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54 records · Page 3

Kaolinite-catalyzed air oxidation of hydrazine: Consideration of several compositional, structural and energetic factors in surface activation

Clay minerals have been shown to have numerous, curious, energetic properties by virtue of ultra-violet light release which can be triggered by gentle environmental changes such as wetting and dewetting by a variety of liquids, unique among them water and hydrazine. Since both water and hydrazine play multiple key roles in the air-oxidation of hydrazine on kaolinite surfaces, this reaction would seem to have prime potential for studying interrelationships of energy storage, release and chemical reactivity of clay surfaces, capacities basic to either the Bernal or Cairns-Smith roles of minerals in the origin of life. Establishment of the capacity for stored electronic energy to significantly alter surface chemistry is important, regardless of the reaction chosen to demonstrate it. Hydrazine air oxidation is overawingly complex, given the possibilities for step-wise control and monitoring of parameters. In the light of recently extended characterization of the kaolinite and model sheet catalysts we used to study hydrazine oxidation and gamma-irradiated silica, previous studies of hydrazine air-oxidation on aluminosilicate surfaces have been reevaluated. Our former conclusion remains intact that, whereas trace structural and surface contaminants do play some role in the catalysis of oxidation, they are not the only, nor even the dominant, catalytic centers. Initial intermediates in the oxidation can now be proposed which are consistent with production via O(-)-centers as well as ferric iron centers. The greater than square dependence of the initial reaction rate on the weight of the clay is discussed in the light of these various mechanistic possibilities.

Coyne, L. M.↗

Improving the bioaccessibility of lipophilic ingredient in its oral intestinal delivery by ultrasound and biological cross‐linker

Abstract BACKGROUND Great efforts have been made to improve the oral bioaccessibility of lipophilic ingredients with multi‐functionalities. Achieving intestinal delivery of lipophilic ingredients and their encapsulation in micelles composed of bile salts and lipid hydrolysates (i.e. fatty acids) is critical for improving oral bioaccessibility. Therefore, oil‐core microcapsules are considered ideal carriers of lipophilic ingredients. Previous studies have reported oil‐core/zein‐shell microcapsules constructed by a one‐step anti‐solvent process. Still, its efficacy as an intestinal delivery system was limited because if the porous shell structure. RESULTS Zein solution was pretreated with ultrasound and tannic acid (TA) cross‐linking. Composite oil‐core microcapsule (COM) with a compact shell structure was successfully prepared by using modified zein solution in the anti‐solvent process. Fourier‐transform infrared spectroscopy and circular dichroism analyses indicated that ultrasound and TA synergistically promote the conformational transition of zein from α‐helix to β‐sheet and enhance the hydrophobic interactions among protein chains. The above changes contribute to the strengthen of shell zein network. Correspondingly, COM presents superior encapsulation efficiency and environmental stability over the simple oil‐core microcapsule (SOM) prepared without the use of ultrasound and TA. Furthermore, antioxidant activity of β‐carotene was well retained during the encapsulation process. In vitro studies indicated that COM was more resistant to digestibility and acid‐induced swelling. More than 87% of β‐carotene could be released in the intestine in a sustainable way. The controllable release behavior thus promoted a significant increase in bioaccessibility of β‐carotene encapsulated in COM compared to SOM (85.9% versus 48.5%). CONCLUSION The COM generated here shows potential for bioaccessibility improvement of lipophilic ingredients. © 2022 Society of Chemical Industry.

Wei, Yun‐Shan↗

Heat and mass transfer in combustion - Fundamental concepts and analytical techniques

Fundamental combustion phenomena and the associated flame structures in laminar gaseous flows are discussed on physical bases within the framework of the three nondimensional parameters of interest to heat and mass transfer in chemically-reacting flows, namely the Damkoehler number, the Lewis number, and the Arrhenius number which is the ratio of the reaction activation energy to the characteristic thermal energy. The model problems selected for illustration are droplet combustion, boundary layer combustion, and the propagation, flammability, and stability of premixed flames. Fundamental concepts discussed include the flame structures for large activation energy reactions, S-curve interpretation of the ignition and extinctin states, reaction-induced local-similarity and non-similarity in boundary layer flows, the origin and removal of the cold boundary difficulty in modeling flame propagation, and effects of flame stretch and preferential diffusion on flame extinction and stability. Analytical techniques introduced include the Shvab-Zeldovich formulation, the local Shvab-Zeldovich formulation, flame-sheet approximation and the associated jump formulation, and large activation energy matched asymptotic analysis. Potentially promising research areas are suggested.

Law, C. K.↗

Laser writing of nitrogen-doped silicon carbide for biological modulation

Conducting or semiconducting materials embedded in insulating polymeric substrates can be useful in biointerface applications; however, attainment of this composite configuration by direct chemical processes is challenging. Laser-assisted synthesis has evolved as a fast and inexpensive technique to prepare various materials, but its utility in the construction of biophysical tools or biomedical devices is less explored. Here, we use laser writing to convert portions of polydimethylsiloxane (PDMS) into nitrogen-doped cubic silicon carbide (3C-SiC). The dense 3C-SiC surface layer is connected to the PDMS matrix via a spongy graphite layer, facilitating electrochemical and photoelectrochemical activity. We demonstrate the fabrication of arbitrary two-dimensional (2D) SiC-based patterns in PDMS and freestanding 3D constructs. To establish the functionality of the laser-produced composite, we apply it as flexible electrodes for pacing isolated hearts and as photoelectrodes for local peroxide delivery to smooth muscle sheets.

59 BASIC BIOLOGICAL SCIENCES↗

Ultraviolet Photooxidation of Smectite-Bound Fe(II) and Implications for the Origin of Martian Nontronites

Clay minerals detected with orbital and in situ instruments in ancient Martian terrains constrain Mars' climate and aqueous alteration history. Early in its history, Mars experienced an atmospheric redox change and iron-bearing clay minerals may preserve the effects of that transition. Ferrous smectites, the thermodynamically predicted product of chemical weathering of basalts under anoxic conditions, may have undergone oxidation by exposure to chemical oxidants in the atmosphere or regolith, or by direct photooxidation at the surface. To assess these potential oxidation pathways, ferrous trioctahedral smectites of varying initial iron content were synthesized and subjected to oxidation by ultraviolet (UV) irradiation. Experimental UV irradiation under an anoxic atmosphere equivalent to approximately 7 years of flux on the Martian surface caused partial oxidation of smectite-bound Fe (Fe3+/ΣFe = 16–18%) and octahedral sheet contraction. Metal-OH vibrational bands in visible/near infrared (VNIR) reflectance spectra of oxidized smectites changed in band depth and asymmetry with higher iron content. X-ray diffraction patterns of UV irradiated samples indicate the formation of a mixed di- and trioctahedral smectite or a secondary nontronite phase, possibly on the surfaces of higher iron content smectites. These experiments suggest that UV irradiation is able to oxidize structurally bound iron in smectites without the presence of other chemical oxidants. Photooxidation may have influenced the mineralogy, both syndepositionally and postdepositionally, of Martian alteration assemblages formed near the surface and this process needs not be limited to one part of their formation history. Plain Language Summary: Martian mineral assemblages observed with orbiters and rover instruments allow us to understand the planet's past climate and aqueous activity. Hydrated minerals that contain Fe(II) are of particular interest as they would have been affected by the early atmosphere becoming more oxidizing overtime, changing the structural iron into Fe(III). In this study, we synthesized Fe(II) smectites with varying iron content and irradiated them with an ultraviolet (UV) light source to test whether they could be photooxidized. Iron in the smectite minerals was incompletely oxidized by UV radiation after being exposed for the equivalent of approximately 7 years of exposure on the early Mars surface. The smectites with higher iron content showed more changes with photooxidation in their visible/near infrared spectra as well as in their X-ray diffraction patterns, two datasets collected by instruments on currently active Martian missions. These results suggest that UV photooxidation is a plausible contributor to the mineralogy and redox state of clay mineral assemblages observed at the Martian surface.

V. B. Rivera Banuchi↗

Kinetic Model for Moisture-Controlled CO 2 Sorption

The understanding of the sorption/desorption kinetics is essential for practical applications of moisture-controlled CO 2 sorption. We introduce an analytic model of the kinetics of moisture-controlled CO 2 sorption and its interpretation in two limiting cases. In one case, chemical reaction kinetics on pore surfaces dominates, in the other case, diffusive transport through the sorbent defines the kinetics. Here, we show that reaction kinetics, which is dominant in the first case, can be expressed as a linear combination of 1st and 2nd order kinetics in agreement with the static isotherm equation derived and validated in a previous paper. The interior transport kinetics can be described by non-linear diffusion equations. By combining all carbon species into a single equation, we can eliminate — in certain limits — the source terms associated with chemical reactions. In this case, the governing equation is ∂θ/∂t = –∇ · (–D eff ∇ θ ). For a sorbent in a form of a flat sheet or a membrane, one can maintain the same functional form of a diffusion equation by introducing a generalized effective diffusivity D M that combines contributions from both surface chemical reaction kinetics and interior diffusive transport kinetics. Experimental data of transient CO 2 flux in a preconditioned commercial anion exchange membrane fit well to the 1st order model as long as very dry states are avoided, validating the theory. The observed DM for a preconditioned commercial anion exchange membrane ranges from 6.6× 10 -14 to 7.1× 10 -14 m 2 s -1 at 35°C. These small values compared to typical ionic diffusivities imply a very slow kinetics, which will be the largest issue that needs to be addressed for practical application. The collected transient CO 2 flux data are used to predict the magnitude of a continuous CO 2 pumping flux in an active membrane that transports CO 2 against a CO 2 concentration gradient. The pumped CO 2 flux is supported by water flux due to a water concentration gradient.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Additive Manufacturing and Experimental Characterization of Nickel-Titanium Shape-Memory Alloy Wick Structures and Heat Pipes for Spacecraft Thermal Control

Shape memory alloys (SMA), such as those based on nickel-titanium (NiTi), are increasingly being applied as multifunctional spacecraft components. For thermal management applications, NiTi flow tubing hinges and self-deploying loop heat pipes have been demonstrated. Emerging additive manufacturing (AM) processes are enabling more complex SMA devices than can be formed from conventional plain wire, tubing, and sheet stock materials. This paper presents our progress toward applying powder bed fusion AM to producing porous NiTi wicks and NiTi-H2O heat pipes, which could be embedded in thermally deploying radiators for spacecraft thermal management. AM near-equiatomic NiTi (55.1 wt% Ni) porous wick specimens were produced with a range of deposition parameters. Transient acetone rate-of-rise experiments were performed to estimate wick permeability (K) and average pore radius (r_pore) values and identify parameter sets with high capillary performance. Surface treatments were evaluated to achieve hydrophilic wick structures. Evaluated treatments included chemical oxide growth with H2O2, oxide and sodium titanate growth with NaOH solution, and ultrasonic cleaning with specialty detergents that can remove hydrocarbon contaminants. The most durable hydrophilic surface conditions were obtained with the NaOH treatment. High performing wick deposition parameters were used to produce a full AM NiTi heat pipe, which was treated with NaOH solution to activate the wick. This heat pipe was operated on a test stand in the inverted configuration (upper evaporator and lower condenser), and demonstrated stable nearly isothermal operation for 150 hrs.

Thermal management↗

Additive Manufacturing and Experimental Characterization of Nickel-Titanium Shape-Memory Alloy Wick Structures and Heat Pipes for Spacecraft Thermal Control

Shape memory alloys (SMA), such as those based on nickel-titanium (NiTi), are increasingly being applied as multifunctional spacecraft components. For thermal management applications, NiTi flow tubing hinges and self-deploying loop heat pipes have been demonstrated. Emerging additive manufacturing (AM) processes are enabling more complex SMA devices than can be formed from conventional plain wire, tubing, and sheet stock materials. This paper presents our progress toward applying powder bed fusion AM to producing porous NiTi wicks and NiTi-H2O heat pipes, which could be embedded in thermally deploying radiators for spacecraft thermal management. AM near-equiatomic NiTi (55.1 wt% Ni) porous wick specimens were produced with a range of deposition parameters. Transient acetone rate-of-rise experiments were performed to estimate wick permeability (K) and average pore radius (r_pore) values and identify parameter sets with high capillary performance. Surface treatments were evaluated to achieve hydrophilic wick structures. Evaluated treatments included chemical oxide growth with H2O2, oxide and sodium titanate growth with NaOH solution, and ultrasonic cleaning with specialty detergents that can remove hydrocarbon contaminants. The most durable hydrophilic surface conditions were obtained with the NaOH treatment. High performing wick deposition parameters were used to produce a full AM NiTi heat pipe, which was treated with NaOH solution to activate the wick. This heat pipe was operated on a test stand in the inverted configuration (upper evaporator and lower condenser), and demonstrated stable nearly isothermal operation for 150 hrs.

Thermal management↗

p-type conductivity and damage recovery in implanted GaN annealed by rapid gyrotron microwave annealing

We demonstrate p-type activation of GaN doped by Mg ion implantation, and in situ during metalorganic chemical vapor deposition through sequential short-duration gyrotron microwave heating cycles at temperatures of 1200–1350 °C. GaN is implanted with 1019 cm−3 Mg ions, capped with AlN, and annealed under 3 MPa N2 overpressure in 5 s heating cycles for less than 60 s total using a high-power gyrotron microwave heating source. Through I–V characterization, photoluminescence spectroscopy, and Raman spectroscopy, we study the evolution of electrical properties, optically active point defects, and material strain in response to implantation and annealing. For Mg-implanted samples, increasing annealing temperature is characterized by an increase in the PL substitutional Mg-related peak (UVL) relative to the shallow-donor vacancy-related peak (GL2). Through comparison of implanted and in situ doped samples, it is demonstrated that the origin of compensating VN lies primarily in implantation rather than degradation from the annealing process. Transmission line measurements and diode I–V measurements show a sheet resistance of 1083 kΩ/□ and a hole concentration of 1.23 × 1015 cm−3, respectively, in the Mg-implanted material annealed at 1350 °C. We conclude that temperature-cycled gyrotron annealing at 1350 °C decreases implant-induced compensating point defects and activates Mg to obtain selective p-type conduction.

Meyers, V. (ORCID:0000000176731553)↗

Robust hierarchical three dimensional nickel cobalt tungstate-MXene nanocomposite for high performance symmetric coin cell supercapacitors

Design of rational electrode materials with hierarchically structured pseudocapacitive materials has been identified as a successful strategy for revamping the electrochemical characteristics of supercapacitors. However, the simultaneous assurance of strong electrical conductivity and higher specific capacitance via a simple and cost-effective synthesis protocol is of concern today. In this work, Ni-CoWO 4 incorporated MXene nanocomposite has been successfully prepared by a facile hydrothermal process. The structure, morphology, stoichiometry, and chemical characterization of the prepared Ni-CoWO 4 , Ti 3 C 2 T x , and Ni-CoWO4@MXene nanocomposite were explored extensively. MXene demonstrated a layered 2D nanoscale structure whereas pure Ni-CoWO 4 was composed of spherical nanoparticles. The composite Ni-CoWO 4 @MXene revealed the morphology of spherical Ni-CoWO 4 nanoparticles decorated on MXene sheets. Furthermore, a series of electrochemical characterizations illustrated the contribution of the delightful morphology of Ni-CoWO 4 @MXene composite to excellent electrochemistry. The resultant Ni-CoWO 4 @MXene electrode exhibited high specific capacitance of 582 Fg -1 at 1 A g -1 and 93.5 % capacitance retention over the 10,000 cycles., which is higher than that of the individual counterparts Ni-CoWO 4 and MXene. The excellent electrochemical performance of Ni-CoWO 4 @MXene is attributed to the synergistic interaction between Ni-CoWO4 nanoparticles and nanolayered MXene that may create new active sites that enhanced the charge transfer, charge/discharge kinetics and the electrical conductivity. Significantly, the unique Ni-CoWO 4 @MXene supercapacitor prototype delivered a higher energy density of 85.7 Wh kg -1 and power density of 0.85 kW kg -1 establishing its superiority over other Cosingle bondW based supercapacitors. A theoretical study was also performed to correlate the improved charge storage capacity of the prepared Ni-CoWO 4 @MXene composite.

25 ENERGY STORAGE↗

Monolayer TiS 2 Nanosheets on Au(111)–Structural Characterization and Effect of Edge Stability for Shape Control

Transition metal dichalcogenides are promising alternatives to noble metal catalysts, e.g., for (photo-)activation of greenhouse gases or hydrogenations. Herein, a direct synthetic route for 2D TiS 2 nanosheets on Au(111) by titanium deposition in the presence of a mild, organic, non-oxidizing sulfur source is presented. High-resolution scanning tunneling microscopy (STM) is used to gain atomic-level insights into the TiS 2 nanosheet morphology. In contrast to the literature, this protocol gains mostly hexagonal and truncated triangular nanosheets with an increased edge contrast in STM, analog to metallic edge states in MoS 2 . Synchrotron-based photoelectron spectroscopy allows insights into compositional details, specifically to distinguish different S sites on the TiS 2 sheets and other S species on the sample. Further, a minimum size is identified (9 S atoms side length), which underlines the importance of moiré reconstructions for stress relief. The TiS 2 sheets coexist with [Au]Ti 1 S 3 clusters, in which a single gold atom is alloyed into the surface and capped by three S atoms. Together with the finding of a critical sheet size, this points toward on-surface Ostwald ripening as a relevant process in the sheet formation. Ab-initio calculations (density functional theory) underscore that the chemical potential of S is an essential descriptor to maintain shape control.

2D nanomaterials↗

Seismoball: A Small Europa Orbiter Drop-Off Probe for Early Exploration of the Europan Surface

Recent magnetometry data received from Galileo indicate that the most likely explanation for the magnetic signature there is indeed a global conducting layer below the surface. This conducting layer is well matched by a salty, mineral rich strata beneath the Europan ice crust or a salt water ocean. Galileo imaging results show a variety of terrain types thought to contain young material; for example, lineaments, chaotic terrain, and eruption features. Additionally, Galileo images have shown indications of areas of up-welling where subsurface material periodically gets pushed to the surface due to the forces of fracturing, butting, and refreezing of the ice sheet. While Europa Orbiter will provide close-flyby high resolution images, as well as magnetometry, spectroscopy and other remote sensing data of the surface, it will not be able to provide essential engineering data like surface hardness and surface ice structure needed to support eventual landed missions. Additionally, ice chemical composition at microscopic scales can only be studied in detail through in situ instrumentation. Seismoball is a small probe designed to be injected into a surface intersect orbit around Europa. Using small reverse thrusters, the probe will be capable of nulling the high horizontal injection velocity as it approaches the 2 km surface injection altitude, thus allowing it to fall to the surface at an impact velocity of < 100m/sec (much less than the DS-2 impact velocities). The external breakaway thruster structure and crushable exterior shell absorb the impact energy while allowing the science instrument suite to remain intact. JPL has already started analyzing the entry dynamics and designing/building a small, low mass probe which will withstand the impact g-forces and fit as a 'carry-on' on board the Europa Orbiter. The probe will carry a suite of 5-6 micro-instruments for imaging the surface (both microscopic and far-field), surface and shallow subsurface ice temperatures, surface hardness, crustal dynamics and periodicity, and compositional chemistry. If selected, this flight development activity will provide a unique science opportunity and adjunct to the primary Orbiter science mission. The final flight system will be designed to accommodate orbiter mass, volume, and power interface constraints, as well as entry dynamics, g-load mitigation, and arbitrary landing orientation.

Tamppari, L.↗

Optimized Carbon Fiber Intermediate Development to Enable High-Volume Manufacturing of Lightweight Automotive Composites

The ongoing pursuit of improved fuel economy and reduced greenhouse gas emissions has resulted in sustained interest for lightweight materials technologies. In this context, carbon fiber composites have captured the imagination of automotive engineers due to the potential to achieve substantial mass reduction when compared to traditional steel construction. That stated, the use of carbon fiber composites in automotive has been limited for the most part to premium supercars and other derivative platforms. In these cases, manufacturing costs are less of an obstacle to implementation, and the performance benefits of carbon fiber have enabled production of structures offering more than 50% weight savings. In practice, translating these low-volume demonstrations onto high-volume vehicle platforms has remained challenging. This can be attributed to several factors, with the absence of suitable high throughput production methodologies being a key impediment. To date, structural, crash critical components have relied upon manufacturing techniques born out of the aerospace industry. This has created a disconnect between automotive production systems that are accustomed to manufacturing multiple parts per minute and the aerospace technologies that have cycle times in the order of hours. Consequently, the focus of this project is the development of manufacturing process technology for carbon fiber composites that can support a mainstream vehicle program at an assumed throughput of 100,000 vehicles per year. In practice, this translates to a part-to-part cycle time of less than 3 minutes. Project participation included contributions from a broad range of academic, industrial and national lab partners. The primary scope of work, being the development of new carbon fiber epoxy compounds that are stable at room temperature and suited to high throughput automated processing. For project management, the work streams were divided into six key areas, with the lead organization in parentheses. • Carbon fiber/epoxy materials formulation development and scale up (Dow) • Simulation of discontinuous near isotropic meso-structure intermediates (Purdue) • Simulation of mechanical performance of compression molded components (Purdue) • Meso-Scale morphological analysis and correlation with structural performance (UTK) • Paint and adhesion durability analysis (MSU) • Demonstrator part design, prototype production, and validation testing (Ford). The primary goal at the commencement of the project was development of a chopped carbon fiber sheet molding compound (SMC) that offered a three times improvement in tensile modulus over a comparable glass-based SMC. In addition to meeting mechanical performance targets, the resin kinetics were modified to achieve a processing cycle time of less than 3 minutes. Other critical-to-quality (CTQ) specifications were also stipulated to account for a broad range of materials and processing characteristics. To achieve the above, staff scientists at Dow Chemical created an extensive series of new epoxy blends for testing and validation. Throughout this development, a key challenge was attaining material performance goals without impacting processing behavior and paintability of finished components. The latter required a new internal mold release system being developed by Dow that was designed to complement the kinetics of the rapid cure epoxy. As a complement to work studies at the industrial partners, the teams from academia executed a series of analytical and experimental studies to investigate potential factors influencing CF-SMC performance. Unit cell models were developed to capture the meso-scale representations of the fiber matrix architecture. Results of this analysis and subsequent morphological investigations led to the design of a novel composite derivative comprising carbon fiber platelets embedded in an epoxy matrix; the platelet size and aspect ratio playing significant role in final composite properties. This approach was a departure from previous research in CF-SMC development whereby bulk filamentization or disassembly of the carbon fiber rovings had been considered the most effective means of achieving both fiber wet through and wet-out. As the course of the academia studies progressed, the aspect ratio of the fiber constituents was further optimized before finalizing material attributes and processing conditions. For the purposes of technology validation, the Ford team led a work stream devoted to the design, fabrication and testing of demonstration components. The carbon fiber SMC material has the potential to displace numerous stampings and castings on an automotive structure but ultimately vehicle closure applications were selected to showcase the abilities of the CF-SMC to achieve both mass reduction and business case for large complex structures. Using target properties established by the Dow staff scientists, the complete closure system for a full-size sedan decklid and a mid-size wagon liftgate were engineered. Prototypes for both applications were fabricated using production representative processing methods to allow for physical testing and performance validation of the CF-SMC structures. Following completion of a testing program that concluded with a FMVSS301 55 mph offset rear crash, the CF-SMC formulation was declared by the Ford team to have met all engineering requirements. To summarize, the joint development activities during this project led to significant technical breakthroughs and achievement of all milestones. The result was the development of a novel, tack-free carbon fiber molding compound that is suited to automated processing. This combined room temperature stability, fast cure kinetics, and internal mold release system facilitates cycle times that are conducive to high-volume production. The VORAFUSE M6400 successfully passed technology validation at Ford and is now eligible for consideration on future production commercial vehicle programs.

36 MATERIALS SCIENCE↗

Geochemical Changes in Response to CO 2 Injection in a CO 2 -EOR Complex in Northern Michigan (Volume II.1)

The Midwest Regional Carbon Sequestration Partnership (MRCSP) was founded in 2003 as part of the U.S. Department of Energy’s (DOE’s) Regional Carbon Sequestration Partnership initiative. Since its founding, MRCSP has made significant strides toward making CCUS a viable option for states in the region. The public/private consortium, funded through the DOE Regional Carbon Sequestration Initiative, brings together nearly 40 industry partners and 10 states. Battelle, as the project lead, oversees research, development and operations and coordinates activities among the partners. The incremental, phased approach has built a valuable knowledge base for the industry and paved the way for commercial-scale adoption of CCUS technologies. From 2008 to 2020, MRCSP Phase III focused on the development of large-scale injection projects. This report is part of a series of reports prepared under the Midwestern Regional Carbon Sequestration Partnership (MRCSP) Phase III (Development Phase). These reports summarize and detail the findings of the work conducted under the Phase III project. The report describes the geochemical monitoring program under MRCSP to use stable and radiogenic isotope geochemistry in concert with analysis of general geochemical parameters of fluids and gases and analysis of core samples to determine geochemical processes occurring in the reef structure because of CO 2 injection. Specifically, brine and gas samples were collected and analyzed to determine changes occurring between reefs prior to and following CO 2 injection. The analytical results for general geochemical parameters were modeled with chemical equilibrium models to determine if the injection of CO 2 resulted in the mineral dissolution or precipitation. Finally, core samples were collected and analyzed to determine if there was evidence of dissolution features or mineral precipitation.

01 COAL, LIGNITE, AND PEAT↗

Comparative Pore Structure and Dynamics for Bacterial Microcompartment Shell Protein Assemblies in Sheets or Shells

Bacterial microcompartments (BMCs) are protein-bound organelles found in some bacteria that encapsulate enzymes for enhanced catalytic activity. These compartments spatially sequester enzymes within semipermeable shell proteins, analogous to many membrane-bound organelles. The shell proteins assemble into multimeric tiles; hexamers, trimers, and pentamers, and these tiles self-assemble into larger assemblies with icosahedral symmetry. While icosahedral shells are the predominant form in vivo , the tiles can also form nanoscale cylinders or sheets. The individual multimeric tiles feature central pores that are key to regulating transport across the protein shell. Our primary interest is to quantify pore shape changes in response to alternative component morphologies at the nanoscale. We used molecular modeling tools to develop atomically detailed models for both planar sheets of tiles and curved structures representative of the complete shells found in vivo . Subsequently, these models were animated using classical molecular dynamics simulations. From the resulting trajectories, we analyzed the overall structural stability, water accessibility to individual residues, water residence time, and pore geometry for the hexameric and trimeric protein tiles from the Haliangium ochraceu m model BMC shell. These exhaustive analyses suggest no substantial variation in pore structure or solvent accessibility between the flat and curved shell geometries. We additionally compare our analysis to hydroxyl radical footprinting data to serve as a check against our simulation results, highlighting specific residues where water molecules are bound for a long time. Although with little variation in morphology or water interaction, we propose that the planar and capsular morphology can be used interchangeably when studying permeability through BMC pores.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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↗

Chemical and isotopic evolution of flowback fluids from the Utica Gas Shale Play, Eastern Ohio USA

For this work, hydraulic fracturing flowback fluids were collected from two Utica/Point Pleasant well pads in eastern Ohio. One site was in the wet gas zone (UPPW), while the site ~50 km south consisted of four wells on the same pad in the dry gas zone (UPPS). Samples of input fluids also were collected before and during hydraulic fracturing. Flowback fluids are Na-Ca-Cl brines with total dissolved salt (TDS) concentrations that increase over several months from ~100 to 200 g/L. The slightly higher TDS of the dry gas fluids are in part due to recycled flowback used as input fluids, and in part due to lower volume of water used in hydraulic fracturing. Concentrations of most major ions (Ca 2+ , Mg 2+ , Na + , Sr2 + , Fe, Mn, Cl – , Br – ) are similar for the five wells sampled, although small but systematic changes occur in the major element ratios over time. Most notably, an increase in the Sr/Cl ratio corresponds to an increase in the 87 Sr/ 86 Sr ratio in the fluids, suggesting interactions with a more radiogenic Sr source in the subsurface. Dissolved Ba concentrations and Ra activities were different between the two sites, reflecting a high SO 4 2– fluid used at the UPPW site, and water-rock reactions occurring during hydraulic fracturing at the UPPS site. Water oxygen (δ 18 O) and hydrogen (δD) isotopes for input fluids used in the UPPW4 well and fresh water used for the UPPS wells fall on the Global Meteoric waterline (GMWL). Flowback fluids from both sites are relatively enriched in δ 18 O and δD compared to the input, but do not appear to follow a simple mixing trend, suggesting reaction and isotopic exchange with carbonates and fractionation due to imbibition in the rock. Cl isotopes, δ 37 Cl in the FP fluids varied from ~ –0.43 to +0.13‰, the largest variation was observed in the earlier stages of flowback, while in the later stages δ 37 Cl exhibited a small but systematic increase over time, suggesting diffusion control of isotopic composition. Some of the trace species measured (dissolved Fe, Mn, thiosulfate and organic acids) do not follow the same trends as the major ions, suggesting contributions from input fluids, or microbially mediated reactions are exerting control on their concentrations. Input water chemistry exerts an important control on the Sr and Ba concentrations in flowback water. High SO 4 2– in the input fluids used for hydraulically fracturing the wet gas well leads to precipitation of barite-celestite in flowback fluids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mining Air for Fuels and Fine Chemicals

The Intergovernmental Panel on Climate Change’s 2021 report underscores that Direct Air Capture (DAC) is an essential component to limiting global warming to 2 °C, yet separating CO 2 from air and its subsequent concentration for conversion into carbon neutral fuels/chemicals or permanent storage remains energy intensive and costly. Further, most DAC technologies rely on repetitive capture and release cycles that reduces the amount of time the DAC materials are able to collect CO 2 and increases wear and tear. Moisture swing (MS) sorption within anion exchange materials utilizes differences in relative humidity to capture and concentrate CO 2 up to 500-fold with negligible energy inputs and low-cost sorbents. Molecular modeling predicts that membranes with a dry and wet side would actively transport CO 2 from its dry side to its wet side against a counter flow of H 2 O evaporating on the dry side, however, existing MS materials are too brittle to be processed into membranes to test this hypothesis. This project brought together experts in DAC materials and design, techno-economic analysis and project management at Arizona State University (ASU), polymer processing at University of Texas at Austin (UTA) and modeling gas transport and exchange at Norther Arizona University (NAU) to develop hollow fiber membranes that use energy from water evaporation to continuously pump CO 2 from air against a concentration gradient to the membranes interior and requiring significantly less energy than current DAC technologies. While this project did not meet its ultimate objectives of demonstrating an active CO 2 pumping membrane, a number of key accomplishments were made in developing low-cost, flexible anion exchange membranes (AEM) at 3.5 m 2 scale, characterizing the ionic and molecular transport within MS materials, and developing several analytical and mathematical models of the MS and pumping process leading to new fundamental knowledge about key rate limiting steps of CO 2 flux in anion exchange membranes at low water activity. Technoeconomic models show that if CO 2 fluxes ≥ 25 µmol CO 2 m -2 s -1 (membrane surface area) are achieved that cost ≤ $\$$100/tonne CO 2 captured, purified and compressed to pipeline quality is possible. The knowledge gained in this research will guide future research in developing new materials toward overcoming these rate limiting steps that in turn could enable transformative and disruptive DAC technologies needed for capturing gigatons of CO 2 per year needed to limiting global warming to 2 °C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗