an underlying material (substrate) from extreme thermal/chemical environments. However, systems that utilize EBCs are susceptible to a number of failure modes including oxidation/delamination. Environmental Barrier Coatings (EBCs) have emerged as a promising means of protecting silicon based ceramic matrix composite (CMC) components for high temperature applications (e.g., aircraft engines). EBCs are often used to protect an underlying material (substrate) such as silicon carbide from extreme thermal/chemical environments. In a typical CMC/EBC system, an EBC may or may not be adhered to an underlying substrate with a bond coat (e.g., silicon). Irrespective, systems that utilize EBCs are susceptible to a number of failure modes including oxidation/delamination, recession, chemical attack and dissolution, thermo-mechanical degradation, erosion, and foreign object damage. Current work at NASA Glenn Research Center is aimed at addressing these failure modes in EBC systems and developing robust analysis tools to aid in the design process. The Higher-Order Theory for Functionally Graded Materials (HOTFGM), a precursor to the High-Fidelity Generalized Method of Cells micromechanics approach, was developed to investigate the coupled thermo-mechanical behavior of functionally graded composites and will be used herein to assess the development and growth of a low-stiffness thermally grown oxide (TGO) layer in EBC/CMC systems without a silicon bond coat. To accomplish this a sensitivity study is conducted to examine the influence of uniformly and non-uniformly grown oxide layer on the associated driving forces leading to mechanical failure (spallation) of EBC layer when subjected to isothermal loading, recession, chemical attack and dissolution, thermomechanical degradation, erosion, and foreign object damage. Current work at NASA Glenn Research Center is aimed at addressing these failure modes in EBC systems and developing robust analysis tools to aid in the design process. The Higher-Order Theory for Functionally Graded Materials (HOTFGM), a precursor to the High-Fidelity Generalized Method of Cells micromechanics approach, was developed to investigate the coupled thermo-mechanical behavior of functionally graded composites (Aboudi et al., 1999, Composites B). For example, HOTFGM was previously used (Arnold et al, 1995, NASA CP 10178, paper 34), to assess interlaminar stresses (including free edge effects) in a substrate with a thermal barrier coating (TBC). In this study, HOTFGM micromechanics analyses will be used to assess the development and growth of a low-stiffness thermally grown oxide (TGO) layer between a silicon carbide substrate and a ytterbium disilicate EBC. In order to realistically simulate TGO growth, an evolution law will be incorporated into HOTFGM. In addition, the effect of TGO roughness will be explored consistent with previous TBC work (Pindera et al., 2000. Material Science and Engineering, A284, pp. 158-175). This model represents a first step in developing a robust analysis tool that can ultimately be used to design durable EBC systems. Additional failure modes will be considered as part of a future work.

environmental barrier coating↗
NASA NTRSDate not supplied

Solid-state battery designed for electric aviation

The demand for higher energy density batteries increases as the demand for portable electronic devices and electric automotive increases, as well as a variety of other applications requiring substantially higher power and energy than attainable with current lithium-ion capabilities which includes the areas of high performance vehicles, military applications, and electric aviation. However, the improvement of energy density is insufficient alone for enabling electric aviation when considering the high flammability and risk of thermal runaway inherent in current state-of-the-art liquid electrolytes. The development of high energy, high power, and safe batteries are required to enable hybrid and fully electric aircraft. Next generation chemistries such as lithium-sulfur provide high theoretical specific energy density suitable for electric aviation without as strict of volumetric requirements observed in the automotive industry. However, due to the phase transition during discharge where sulfur generates a series of soluble intermediate polysulfides, which are lost to the liquid electrolyte, cause detrimental side effects, and severely limit cycle life battery performance is severely reduced. Additionally, the low electrical conductivity of sulfur requires a large amount of inactive carbon dramatically increasing parasitic mass. The dissolution issue make sulfur a desirable candidate to pair with a solid-state electrolyte in order to avoid polysulfide dissolution and shuttling. In addition, inorganic solid-electrolytes have low flammability providing the improved safety required. Combining this chemistry with a solid-state electrolyte provides a path for achieving the energy and safety required for electric aviation. The development of scalable thin solid-state electrolytes paired with lithium-sulfur chemistry will be discussed and how their development will aid in enabling a unique application.

Donald A. Dornbusch↗
NASA NTRSDate not supplied

Assessing Organic Preservation and the Implications for Potential Biosignatures in the Bastide Member of the Séítah Formation, Jezero Crater

Introduction: Olivine has the highest CO2 trapping potential of ultramafic minerals, due to its rapid rate of dissolution and high percentage of divalent cations/unpolymerized silicate tetrahedra [1]. It generates divalent carbonates from CO2 and sequesters CO2 into the mineral matrix of the target lithology. The co-occurrence of olivine and carbonate within abraded targets from the Bastide Member of the Séítah Formation (Fm) of the Jezero crater floor [2] suggests the carbonation of olivine occurred within the mineral matrix hosted in a subsurface system. Hydrothermal origins for the subsurface system are hypothesized from orbital data [3]. This is supported by the detection of hydration features within the rock as well as the carbonate features are solely detected within the abrasion patch but not the rock’s surface. Organic preservation potential of abrasion patches: We incorporated the SHERLOC/WATSON results acquired from the Dourbes, Garde, and Quartier abrasion patches in the Séítah Fm to investigate the organomineral associations, and determine the biosignature preservation potential of these rocks. Dourbes is dominated by olivine and has minor amounts of carbonate, hydrated Ca-sulfate, and amorphous or microcrystalline silicate. Fluorescence features (330-340 nm) are detected in discrete locales and could be consistent with double ring aromatic organic molecules; yet, these features do not appear to be associated with an identified mineral phase. Dark subhedral to euhedral olivine grains within the Garde abrasion patch often co-occur with carbonate-consistent spectral signatures in all analyzed scans. The availability of Fe2+ is a known influence on olivine dissolution rates [1] and SuperCam estimates of the olivine composition (Forsterite-60 average for Sols 202-234) may thereby provide a constraint on the carbonation extent. Carbonated olivine phenocrysts within the matrix may be due to aqueous alteration, as the carbonation of nodules is consistent with observations in other hydrothermal systems and within Martian meteorites (ALH84001) [4]. In comparison, the Quartier abrasion patch represents an extensively altered endmember within the Bastide Member of the Séítah Fm. It contains a fluorescence doublet at 305/325 nm that coexists with multiple species of Na-sulfate and Mg-sulfate, Mg-carbonates, olivine [5]. Aqueous alteration and implications for habitability: The identification of primary and secondary mineral phases observed in the Bastide Member suggests the release of cations from primary ultramafic minerals through aqueous alteration. Within Garde, the carbonate detected appears to be Mg-rich and likely formed from the in situ alteration of Mg-rich olivine within the region as carbonate has only been detected within the rock via in situ analysis. Carbonates derived from abiotic and biotic reactions preserve biosignatures (i.e. indices of habitability) on Earth. The detected carbonate phase found in association with fluorescent features within the rock matrix may also indicate potential organic compounds preserved in a putative hydrothermal system. Fluorescent features (~330 nm) are unique to Garde and Dourbes, though they are co-located to carbonate signatures solely within Garde, and between the light toned minerals. Identification of these fluorescent features may be consistent with 1-2 ring aromatic compounds. The limit of detection for Raman is multiple orders of magnitude greater than the limit of detection required for fluorescence [6]. Implications for provenance: Hydrothermal systems represent disequilibrium chemical conditions that are hypothesized to have supported the emergence of life and also preserve ancient carbon within precipitated carbonates [7]. Hydrothermal system associated carbonates are capable of preserving biosignatures up to an estimated ~3.77 – 4.28 Gya [8]. Thus, carbonated olivine found within the Séítah Fm may represent a high-potential biosignature preserving environment on Mars. The formation of carbonates by an aqueous alteration process, such as carbonation of olivine is also consistent with hypotheses for carbonate within the greater regional-olivine bearing unit [2,3], which contains Garde, Dourbes, and Quartier. Acknowledgments: This work was carried out at the Jet Propulsion Laboratory, The California Institute of Technology under a contract from NASA. References: [1] Wood et al., (2019) ES&T, 6, 10. [2] Stack, K. et al., (2020) Space Sci Rev, 216, 127. [3] Tarnas, J. et al., (2021) JGR: Planets, 126, 11. [4] Steele et al., (2007) Meteorit. Planet. Sci., 42, 9. [5] Murphy, A.E. et al., (2022) LPSC [6] Bhartia et al., (2021) Space Sci Rev, 217, 58. [7] Luther (2021) GRL, 48, e2021GL094869. [8] Dodd et al., (2017) Nature, 543, 60-64

E L Cardarelli↗
NASA NTRSDate not supplied

Testing Destruction of Clay Minerals By Silica-Poor Brines in Gale Crater, Mars Using Laboratory and Field Experiments

The Mars Science Laboratory (MSL) Curiosity rover landed in Gale crater to investigate the cause for mineralogical changes seen from orbit, including the clay-sulfate mineral transition observed on its central mound, Aeolis Mons. The lower strata show spectral signatures of clay minerals, hematite, and hydrated Mg sulfates, and the upper strata are dominated by hydrated Mg sulfate signatures. This significant transition has been observed in other locations on Mars, and therefore processes related to the clay mineral-sulfate transition are likely important broadly across Mars. The bulk mineralogy of ~3.7 Ga sedimentary rocks in Gale crater is a product of variations in sediment sources and depositional processes, with overprinting by episodes of early and late diagenetic alteration. Sedimentary analyses of the smectite clay minerals observed in the Glen Torridon (GT) region of Mount Sharp suggest formation in a lacustrine aqueous environment. Examination of the Vera Rubin ridge (VRR) strata indicate that it was formed at the same time as GT and later altered by extensive diagenesis. Recent work suggests that the observed mineral transition from smectites and talc-serpentinites in GT to iron oxides and oxyhydroxides and VRR may have resulted from extensive diagenetic alteration by density driven, silica-poor brines sourced from the overlying sulfur-bearing unit on Mount Sharp. This process of alteration by silica-poor brines is observed in limited locations on Earth. We are therefore working to demonstrate the impacts of silica poor brines on clay mineral alteration in laboratory column and terrestrial analog burial experiments. Column experiments allow the investigation of dissolution and precipitation under conditions that represent a closer analog to natural environments, while burial experiments allow examination of weathering reactions of a known starting material after a specific period of time in a natural field environment. Both methods are valuable for interpreting the water-rock interactions between clay minerals and brines. In preparation for these longer-term column and burial experiments, we are performing preliminary batch dissolution experiments on materials relevant to Glen Torridon: nontronite and serpentinite. We are using magnesium sulfate brine solutions relevant to those proposed on Mars. The results of this study can provide constraints on the characteristics of the diagenetic fluids that formed the altered minerals in Gale crater. They can also provide insights into the role of brine density-driven diagenesis in past aqueous environments on Mars, which have been proposed to be widespread.

J E Valdueza↗
NASA NTRSDate not supplied

Nodal Modeling of Submerged Helium Injection Pressurization of a Cryogenic Propellant Tank

Subcooling of cryogenic propellant by helium injection is one of the most effective methods for suppressing bulk boiling and keeping subcooled propellant conditions for pre-launch, launch, and post-launch pressurization applications. For tank pressurization, submerged helium injection can substantially reduce helium consumption by infusing gaseous propellant into the tank ullage. This paper describes a thermodynamic model of the helium bubbling process in liquid oxygen to estimate the amount of oxygen vapor absorbed by the rising helium bubbles and the amount of subcooling of liquid oxygen due to evaporative heat and mass transfer. The physics of helium dissolution during the pressurization process is also modeled, primarily for liquid hydrogen propellant where the dissolution is more significant. The analyses were performed in a simulation model of tank pressurization built with Generalized Fluid System Simulation Program (GFSSP), a general-purpose flow network code developed at NASA/Marshall Space Flight Center. The numerical predictions of subcooling have been compared with the experimental data of Cho et al. which investigated the propellant subcooling effect as a function of system pressure, helium injection temperature, and flowrate for a non-drained submerged injection system. The numerical predictions of helium consumption have been compared with the test data from a NASA Centaur test vehicle which included both direct and submerged injection with draining of propellants. Hydrogen propellant testing of the Cryogenic Propellant Storage and Transfer Engineering Developmental Unit (CPST EDU) conducted at NASA/Glenn Research Facility was also analyzed. The data used for the model validation were taken in 1-g, but the model was developed to be applicable in both multi-g and micro-g environments.

tank pressurization↗
NASA NTRSDate not supplied

Acid Alteration of Clay Minerals With Implication for Mars’ Surface Processes

The co-occurrence of phyllosilicates (clays) and sulfate stratigraphies at many locations on Mars are associated with a sharp change in surface conditions from neutral/alkaline pH during the Noachian (4.1-3.7 Ga) which favored the formation of clays to acidic conditions during the Hesperian (3.7-2.9 Ga) which favored the formation of sulfates. Yet, if these two contrasting geosystems were temporarily sequential, it is unknown how the Hesperian acidic conditions altered the previously formed clay units. We performed laboratory batch experiments to fingerprint the diagnostic features produced during interactions of Mars-analog clays and acidic solutions. Two clays, and silicon (IV) oxide, were reacted with solution of either sulfuric acid or filtered natural acid rock drainage (ARD) in plastic bottles. The solutions were adjusted at four pH values (1, 3, 5, and 7) and reacted at 4, 30, and 80°C for 3, 7, and 14 days. At the end of the experiments, the filtered supernatants were analyzed by ICP-MS while the solids were characterized by X-Ray Diffraction; Energy-Dispersive X-Ray Fluorescence analyses; Raman and Short-Wave Infrared spectroscopies and Scanning Electron Microscopy. Results show that the solution chemistry played a key role in the evolution of the clay-solution systems. In H2SO4 systems, the solution pH steadily increased due to partial clay dissolution with no secondary phase formation detected. Contrary, in the ARD systems, the pH decreased due to the ample presence of Fe which controlled both the reactivity of clays by the growth of protecting surface coatings and the solution pH by the precipitation of Fe nanophases; secondary phase detected included goethite, jarosite, gypsum, and siderite. These results indicate that, on Mars, the chemical interaction between clays and acidic solutions was complex and dependent on the solution chemistry. Acidic, sulfate-rich solutions have a high dissolution capacity and could have induced widespread clay disintegration. Notably, if Fe-rich ARD was involved, the clays on Mars could have remained stable during acidic Hesperian period due to formation of protective coatings. Comparison of our results with martian observations will be performed to determine how acidic conditions could potentially affect clays in sedimentary settings, including the Gale crater.

L. Lefticariu↗
DOE OSTI2015

Four-point Bend Testing of Irradiated Monolithic U-10Mo Fuel

This paper presents results of recently completed studies aimed at characterizing the mechanical properties of irradiated U-10Mo fuel in support of monolithic base fuel qualification. Mechanical properties were evaluated in four-point bending. Specimens were taken from fuel plates irradiated in the RERTR-12 and AFIP-6 Mk. II irradiation campaigns, and tests were conducted in the Hot Fuel Examination Facility (HFEF) at Idaho National Laboratory (INL). The monolithic fuel plates consist of a U-10Mo fuel meat covered with a Zr diffusion barrier layer fabricated by co-rolling, clad in 6061 Al using a hot isostatic press (HIP) bonding process. Specimens exhibited nominal (fresh) fuel meat thickness ranging from 0.25 mm to 0.64 mm, and fuel plate average burnup ranged from approximately 0.4 x 1021 fissions/cm 3 to 6.0 x 1021 fissions/cm 3 . After sectioning the fuel plates, the 6061 Al cladding was removed by dissolution in concentrated NaOH. Pre- and post-dissolution dimensional inspections were conducted on test specimens to facilitate accurate analysis of bend test results. Four-point bend testing was conducted on the HFEF Remote Load Frame at a crosshead speed of 0.1 mm/min using custom-designed test fixtures and calibrated load cells. All specimens exhibited substantially linear elastic behavior and failed in a brittle manner. The influence of burnup on the observed slope of the stress-strain curve and the calculated fracture strength is discussed.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2014

WETTING AND REACTIVE AIR BRAZING OF BSCF FOR OXYGEN SEPARATION DEVICES

Reactive air brazes Ag-CuO and Ag-V2O5 were evaluated for brazing Ba0.5Sr0.5Co0.8Fe0.2O(3-δ) (BSCF). BSCF has been determined in previous work to have the highest potential mixed ionic/electronic conducting (MIEC) ceramic material based on the design and oxygen flux requirements of an oxy-fuel plant such as an integrated gasification combined cycle (IGCC) used to facilitate high-efficiency carbon capture. Apparent contact angles were observed for Ag-CuO and Ag-V2O5 mixtures at 1000 °C for isothermal hold times of 0, 10, 30, and 60 minutes. Wetting apparent contact angles (θ<90°) were obtained for 1%, 2%, and 5% Ag-CuO and Ag-V2O5 mixtures, with the apparent contact angles between 74° and 78° for all compositions and furnace dwell times. Preliminary microstructural analysis indicates that two different interfacial reactions are occurring: Ag-CuO interfacial microstructures revealed the same dissolution of copper oxide into the BSCF matrix to form copper-cobalt-oxygen rich dissolution products along the BSCF grain boundaries and Ag-V2O5 interfacial microstructures revealed the infiltration and replacement of cobalt and iron with vanadium and silver filling pores in the BSCF microstructure. The Ag-V2O5 interfacial reaction product layer was measured to be significantly thinner than the Ag-CuO reaction product layer. Using a fully articulated four point flexural bend test fixture, the flexural fracture strength for BSCF was determined to be 95 ± 33 MPa. The fracture strength will be used to ascertain the success of the reactive air braze alloys. Based on these results, brazes were fabricated and mechanically tested to begin to optimize the brazing parameters for this system. Ag-2.5% CuO braze alloy with a 2.5 minute thermal cycle achieved a hermetic seal with a joint flexural strength of 34 ± 15 MPa and Ag-1% V2O5 with a 30 minute thermal cycle had a joint flexural strength of 20 ± 15 MPa.

Ag-CuO↗
DOE OSTI2016

Uranium and strontium fate in waste-weathered sediments: Scaling of molecular processes to predict reactive transport

Objectives of the project: 1. Determine the process coupling that occurs between mineral transformation and contaminant (U and Sr) speciation in acid-uranium waste weathered Hanford sediments. 2. Establish linkages between molecular-scale contaminant speciation and meso-scale contaminant lability, release and reactive transport. 3. Make conjunctive use of molecular- to bench-scale data to constrain the development of a mechanistic, reactive transport model that includes coupling of contaminant sorption-desorption and mineral transformation reactions. Hypotheses tested: - Uranium and strontium speciation in legacy sediments from the U-8 and U-12 Crib sites can be reproduced in bench-scale weathering experiments conducted on unimpacted Hanford sediments from the same formations. - Reactive transport modeling of future uranium and strontium releases from the vadose zone of acid-waste weathered sediments can be effectively constrained by combining molecular-scale information on contaminant bonding environment with grain-scale information on contaminant phase partitioning, and meso-scale kinetic data on contaminant release from the waste-weathered porous media. - Although field contamination and laboratory experiments differ in their diagenetic time scales (decades for field vs. months to years for lab), sediment dissolution, neophase nucleation, and crystal growth reactions that occur during the initial disequilibrium induced by waste-sediment interaction leave a strong imprint that persists over subsequent longer-term equilibration time scales and, therefore, give rise to long-term memory effects. Enabling capabilities developed: Our team developed an iterative measure-model approach that is broadly applicable to elucidate the mechanistic underpinnings of reactive contaminant transport in geomedia subject to active weathering. Experimental design: Hypotheses were tested by comparing (with a similar set of techniques) the geochemical transformations and transport behaviors that occured in bench-scale studies of waste-sediment interaction with parallel model systems studies of homogeneous nucleation and neo-phase dissolution. Initial plans were to compare results with core sample extractions from the acid uranium waste impacted U-8 and U-12 Cribs at Hanford (see original proposal and letter of collaboration from J. Zachara). However, this part of the project was impossible because funding for core extractions were eliminated from the DoE budget. Three distinct crib waste aqueous simulants (whose composition is based on the most up-to-date information from field site investigations) were reacted with Hanford sediments in batch and column systems. Coupling of contaminant uptake to mineral weathering was monitored using a suite of methods both during waste-sediment interaction, and after, when waste-weathered sediments were subjected to infusion with circumneutral background pore water solutions. Our research was designed to adapt as needed to maintain a strong dialogue between laboratory and modeling investigations so that model development was increasingly constrained by emergent data and understanding. Potential impact of the project to DOE: Better prediction of contaminant uranium transport was achieved by employing multi-faceted lines of inquiry to build a strong bridge between molecular- and field-scale information. By focusing multiple lines and scales of observation on a common experimental design, our collaborative team revealed non-linear and emergent behavior in contaminated weathering systems. A goal of the current project was to expand our modeling capabilities, originally focused on hyperalkaline legacy waste streams, to include acidic weathering reactions that, as described above, were expected to result in profoundly different products. We were able to achieve this goal, and showed that these products nonetheless undergo analogous silicate and non-silicate transformation, ripening and aging processes. Our prediction that these weathering reactions would vary with waste stimulant chemistry resulted in data that was incorporated directly into a reactive transport model structure.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Long-term Sustainability of Fracture Conductivity in Geothermal Systems using Proppants

Long-term sustainability of fracture conductivity is critical for commercial success of engineered geothermal system (EGS) and hydrogeothermal field sites. The injection of proppants has been suggested as a means to enhance the conductivity in these systems. Several studies have examined the chemical behavior of proppants that are not at chemical equilibrium with the reservoir rock and water. These studies have suggested that in geothermal systems, geochemical reactions can lead to enhance proppant dissolution and deposition alteration minerals. We hypothesize that proppant dissolution will decrease the strength of the proppant and can potentially reduce the conductivity of the fracture. To examine the geomechanical strength of proppants, we have performed modified crushing tests of proppants and reservoir rock material that was subjected to geothermal reservoir temperature conditions. The batch reactor experiments heated crushed quartz monzonite rock material, proppants (either quartz sand, sintered bauxite or kryptospheres) with Raft River geothermal water to 250 ºC for a period of 2 months. Solid and liquid samples were shipped to University of Utah for chemical characterization with ICP-OES, ICP-MS, and SEM. A separate portion of the rock/proppant material was subjected to a modified American Petroleum Institute ISO 13503-2 proppant crushing test. This test is typically used to determine the maximum stress level that can be applied to a proppant pack without the occurrence of unacceptable proppant crushing. We will use the test results to examine potential changes in proppant/reservoir rock geomechanical properties as compared to samples that have not been subjected to geothermal conditions. These preliminary results will be used to screen the proppants for long term use in EGS and hot hydrogeothermal systems.

fracture sustainability↗
DOE OSTI2017

Effective Diffusion Coefficient of Dissolved Metal Ions during 1D Pit Growth

Transport-limited dissolution of metals in corrosion pits is associated with the product of the metal ion diffusion coefficient and total concentration of metal ions (DM+·Ctot). In one dimensional (1D) pit dissolu-tion, the concentration of ionic species varies with location in the pit; at the dissolving pit bottom, the saturation of metal ion and supporting anion is ex-pected under transport control conditions, while the metal ion is nearly depleted at the pit mouth. To describe metal ion transport through pit solution with constantly-changing concentration, an effective diffusion coefficient (Deff) is proposed in this study with consideration of the combined effects of vis-cosity, temperature and electric field inside a grow-ing 1D pit. The modeled Deff·Ctot values were calcu-lated and compared with experimental DM+·Ctot val-ues for S13Cr 1D pit dissolution in different bulk chloride concentrations at 85°C. The modeled Deff·Ctot values were very close to the experimental values, validating the modeling approach suggested in this study.

Jun, Jiheon↗
DOE OSTI2017

Method of accurate thickness measurement of boron carbide coating on copper foil

A method is disclosed of measuring the thickness of a thin coating on a substrate comprising dissolving the coating and substrate in a reagent and using the post-dissolution concentration of the coating in the reagent to calculate an effective thickness of the coating. The preferred method includes measuring non-conducting films on flexible and rough substrates, but other kinds of thin films can be measure by matching a reliable film-substrate dissolution technique. One preferred method includes determining the thickness of Boron Carbide films deposited on copper foil. The preferred method uses a standard technique known as inductively coupled plasma optical emission spectroscopy (ICPOES) to measure boron concentration in a liquid sample prepared by dissolving boron carbide films and the Copper substrates, preferably using a chemical etch known as ceric ammonium nitrate (CAN). Measured boron concentration values can then be calculated.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Nitride stabilized core/shell nanoparticles

Nitride stabilized metal nanoparticles and methods for their manufacture are disclosed. In one embodiment the metal nanoparticles have a continuous and nonporous noble metal shell with a nitride-stabilized non-noble metal core. The nitride-stabilized core provides a stabilizing effect under high oxidizing conditions suppressing the noble metal dissolution during potential cycling. The nitride stabilized nanoparticles may be fabricated by a process in which a core is coated with a shell layer that encapsulates the entire core. Introduction of nitrogen into the core by annealing produces metal nitride(s) that are less susceptible to dissolution during potential cycling under high oxidizing conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Method for generating O.sub.2-rich gas from air using water

The present disclosure is directed to a method for enriching an inlet air stream utilizing a number of enrichment sub-units connected in series, where each enrichment sub-unit conducts both a dissolution and degasification cycle. Each enrichment sub-unit comprises a compressor, an aeration unit, a deaeration unit, and a pump for the recirculation of water between the aeration and deaeration units. The methodology provides a manner in which the relationship between the respective Henry's coefficients of the oxygen and nitrogen in water may be exploited to enrich the O.sub.2 volume percent and diminish the N.sub.2 volume percent over repeated dissolution and degasification cycles. By utilizing a number of enrichment sub-units connected in series, the water contained in each enrichment sub-unit acts to progressively increase the O.sub.2 volume percent. Additional enrichment sub-units may be added and utilized until the O.sub.2 volume percent equals or exceeds a target O.sub.2 volume percent. In a particular embodiment, air having a general composition of about 78 vol. % N.sub.2 and 21 vol. % O.sub.2 is progressively enriched to provide a final mixture of about 92% vol. % O.sub.2 and 8% vol. % N.sub.2.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Presence and Impact of Surface Films formed on Mg in Chloroaluminate Electrolytes.

The impact of surface film formation on Mg is explored during electrodeposition and electrodissolution in two high activity, aprotic electrolytes: the all phenyl complex (APC) and the magnesium aluminum chloride complex (MACC). Where past studies have argued such films are benign, results show that interfacial films are responsible for controlling the Mg deposit structure when deposition and dissolution are conducted at the rates required for practical Mg batteries. Chronopotentiometry is shown to provide clear signatures of the impact of interfacial films on deposition and dissolution. The particular combination of cycling punctuated by periods of open circuit equilibration is shown to yield a noticeable decrease in coulombic efficiency over a 50 cycle sequence. High resolution electron imaging shows that cycling results in porosity development and accumulation of electrolyte constituents within the deposit. Reduced coulombic efficiency signaling Mg loss appears related to progressive isolation of a fraction of the deposit. Mg and electrolyte loss must be compensated for in a practical cell through the introduction of excess inventory and resulting in a reduced energy density of the system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Fracture mechanics of shales under chemically reactive conditions

Fracture growth processes under subsurface conditions are known to be affected by fluid chemical environment. Chemical effects on fracture growth are likely to be relevant during host rock and organic matter diagenesis and catagenesis, hydraulic fracturing, in systems undergoing enhanced oil recovery, in geothermal systems, and in CO 2 sequestration reservoirs. To address the chemical effects on opening-mode fracture growth under a wide range in fluid chemical conditions and for different rock types we conducted double-torsion fracture mechanics tests to determine mode-I fracture toughness (KIC), subcritical index (SCI), and the stress-intensity factor vs fracture velocity (K-V) behavior. We tested sandstones, shales and, altered crystalline rocks. Samples were tested in aqueous conditions with variable salinity, solution pH, and at temperatures of up to 70 °C. Fracture growth in shales is highly sensitive to the environmental conditions, with a reduction of KIC of up to 47% from ambient air to water-saturated conditions. The primary interactions between shales and reactive solutions are clay-water and carbonate dissolution. For clay-rich Woodford and Mancos shales, solutions with higher salinity reduce subcritical fracture growth, while acidic conditions favor fracture growth in carbonate-rich Marcellus shale. Increasing the solution temperature promotes fracture growth. In sandstone, chemical effects on fracture parameters are most pronounced for clay- and carbonate-rich samples. Both KIC and SCI are lower in water than in air for nearly all sandstone lithologies tested. SCI is further reduced in chlorite-cemented Tuscaloosa Sandstone in acidic solutions. Mount Simon Sandstone is also sensitive to pH, most significantly in diagenetically bleached samples. Compositionally mature Aztec Sandstone is affected by water saturation, but shows little sensitivity to chemical environment. Silicified gabbro shows a slight reduction in KIC but a >60% reduction in SCI in aqueous environments compared to ambient conditions. The reduction in SCI is most pronounced in alkaline and saline solutions, suggesting silica dissolution and cation exchange at the fracture tip facilitate subcritical fracture growth. Limited reduction in KIC is attributed to low permeability. Overall, our results demonstrate that fracture properties depend strongly on water saturation, on fluid composition and pH, and on temperature, with an increase in temperature lowering fracture resistance.

58 GEOSCIENCES↗
DOE OSTI2015

Rock fracture processes in chemically reactive environments

Rock fracture is traditionally viewed as a brittle process involving damage nucleation and growth in a zone ahead of a larger fracture, resulting in fracture propagation once a threshold loading stress is exceeded. It is now increasingly recognized that coupled chemical-mechanical processes influence fracture growth in wide range of subsurface conditions that include igneous, metamorphic, and geothermal systems, and diagenetically reactive sedimentary systems with possible applications to hydrocarbon extraction and CO 2 sequestration. Fracture processes aided or driven by chemical change can affect the onset of fracture, fracture shape and branching characteristics, and fracture network geometry, thus influencing mechanical strength and flow properties of rock systems. We are investigating two fundamental modes of chemical-mechanical interactions associated with fracture growth: 1. Fracture propagation may be aided by chemical dissolution or hydration reactions at the fracture tip allowing fracture propagation under subcritical stress loading conditions. We are evaluating effects of environmental conditions on critical (fracture toughness KIc) and subcritical (subcritical index) fracture properties using double torsion fracture mechanics tests on shale and sandstone. Depending on rock composition, the presence of reactive aqueous fluids can increase or decrease KIc and/or subcritical index. 2. Fracture may be concurrent with distributed dissolution-precipitation reactions in the hostrock beyond the immediate vicinity of the fracture tip. Reconstructing the fracture opening history recorded in crack-seal fracture cement of deeply buried sandstone we find that fracture length growth and fracture opening can be decoupled, with a phase of initial length growth followed by a phase of dominant fracture opening. This suggests that mechanical crack-tip failure processes, possibly aided by chemical crack-tip weakening, and distributed solution-precipitation creep in the hostrock can independently affect fracture opening displacement and thus fracture aperture profiles and aperture distribution.

58 GEOSCIENCES↗
DOE OSTI2017

MAMBA

MAMBA is a general-purpose, liquid-solid surface chemistry solver that simulates the thermo-chemical evolution of compositions on cylindrical metal surfaces. MAMBA models conduction and convection heat transfer through porous media in one (radial) or three (radial, azimuthal, and axial) dimensions, including boiling heat transfer through "chimneys" in a porous CRUD layer. Thermo-chemistry models in MAMBA account for the growth corrosion and CRUD layers on the surface of the metal and can incorporate precipitation of additional species within the porous CRUD. MAMBA also accounts for the erosion of the surface layer through turbulent kinetic energy of a flowing liquid and the dissolution of species into the liquid as temperature changes occur. MAMBA currently includes thermo-chemistry models that account for soluble and precipitate dissolution of species from heat exchanger tubes and stainless steel piping as well as the species associated with CRUD formation on the surface of nuclear fuel rods.

Collins, Benjamin S↗