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NASA NTRS2004

Science Goal Monitor: Science Goal Driven Automation for NASA Missions

Infusion of automation technologies into NASA s future missions will be essential because of the need to: (1) effectively handle an exponentially increasing volume of scientific data, (2) successfully meet dynamic, opportunistic scientific goals and objectives, and (3) substantially reduce mission operations staff and costs. While much effort has gone into automating routine spacecraft operations to reduce human workload and hence costs, applying intelligent automation to the science side, i.e., science data acquisition, data analysis and reactions to that data analysis in a timely and still scientifically valid manner, has been relatively under-emphasized. In order to introduce science driven automation in missions, we must be able to: capture and interpret the science goals of observing programs, represent those goals in machine interpretable language; and allow spacecrafts onboard systems to autonomously react to the scientist's goals. In short, we must teach our platforms to dynamically understand, recognize, and react to the scientists goals. The Science Goal Monitor (SGM) project at NASA Goddard Space Flight Center is a prototype software tool being developed to determine the best strategies for implementing science goal driven automation in missions. The tools being developed in SGM improve the ability to monitor and react to the changing status of scientific events. The SGM system enables scientists to specify what to look for and how to react in descriptive rather than technical terms. The system monitors streams of science data to identify occurrences of key events previously specified by the scientist. When an event occurs, the system autonomously coordinates the execution of the scientist s desired reactions. Through SGM, we will improve om understanding about the capabilities needed onboard for success, develop metrics to understand the potential increase in science returns, and develop an operational prototype so that the perceived risks associated with increased use of automation can be reduced.

Koratkar, Anuradha↗

NASA NTRS2006

Fuel-Air Mixing and Combustion in Scramjets

At flight speeds, the residence time for atmospheric air ingested into a scramjet inlet and exiting from the engine nozzle is on the order of a millisecond. Therefore, fuel injected into the air must efficiently mix within tens of microseconds and react to release its energy in the combustor. The overall combustion process should be mixing controlled to provide a stable operating environment; in reality, however, combustion in the upstream portion of the combustor, particularly at higher Mach numbers, is kinetically controlled where ignition delay times are on the same order as the fluid scale. Both mixing and combustion time scales must be considered in a detailed study of mixing and reaction in a scramjet to understand the flow processes and to ultimately achieve a successful design. Although the geometric configuration of a scramjet is relatively simple compared to a turbomachinery design, the flow physics associated with the simultaneous injection of fuel from multiple injector configurations, and the mixing and combustion of that fuel downstream of the injectors is still quite complex. For this reason, many researchers have considered the more tractable problem of a spatially developing, primarily supersonic, chemically reacting mixing layer or jet that relaxes only the complexities introduced by engine geometry. All of the difficulties introduced by the fluid mechanics, combustion chemistry, and interactions between these phenomena can be retained in the reacting mixing layer, making it an ideal problem for the detailed study of supersonic reacting flow in a scramjet. With a good understanding of the physics of the scramjet internal flowfield, the designer can then return to the actual scramjet geometry with this knowledge and apply engineering design tools that more properly account for the complex physics. This approach will guide the discussion in the remainder of this section.

Drummond, J. Philip↗

NASA NTRS1994

Association Reactions at Low Pressure: 5. The CH(sub 3)+/HCN System. A Final Word?

The reaction of the methyl cation with hydrogen cyanide is revisited. We have confidence that we have resolved a long standing apparent contradiction of experimental results. A literature history is presented along with one new experiment and a reexamination of an old experiment. In this present work it is shown that all of the previous studies had made consistent observations. Yet, each of the previous studies failed to observe all of the information present. The methyl cation does react with HCN by radiative association, a fact which had been in doubt. The product ions formed in the two-body and three-body processes react differently with HCN. The collisionally stabilized association product formed by a three-body mechanism does not react with HCN and is readily detected in the experiments. The radiatively stabilized association product, formed by a slow two-body reaction, is not detected because it reacts with HCN by a fast proton transfer reaction forming the protonated HCN ion.

methyl cation↗

NASA NTRS2007

NDE Development for Inspection of the Ares I Crew Launch Vehicle

NASA is designing a new crewed launch vehicle called Ares I to replace the Space Shuttle after its scheduled retirement in 2010. This new launch vehicle will build on the Shuttle technology in many ways including using a first stage based upon the Space Shuttle Solid Rocket Booster, advanced aluminum alloys for the second stage tanks, and friction stir welding to assemble the second stage. Friction stir welding uses a spinning pin that is inserted in the joint between two panels that are to be welded. The pin mechanically mixes the metal together below the melting temperature to form the weld. Friction stir welding allows high strength joints in metals that would otherwise lose much of their strength as they are melted during the fusion welding process. One significant change from the Space Shuttle that impacts NDE is the implementation of self-reacting friction stir welding for non-linear welds on the primary metallic structure. The self-reacting technique differs from the conventional technique because the load of the pin tool pressing down on the metal being joined is reacted by a nut on the end of the tool rather than an anvil behind the part. No spacecraft has ever flown with a self-reacting friction stir weld, so this is a major advancement in the manufacturing process, bringing with it a whole new set of challenges for NDE to overcome. Another impact is the proposed usage of an aluminum face sheet, phenolic honeycomb sandwich structure for a common bulkhead between the fuel and oxidizer tanks. This design was used on the second stage of Saturn IB and the second and third stages of Saturn V, but both the manufacturing and subsequent inspection were very costly and time consuming so a more efficient inspection method is sought. The current state of development of these inspections will be presented, along with other information pertinent to NDE of the Ares I.

Richter, Joel↗

NASA NTRS2010

Low-Friction, Low-Profile, High-Moment Two-Axis Joint

The two-axis joint is a mechanical device that provides two-degrees-of-freedom motion between connected components. A compact, moment-resistant, two-axis joint is used to connect an electromechanical actuator to its driven structural members. Due to the requirements of the overall mechanism, the joint has a low profile to fit within the allowable space, low friction, and high moment-reacting capability. The mechanical arrangement of this joint can withstand high moments when loads are applied. These features allow the joint to be used in tight spaces where a high load capability is required, as well as in applications where penetrating the mounting surface is not an option or where surface mounting is required. The joint consists of one base, one clevis, one cap, two needle bearings, and a circular shim. The base of the joint is the housing (the base and the cap together), and is connected to the grounding structure via fasteners and a bolt pattern. Captive within the housing, between the base and the cap, are the rotating clevis and the needle bearings. The clevis is attached to the mechanical system (linear actuator) via a pin. This pin, and the rotational movement of the clevis with respect to the housing, provides two rotational degrees of freedom. The larger diameter flange of the clevis is sandwiched between a pair of needle bearings, one on each side of the flange. During the assembly of the two-axis joint, the circular shims are used to adjust the amount of preload that is applied to the needle bearings. The above arrangement enables the joint to handle high moments with minimal friction. To achieve the high-moment capability within a low-profile joint, the use of depth of engagement (like that of a conventional rotating shaft) to react moment is replaced with planar engagement parallel to the mounting surface. The needle bearings with the clevis flange provide the surface area to react the clevis loads/moments into the joint housing while providing minimal friction during rotation. The diameter of the flange and the bearings can be increased to react higher loads and still maintain a compact surface mounting capability. This type of joint can be used in a wide variety of mechanisms and mechanical systems. It is especially effective where precise, smooth, continuous motion is required. For example, the joint can be used at the end of a linear actuator that is required to extend and rotate simultaneously. The current design application is for use in a spacecraft docking-system capture mechanism. Other applications might include industrial robotic or assembly line apparatuses, positioning systems, or in the motion-based simulator industry that employs complex, multi-axis manipulators for various types of motions.

Lewis, James L.↗

NASA NTRS2010

Development of Weld Inspection of the Ares I Crew Launch Vehicle Upper Stage

NASA is designing a new crewed launch vehicle called Ares I to replace the Space Shuttle after its scheduled retirement in 2010. This new launch vehicle will build on the Shuttle technology in many ways including using a first stage based upon the Space Shuttle Solid Rocket Booster, advanced aluminum alloys for the second stage tanks, and friction stir welding to assemble the second stage. Friction stir welding uses a spinning pin that is inserted in the joint between two panels that are to be welded. The pin mechanically mixes the metal together below the melting temperature to form the weld. Friction stir welding allows high strength joints in metals that would otherwise lose much of their strength as they are melted during the fusion welding process. One significant change from the Space Shuttle that impacts NDE is the implementation of self-reacting friction stir welding for non-linear welds on the primary metallic structure. The self-reacting technique differs from the conventional technique because the load of the pin tool pressing down on the metal being joined is reacted by a nut on the end of the tool rather than an anvil behind the part. No spacecraft has ever flown with a self-reacting friction stir weld, so this is a major advancement in the manufacturing process, bringing with it a whole new set of challenges for NDE to overcome. The metal microstructure and possible defects are different from other weld processes. Friction plug welds will be used to close out the hole remaining in the radial welds when friction stir welded. This plug welding also has unique challenges in inspection. The current state of development of these inspections will be presented, along with other information pertinent to NDE of the Ares I.

Russell, Sam↗

NASA NTRS2010

Integral Battery Power Limiting Circuit for Intrinsically Safe Applications

A circuit topology has been designed to guarantee the output of intrinsically safe power for the operation of electrical devices in a hazardous environment. This design uses a MOSFET (metal oxide semiconductor field-effect transistor) as a switch to connect and disconnect power to a load. A test current is provided through a separate path to the load for monitoring by a comparator against a preset threshold level. The circuit is configured so that the test current will detect a fault in the load and open the switch before the main current can respond. The main current passes through the switch and then an inductor. When a fault occurs in the load, the current through the inductor cannot change immediately, but the voltage drops immediately to safe levels. The comparator detects this drop and opens the switch before the current in the inductor has a chance to respond. This circuit protects both the current and voltage from exceeding safe levels. Typically, this type of protection is accomplished by a fuse or a circuit breaker, but in order for a fuse or a circuit breaker to blow or trip, the current must exceed the safe levels momentarily, which may be just enough time to ignite anything in a hazardous environment. To prevent this from happening, a fuse is typically current-limited by the addition of the resistor to keep the current within safe levels while the fuse reacts. The use of a resistor is acceptable for non-battery applications where the wasted energy and voltage drop across the resistor can be tolerated. The use of the switch and inductor minimizes the wasted energy. For example, a circuit runs from a 3.6-V battery that must be current-limited to 200 mA. If the circuit normally draws 10 mA, then an 18-ohm resistor would drop 180 mV during normal operation, while a typical switch (0.02 ohm) and inductor (0.97 ohm) would only drop 9.9 mV. From a power standpoint, the current-limiting resistor protection circuit wastes about 18 times more power than the switch and the inductor configuration. In the fault condition, both the resistor and the inductor react immediately. The resistor reacts by allowing more current to flow and dropping the voltage. Initially, the inductor reacts by dropping the voltage, and then by not allowing the current to change. When the comparator detects the drop in voltage, it opens the switch, thus preventing any further current flow. The inductor alone is not sufficient protection, because after the voltage drop has settled, the inductor would then allow the current to change, in this example, the current would be 3.7 A. In the fault condition, the resistor is flowing 200 mA until the fuse blows (anywhere from 1 ms to 100 s), while the switch and inductor combination is flowing about 2 A test current while monitoring for the fault to be corrected. Finally, as an additional safety feature, the circuit can be configured to hold the switch opened until both the load and source are disconnected.

Burns, Bradley M.↗

NASA NTRS2011

Exploring the Fate of Nitrogen Heterocycles in Complex Prebiotic Mixtures

A long standing question in the field of prebiotic chemistry is the origin of the genetic macromolecules DNA and RNA. DNA and RNA have very complex structures with repeating subunits of nucleotides, which are composed of nucleobases (nitrogen heterocycles) connected to sugar-phosphate. Due to the instability of some nucleobases (e.g. cytosine), difficulty of synthesis and instability of D-ribose, and the likely scarcity of polyphosphates necessary for the modern nucleotides, alternative nucleotides have been proposed for constructing the first genetic material. Thus, we have begun to investigate the chemistry of nitrogen heterocycles in plausible, complex prebiotic mixtures in an effort to identify robust reactions and potential alternative nucleotides. We have taken a complex prebiotic mixture produced by a spark discharge acting on a gas mixture of N2, CO2, CH4, and H2, and reacted it with four nitrogen heterocycles: uracil, 5-hydroxymethyluracil, guanine, and isoxanthopterin (2-amino-4,7-dihydroxypteridine). The products of the reaction between the spark mixture and each nitrogen heterocycle were characterized by liquid chromatography coupled to UV spectroscopy and Orbitrap mass spectrometry. We found that the reaction between the spark mixtUl'e and isoxanthopterin formed one major product, which was a cyanide adduct. 5-hydroxymethyluracil also reacted with the spark mixture to form a cyanide adduct, uracil-5-acetonitrile, which has been synthesized previously by reacting HCN with S-hydroxymethyluracil. Unlike isoxanthopterin, the chromatogram of the 5-hydroxymethyluracil reaction was much more complex with multiple products including spark-modified dimers. Additionally, we observed that HMU readily self-polymerizes in solution to a variety of oligomers consistent with those suggested by Cleaves. Guanine and uracil, the biological nucleobases, did not react with the spark mixture, even at high temperature (100 C). This suggests that there are alternative nucleobases which are more reactive under prebiotic conditions and may have been involved in producing precursor nucleotides.

Smith, Karen E.↗

NASA NTRS2016

Impact of Flight Enthalpy, Fuel Simulant, and Chemical Reactions on the Mixing Characteristics of Several Injectors at Hypervelocity Flow Conditions

The high total temperatures or total enthalpies required to duplicate the high-speed flight conditions in ground experiments often place stringent requirements on the material selection and cooling needs for the test articles and intrusive flow diagnostic equipment. Furthermore, for internal flows, these conditions often complicate the use of nonintrusive diagnostics that need optical access to the test section and interior portions of the flowpath. Because of the technical challenges and increased costs associated with experimentation at high values of total enthalpy, an attempt is often made to reduce it. This is the case for the Enhanced Injection and Mixing Project (EIMP) currently underway in the Arc-Heated Scramjet Test Facility at the NASA Langley Research Center. The EIMP aims to investigate supersonic combustion ramjet (scramjet) fuel injection and mixing physics, improve the understanding of underlying physical processes, and develop enhancement strategies and functional relationships between mixing performance and losses relevant to flight Mach numbers greater than 8. The experiments will consider a "direct-connect" approach and utilize a Mach 6 nozzle to simulate the combustor entrance flow of a scramjet engine. However, while the value of the Mach number is matched to that expected at the combustor entrance in flight, the maximum value of the total enthalpy for these experiments is limited by the thermal-structural limits of the uncooled experimental hardware. Furthermore, the fuel simulant is helium, not hydrogen. The use of "cold" flows and non-reacting mixtures of fuel simulants for mixing experiments is not new and has been extensively utilized as a screening technique for scramjet fuel injectors. In this study, Reynolds-averaged simulations are utilized (RAS) to systematically verify the implicit assumptions used by the EIMP. This is accomplished by first performing RAS of mixing for two injector configurations at planned nominal experimental conditions. The mixing parameters of interest, such as mixing efficiency and total pressure recovery, are then computed and compared to the values obtained from RAS under the true enthalpy conditions and using helium and hydrogen. Finally, the impact of combustion on mixing, often deemed small enough to neglect at hypervelocity conditions, is assessed by comparing the results obtained from the hydrogen-fueled reacting and non-reacting RAS. For reacting flows, in addition to mixing efficiency and total pressure recovery, the combustion efficiency and thrust potential are also considered. In all of the simulations, the incoming air Mach number and the fuel-to-air ratio are the same, while the total pressure, total enthalpy, and the fuel simulant vary depending on the case considered. It is found that under some conditions the "cold" flow experiments are a good approximation of the flight.

Drozda, Tomasz G.↗

NASA NTRS2017

Effect of Air Swirler Configuration on Lean Direct Injector Flow Structure and Combustion Performance with a 7-Point Lean Direct Injector Array

Studies of various injector configurations in a 7-point Lean Direct Injector (LDI) array are reported for both non-reacting (cold) flow and for Jet-A/air reacting flows. For cold flow, central recirculation zone (CRZ) formation is investigated and for reacting flows, combustor operability and dynamics are of interest. 2D Particle Image Velocimetry (PIV) measurements are described for the cold flow experiments and flame chemiluminescence imaging and dynamic pressure results are discussed for the reacting flow cases. PIV results indicate that for this configuration the close spacing between swirler elements leads to strong interaction that affects whether a CRZ forms, and pilot recess and counter-swirl helps to isolate swirlers from one another. Dynamics results focus on features identified near 500-Hz.

aircraft combustors↗

NASA NTRS2019

100-kHz Rate Rayleigh Imaging for Combustion and Flow Diagnostics

Two-dimensional (2D) Rayleigh scattering (RS) imaging at an ultrahigh repetition rate of 100 kHz is demonstrated in non-reacting and reacting flows employing a high-energy burst-mode laser system. Image sequences of flow mixture fraction were directly derived from high-speed RS images. Additionally, a 2D instantaneous flow velocity field at 100 kHz was obtained through optical-flow-based analysis of the RS images. The technique was also applied to study turbulent flames having a near-constant Rayleigh cross section. The demonstrated high-speed RS technique in conjunction with optical-flow-based analysis provides non-intrusive, simultaneous measurements of the flow mixing and velocity field, extending the measurement capability of the RS technique to high-speed non-reacting and reacting flows.

Jiang, Naibo↗

NASA NTRSDate not supplied

Comparison Between DSMC and CFD for Hypersonic Planetary Entry Simulations

Hypersonic planetary entry flows span a wide range of Knudsen numbers between rarefied and continuum flows. While computational fluid dynamics (CFD) techniques cannot provide an accurate solution for flows in the rarefied regime, the direct simulation Monte Carlo (DSMC) method is capable of providing accurate solutions for flows in both in the rarefied and continuum regimes but becomes prohibitively expensive as the Knudsen number decreases. For the purpose of thermal protection systems (TPS) design and post-flight reconstruction, various selected points along an entry trajectory are often solved using hypersonic solvers. The quantities of interest that are obtained from that exercise are generally surface quantities, such as pressure, heat flux and enthalpy. Then, material response solvers are used to either design the heat shield to an optimal thickness based on a choice of material, or to provide in-depth heating profiles through the material at various select locations, and compare with flight instrumentation such as the ones that flew on NASA’s two most recent Mars missions, MSL and Mars2020. While most of the heating is generally experienced during the continuum part of the entry, the heating within the rarefied regime is significant for some atmospheres, and hence the flow solutions need to be computed using the DSMC method. Ensuring consistency between hypersonic CFD and the DSMC is crucial so that reliable surface quantities can be passed to material response solvers. Studies were performed to compare the two methods at various select locations, for both non-reacting argon flows as well reacting CO2/N2 flows. Preliminary conclusions show that, for non-reacting flows, the agreement between the two methods for surface heating is excellent (within expected uncertainties) for a freestream Knudsen number of 0.0006, and gets progressively worse as the Knudsen number increases to 0.06. Continuum breakdown analyses were performed and showed that, in general, the Gradient Length Local Knudsen number (KnGLL) from Boyd [1] and associated criteria (KnGLL > 0.05) can be accurately used to predict zones of breakdown in the flow, and associated errors for surface quantities. Furthermore, when studying reacting flow, our studies showed that while flow quantities are highly dependent on relaxation parameters and chemistry rates, it is possible to obtain a good agreement for surface heating, as long as the continuum breakdown in minimal (see Fig. 1). Finally, we studied the impact of the grid refinement on the surface quantities in DSMC.

DSMC↗

NASA NTRSDate not supplied

Comparison Between DSMC and CFD for Hypersonic Planetary Entry Simulations

Hypersonic planetary entry flows span a wide range of Knudsen numbers between rarefied and continuum flows. While computational fluid dynamics (CFD) techniques cannot provide an accurate solution for flows in the rarefied regime, the direct simulation Monte Carlo (DSMC) method is capable of providing accurate solutions for flows in both in the rarefied and continuum regimes but becomes prohibitively expensive as the Knudsen number decreases. For the purpose of thermal protection systems (TPS) design and post-flight reconstruction, various selected points along an entry trajectory are often solved using hypersonic solvers. The quantities of interest that are obtained from that exercise are generally surface quantities, such as pressure, heat flux and enthalpy. Then, material response solvers are used to either design the heat shield to an optimal thickness based on a choice of material, or to provide in-depth heating profiles through the material at various select locations, and compare with flight instrumentation such as the ones that flew on NASA’s two most recent Mars missions, MSL and Mars2020. While most of the heating is generally experienced during the continuum part of the entry, the heating within the rarefied regime is significant for some atmospheres, and hence the flow solutions need to be computed using the DSMC method. Ensuring consistency between hypersonic CFD and the DSMC is crucial so that reliable surface quantities can be passed to material response solvers. Studies were performed to compare the two methods at various select locations, for both non-reacting argon flows as well reacting CO2/N2 flows. Preliminary conclusions show that, for non-reacting flows, the agreement between the two methods for surface heating is excellent (within expected uncertainties) for a freestream Knudsen number of 0.0006, and gets progressively worse as the Knudsen number increases to 0.06. Continuum breakdown analyses were performed and showed that, in general, the Gradient Length Local Knudsen number (KnGLL) from Boyd and associated criterion (KnGLL > 0.05) seems conservative in predicting zones of breakdown in the flow, and associated errors for surface quantities. Updated criteria of KnGLL = 2.0 and 0.5 appear to be more appropriate for surface and flow quantities, respectively. Furthermore, when studying reacting flows, our studies showed that while flow quantities are highly dependent on relaxation parameters and chemistry rates, it is possible to obtain a good agreement for surface heating, as long as the continuum breakdown is minimal.

DSMC↗

DOE OSTI2021

Method for direct conversion of carbon dioxide to dialkyl carbonates using ethylene oxide as feedstock

A method for co-production of high purity dimethyl carbonate and mono-ethylene glycol by applying a reactor, such as a membrane reactor and/or an adsorbent-catalytic reactor by capturing and reacting carbon dioxide with methanol and ethylene oxide. Carbon dioxide may be recovered from primary sources (utilities and industrial processes) by a membrane or solid adsorbent, and subsequently converted to an intermediate hydroxy-ethyl-methyl carbonate by reacting with ethylene oxide and methanol. For high-purity carbon dioxide (obtained by carbon capture technologies or from an ethanol fermentation process), the membrane reactor is replaced with a catalytic reactor for direct conversion of carbon dioxide to hydroxy-ethyl-methyl carbonate by reacting with ethylene oxide and methanol. The hydro-ethyl-methyl carbonate is further reacted with methanol for conversion to dimethyl carbonate. A combination of heterogeneous and homogeneous catalysts is implemented for an effective conversion of carbon dioxide. An integrated reactive distillation process using side reactors is used for facilitating catalytic reaction for production of high purity dimethyl carbonate.

Panchal, Chandrakant B.↗

DOE OSTI2023

Impact of carbamate formation on the surface tension of epoxy‐amine curing systems

Abstract Epoxy‐amine reactive systems, including their surface tension, have been studied due to their use and importance in composites and adhesives in laboratory and industrial applications. Understanding how the system's surface tension changes during curing could help target applications for tailored composites. Using the Wilhelmy plate method, surface tensions for epoxy‐curing agent systems were investigated under different environments. While the epoxy exhibited an expected negative temperature coefficient of −0.096 mN/m/°C, the curing agent exhibited a positive temperature coefficient of 0.073 mN/m/°C, which is due to the curing agent reacting with atmospheric CO 2 to form carbamate through a zwitterion pathway and functional groups accumulating at the surface of the reacting systems. Carbamate formation results in a surface tension below that of the individual constituents in the epoxy‐amine curing agent system. Fourier transform infrared (FTIR) spectroscopy was used to verify in situ formation of carbamate, and by reducing the system's temperature, it was demonstrated that the system surface tension profiles displayed micellar surfactant‐like characteristics. FTIR was used to explore the difference in composition between the surface and the bulk, in particular carbamate formation at the surface, resulting in a lowering of the surface tension of reacting systems.

Shenk, Timothy M.↗

DOE OSTI2021

Oxidation and Associated Pore Structure Modification During Experimental Alteration of Granite

Weathering plays a crucial role in a number of environmental processes, and the microstructure and evolution of multi-scale pore space is a critically important factor in the weathering of geological formations. In igneous rocks the infiltration of meteoric water into initially relatively dry material can cause the rock to begin to disaggregate, increasing porosity and surface area, and allowing further disaggregation and weathering to occur. These processes, in turn, allow biota to colonize the rock, further enhancing the weathering rate. In some igneous rocks this may be driven by oxidation of primary minerals. One such mineral, biotite, has been repeatedly mentioned as a cause of cracking during oxidation. However, the scale-dependence of the processes by which this occurs are poorly understood. We cannot, therefore, accurately extrapolate laboratory reaction rates to the field in predictive numerical models. In order to better understand the effects of oxidation and test the hypothesis that fracture and disaggregation are initiated by swelling of oxidizing biotites, we reacted granite cores in a selenic acid-rich aqueous solution at 200°C for up to 438 days. Elevated temperatures and selenic acid were used to provide relatively fast reaction rates and highly oxidizing conditions in sealed reaction vessels. These experiments were analyzed using a combination of imaging, X-ray diffraction, Mössbauer spectroscopy, and small- and ultra-small angle neutron scattering to interrogate porosity and microfracture formation. The experimental results show little observable biotite swelling, but significant transport and growth of iron oxides and/or clays along grain boundaries throughout the sample. Significant increases in porosity were also observed at the sample rim, likely associated with feldspar alteration. Fractures and transport were observed throughout the core, suggesting that stresses due to crystallization pressures caused by the growing iron phases may be the initiating factors in granite weathering, possibly followed by biotite swelling after sufficient permeability is achieved.

Anovitz, Lawrence M.↗

DOE OSTI2022

Morphological and crystallographic controls in the replacement of calcite and aragonite by cerussite and otavite

Mineral replacement reactions are essential solid-fluid interactions in natural and industrial processes including metasomatism, diagenesis, and metamorphism, and sequestration of metal toxins from polluted water. In this paper, we explore the morphological evolution of aragonite and calcite (polymorphs of CaCO 3 ) during their replacement by cerussite (PbCO 3 , an isomorph of aragonite) and otavite (CdCO 3 , an isomorph of calcite) in acidic aqueous solutions (with initial pH 3 to 4). Observations using scanning electron and synchrotron-based transmission X-ray microscopies reveal the formation of pseudomorphic shells (~5 to 10 µm thick) of cerussite and otavite when Pb 2+ is reacted with either calcite or aragonite and when Cd 2+ is reacted with aragonite. The formation of pore space at the substrate-precipitate interface and within the precipitate is found to be key in promoting chemical exchange between the dissolving phase and the solution. In contrast, minimal reactivity is observed when Cd 2+ is reacted with calcite. These results demonstrate that the lack of substrate-precipitate epitaxy (either because of inconsistent symmetries or due to large lattice constant mismatch) is a critical factor that enables replacement of primary CaCO 3 minerals by Pb- or Cd-bearing secondary minerals while the presence of epitaxial relationships inhibit those reactions. When calcite and aragonite coexist, the replacement of aragonite by cerussite and otavite occurs preferentially over calcite. We postulate that the relative reactivity of calcite and aragonite to Pb 2+ and Cd 2+ can be determined by interplay between morphological and crystallographic properties of CaCO 3 materials as well as solution chemistry. Our results demonstrate that coupled dissolution-precipitation processes of carbonate minerals play an important role in controlling mobility and bioavailability of lead and cadmium in environments where acidic metal-contaminated water interacts with carbonate-rich rocks and soils.

58 GEOSCIENCES↗

DOE OSTI2025

Nickel hydroxide–nickel carbonate competitive growth on carbonate surfaces

The thermodynamic and kinetic factors controlling the competitive heterogeneous nucleation and growth of ubiquitous metal carbonate and hydroxide phases are poorly understood. In this work, calcite (CaCO 3 ) and magnesite (MgCO 3 ) powders were reacted with NiCl 2 (0–600 μM) for 7 days at 22 °C and 5 °C. The reacted powders were analyzed with X-ray photoelectron spectroscopy (XPS), scanning electron microscopy, and energy-dispersive X-ray spectroscopy to characterize the Ni surface precipitates formed. Evidence from these techniques pointed to the formation of mixed Ni carbonate-Ni hydroxide amorphous surface precipitates. On calcite, XPS detected primarily Ni(OH) 2 despite the initial solutions being more supersaturated with respect to gaspéite (NiCO 3 ) than to theophrastite (Ni(OH) 2 ) by a factor of 17–18. In contrast, NiCO 3 was the dominant component detected by XPS on magnesite in the same conditions. Decreasing the temperature had the effect of increasing the proportion of NiCO 3 to the detriment of Ni(OH) 2 . The experimental observations were consistent with low lattice/cation size mismatch favoring NiCO 3 nucleation and temperature most influencing Ni(OH) 2 nucleation. Comparison to previous work on Co-reacted powders indicated the differences in lattice/cation size mismatch and/or water exchange rate impacted the composition of the surface precipitates more than the relative thermodynamic stabilities of the competing minerals. This work explored the heterogeneous growth regime of Ni carbonate and hydroxide phases on carbonate surfaces and shed light on the factors that control the competition between surface precipitates when mineral surfaces are in contact with aqueous solutions supersaturated with respect to multiple mineral phases. In conclusion, these results contribute to geochemists’ efforts toward interpreting data from geochemical systems with elevated Ni concentrations, improving Ni environmental remediation and recovery strategies, and predicting the fate and transport of Ni in geochemical systems.

Heterogeneous nucleation↗