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DOE OSTI2023

A single, improbable B cell receptor mutation confers potent neutralization against cytomegalovirus

Cytomegalovirus (CMV) is a leading cause of infant hearing loss and neurodevelopmental delay, but there are no clinically licensed vaccines to prevent infection, in part due to challenges eliciting neutralizing antibodies. One of the most well-studied targets for CMV vaccines is the viral fusogen glycoprotein B (gB), which is required for viral entry into host cells. Within gB, antigenic domain 2 site 1 (AD-2S1) is a target of potently neutralizing antibodies, but gB-based candidate vaccines have yet to elicit robust responses against this region. We mapped the genealogy of B cells encoding potently neutralizing anti-gB AD-2S1 antibodies from their inferred unmutated common ancestor (UCA) and characterized the binding and function of early lineage ancestors. Surprisingly, we found that a single amino acid heavy chain mutation A33N, which was an improbable mutation rarely generated by somatic hypermutation machinery, conferred broad CMV neutralization to the non-neutralizing UCA antibody. Structural studies revealed that this mutation mediated key contacts with the gB AD-2S1 epitope. Collectively, these results provide insight into potently neutralizing gB-directed antibody evolution in a single donor and lay a foundation for using this B cell-lineage directed approach for the design of next-generation CMV vaccines.

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS2004

DNA in a Tunnel: A Comfy Spot for Recognition - or -The Structure of BsoBI Complexed with DNA. What can we Learn about Function via Structure Determination and how can this be Applied to Bone or Muscle Biology?

The structure and function of a biologically active molecule are related. To understand its function, it is necessary (but not always sufficient) to know the structure of the molecule. There are many ways of relating the molecular function with the structure. Mutation analysis can identify pertinent amino acids of an enzyme, or alternatively structure comparison of the of two similar molecules with different function may lead to understanding which parts are responsible for a functional aspect, or a series of "structural cartoons" - enzyme structure, enzyme plus substrate, enzyme with transition state analog, and enzyme with product - may give insight in the function of a molecule. As an example we will discuss the structure and function of the restriction enzyme BsoBI from Bacillus stearothemzophilus in complex with its cognate DNA. The enzyme forms a unique complex with DNA in that it completely encircles the DNA. The structure reveals the enzyme-DNA contacts, how the DNA is distorted compared with the canonical forms, and elegantly shows how two distinct DNA sequences can be recognized with the same efficiency. Based on the structure we may also propose a hypothesis how the enzymatic mechanism works. The knowledge gained thru studies such as this one can be used to alter the function by changing the molecular structure. Usually this is done by design of inhibitors specifically active against and fitting into an active site of the enzyme of choice. In the case of BsoBI one of the objectives of the study was to alter the enzyme specificity. In bone biology there are many candidates available for molecular study in order to explain, alter, or (temporarily) suspend activity. For example, the understanding of a pathway that negatively regulates bone formation may be a good target for drug design to stimulate bone formation and have good potential as the basis for new countermeasures against bone loss. In principle the same approach may aid muscle atrophy, radiation damage, immune response changes and other risks identified for long-duration Space travel.

vanderWoerd, Mark↗

NASA NTRS2003

Fault Tolerant Homopolar Magnetic Bearings

Magnetic suspensions (MS) satisfy the long life and low loss conditions demanded by satellite and ISS based flywheels used for Energy Storage and Attitude Control (ACESE) service. This paper summarizes the development of a novel MS that improves reliability via fault tolerant operation. Specifically, flux coupling between poles of a homopolar magnetic bearing is shown to deliver desired forces even after termination of coil currents to a subset of failed poles . Linear, coordinate decoupled force-voltage relations are also maintained before and after failure by bias linearization. Current distribution matrices (CDM) which adjust the currents and fluxes following a pole set failure are determined for many faulted pole combinations. The CDM s and the system responses are obtained utilizing 1D magnetic circuit models with fringe and leakage factors derived from detailed, 3D, finite element field models. Reliability results are presented vs. detection/correction delay time and individual power amplifier reliability for 4, 6, and 7 pole configurations. Reliability is shown for two success criteria, i.e. (a) no catcher bearing contact following pole failures and (b) re-levitation off of the catcher bearings following pole failures. An advantage of the method presented over other redundant operation approaches is a significantly reduced requirement for backup hardware such as additional actuators or power amplifiers.

Li, Ming-Hsiu↗

DOE OSTI2022

UV‐induced degradation of high‐efficiency silicon PV modules with different cell architectures

Abstract Degradation from ultraviolet (UV) radiation has become prevalent in the front of solar cells due to the introduction of UV‐transmitting encapsulants in photovoltaic (PV) module construction. Here, we examine UV‐induced degradation (UVID) in various commercial, unencapsulated crystalline silicon cell technologies, including bifacial silicon heterojunction (HJ), interdigitated back contact (IBC), passivated emitter and rear contact (PERC), and passivated emitter rear totally diffused (PERT) solar cells. We performed UV exposure tests using UVA‐340 fluorescent lamps at 1.24 W·m −2 (at 340 nm) and 45°C through 4.02 MJ·m −2 (2000 h). Our results showed that modern cell architectures are more vulnerable to UVID, leading to a significant power decrease (−3.6% on average; −11.8% maximum) compared with the conventional aluminum back surface field (Al‐BSF) cells (<−1% on average). The power degradation is largely caused by the decrease in short‐circuit current and open‐circuit voltage. A greater power decrease is observed in bifacial cells with rear‐side exposure compared with those with front‐side exposure, indicating that the rear side is more susceptible to UV damage. Secondary ion mass spectroscopy (SIMS) confirmed an increase in hydrogen concentration near the Si/passivation interface in HJ and IBC cells after UV exposure; the excess of hydrogen could result in hydrogen‐induced degradation and subsequently cause higher recombination losses. Additionally, surface oxidation and hot‐carrier damage were identified in PERT cells. Using a spectral‐based analysis, we obtained an acceleration factor of 5× between unpackaged cells (containing a silicon nitride antireflective coating on the front) in the UV test and an encapsulated module (with the front glass and encapsulant blocking 90% of the UV at 294 nm and 353 nm, respectively) in outdoor conditions. From the analytical calculations, we show that a UV‐blocking encapsulant can reduce UV transmission in the module by an additional factor of ~50.

14 SOLAR ENERGY↗

DOE OSTI2023

Consideration of Nonideal Detonation Regimes Influenced by Wave Modes in a Water-Cooled Rotating Detonation Engine Using OH* Chemiluminescence

Although inherently unstable, existing research in rotating detonation combustion supports its application in notionally steady processes resulting in greater availability compared to conventional, constant pressure combustion. Further improvements rely on a more in-depth understanding of system losses and identifying conditions which optimize device performance. Within this study, the presence and proportion of ideal and nonideal combustion regimes are compared across a variety of process conditions and wave modes. Here, large-scale data analysis seeks to summarize proportional heat release associated with commensal, parasitic, and detonative combustion averaged across individual traces of OH* chemiluminescent data acquired at the detonation plane. Means of regime partitioning based on the anatomy of the time-resolved OH* signal are proposed to ensure consistent analysis throughout the current and future studies concerning combustion regimes. Of particular interest is the possible influence of wave on the nonideal combustion in relative proportion to the desired detonation. Results showed improved percent detonation with increasing significance for the following trends: decreasing equivalence ratio, increasing wave count, decreasing wave velocity, and increasing detonation time. Increased wave number, brought on by decreased equivalence ratios and wave velocities, is thought to decrease fill region surface area, and therefore, decrease nonideal contact burning. Additional analysis is performed to consider possible trend variation due to the presence of stable galloping waves, which were found to have minimal influence on relative percent detonation values. The outcome of this study suggests operational states, which correspond to increased wave quantities for increased proportions of reactants consumed by the targeted detonative combustion regime.

42 ENGINEERING↗

DOE OSTI2024

Monitoring of Photovoltaic (PV) Performance and Degradation: Integrated Renewable Energy Systems (IRES) - PV Monitoring Task

The Integrated Renewable Energy System (IRES) testbed demonstration at the Pacific Northwest National Laboratory (PNNL) Sequim campus includes development of a suite of capabilities for tracking the performance of photovoltaic (PV) renewable energy components located on a floating platform (floating PV) and on a shoreline building rooftop. The marine environment represents potentially harsh and corrosive conditions for PV modules. Compared to terrestrial PV, potential concerns for offshore PV arising from high humidity and occasional contact with saltwater, marine wildlife, and aquaculture. These environmental factors can reduce electricity generation efficiency and increase the risk of electrical faults, polymer insulation or jacketing degradation and hydrolysis of the PV cell encapsulant materials. Offshore PV modules may also be exposed to lower temperatures and buoyant and vibrating motions with a floating platform. It is not clear how the long-term performance of floating PV will be affected by these factors. To understand expected energy generation through solar cells on a floating platform, monitoring of the performance of PV modules in the marine environment is needed. This report outlines a plan for long-term testing of IRES PV components utilizing resources of the PNNL Material Aging and Detection (MAaD) Science team and the Marine and Coastal Research Laboratory (MCRL). Equipment applicable for onsite testing and real-time monitoring of the PV performance associated with environmental conditions including temperature, solar irradiance, shading and soiling is included. In case of performance loss, equipment for fault detection, failure analysis, material testing, and further troubleshooting are also available. Through establishment of this capabilities, the enabling IRES project sets the stage for future research to advance off-shore and near-shore energy options for businesses and communities.

14 SOLAR ENERGY↗

NASA NTRS1981

Microstructure of Al2O3 scales formed on NiCrAl alloys

The structure of transient scales formed on pure and Y or Zr-doped Ni-15Cr-13Al alloys oxidized for 0.1 hr at 1100 C was studied by the use of transmission electron microscopy. Crystallographically oriented scales were found on all three alloys, but especially for the Zr-doped NiCrAl. The oriented scales consisted of alpha-(Al,Cr)2O3, Ni(Al,Cr)2O4 and gamma-Al2O3. They were often found in intimate contact with each other such that the close-packed planes and directions of one oxide phase were aligned with those of another. The prominent structural features of the oriented scales were approximately equal to micrometer subgrains; voids, antiphase domain boundaries and aligned precipitates were also prevalent. Randomly oriented alpha-Al2O3 was also found and was the only oxide ever observed at the immediate oxide metal interface. These approximately 0.15 micrometer grains were populated by intragranular voids which decreased in size and number towards the oxide metal interface. A sequence of oxidation was proposed in which the composition of the growing scale changed from oriented oxides rich in Ni and Cr to oriented oxides rich in Al. At the same time the structure changed from cubic spinels to hexagonal corundums with apparent precipitates of one phase in the matrix of the other. Eventually randomly oriented pure alpha-Al2O3 formed as the stable oxide with an abrupt transition: there was no gradual loss of orientation, no gradual compositional change or no gradual decrease in precipitate density.

Smialek, J. L.↗

NASA NTRS1981

Performance of jet- and inner-ring-lubricated 35 millimeter bore ball bearings operating to 2.5 million DN

Parametric tests were conducted with a 35 millimeter bore, angular contact ball bearing having a single outer land guided cage. Lubrication was achieved by flowing oil through axial grooves and radial holes machined in the inner ring of the bearing. Test conditions were a thrust load of 667 N (150 lb), shaft speeds from 48,000 to 72,000 rpm, and an oil inlet temperature of 394 K (250 F). Data from tests where the distribution of the total oil supplied to the inner ring was 50 percent for bearing lubrication and 50 percent for bearing inner ring cooling were compared with those where the distribution pattern was 25 percent lubrication and 75 percent cooling. Successful operation was experienced with both the 50-50 and 25-75 percent flow distribution patterns to 2.5 million DN. The 50-50 percent flow pattern provided the cooler bearing operation of the two inner ring lubricated bearings. The jet lubricated bearing had lower outer ring and higher inner ring temperatures than the inner ring lubricated bearings. Maximum power loss of 2.8 kW (3.7 hp) was experienced with the 25-75 percent flow distribution, and maximum percent cage slip of 7.0 occurred at 72,300 rpm with the 50-50 percent flow distribution.

Schuller, F., T.↗

DOE OSTI2024

Quench protection for high-temperature superconductor cables using active control of current distribution

Superconducting magnets of future fusion reactors are expected to rely on composite high-temperature superconductor (HTS) cable conductors. In presently used HTS cables, current sharing between components is limited due to poorly defined contact resistances between superconducting tapes or by design. The interplay between contact and termination resistances is the defining factor for power dissipation in these cables and ultimately defines their safe operational margins. However, the current distribution between components along the composite conductor and inside its terminations is a priori unknown, and presently, no means are available to actively tune current flow distribution in real-time to improve margins of quench protection. Also, the lack of ability to electrically probe individual components makes it impossible to identify conductor damage locations within the cable. In this work, we address both problems by introducing active current control of current distribution between components using cryogenically operated metal-oxide-semiconductor-field-effect transistors (MOSFETs). We demonstrate through simulation and experiments how real-time current controls can help to drastically reduce heat dissipation in a developing hot spot in a two-conductor model system and help identify critical current degradation of individual cable components. Finally, prospects of other potential uses of MOSFET devices for improved voltage detection, AC loss-driven active quench protection, and remnant magnetization reduction in HTS magnets are also discussed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2020

Electrolyte-phobic Surface for the Next-Generation Nanostructured Battery Electrodes

Nanostructured electrodes are among the most important candidates rationally designed to enable high capacity battery chemistry. Nanostructures can solve issues such as the volume change and mechanical fragmentations. However, the high surface area they usually possess would decrease the Coulombic efficiencies, since the side chemical reactions scale with surface area. Moreover, electrodes comprised of nanomaterials have significant intakes of liquid electrolytes, which reduces the overall energy density and increases the cost of the battery. Here we present a new strategy of limiting effective surface area by introducing an “electrolyte-phobic surface”. In this study, a porous Si anode functions as a model material to demonstrate this concept. Silicon boasts high theoretical capacity, but experiences large volume change during its lithiation and delithiation processes. Porous Si can address this volume change problem with the buffer effect of its inner pores. However, porous silicon shows low initial Coulombic efficiencies and high irreversible lithium loss, owing to its intrinsic high surface area. In this report, a covalently linked perfluorinated surface coating layer on porous Si particles serves as an electrolyte-phobic protection layer, minimizing the accessible surface area for the electrolytes, decreasing the side reactions between the electrolyte and Si surface, and thus significantly enhancing the initial Coulombic efficiencies, up to ~88% compared to ~60% for the pristine porous silicon. Meanwhile, the electrolyte-phobic protection layer of Si particles keeps the silicon surface compatible with the conventional polyvinylidene fluoride (PVDF) binder, which helps to stabilize the Si electrode for long-term battery cycling.

Qian, Chenxi↗

DOE OSTI2026

Measurement of Transverse Resistance for Stacks of Non-insulated REBCO Tapes

Transverse resistance among adjacent conductors is a key parameter to calculate AC losses in superconducting cables with non-insulated conductors. The transverse pressure insert (TPI) previously developed and used at Fermilab was modified to measure transverse resistance of stacks made of non-insulated REBCO tapes as a function of transverse pressure at liquid nitrogen temperature. Pressure up to 322 MPa was applied with a hydraulic cylinder. A small current up to 10 A was flown in the stack sample through REBCO tape leads spliced above and below the stack. The latter had a bending radius larger than 6 mm to prevent the critical current degradation in REBCO leads. The voltage was measured just outside the compressed area. Stack samples included stacks of bare 4-mm wide REBCO tapes, as well as REBCO tapes alternated with 4-mm wide stainless-steel ribbons of 40 μm and 30 μm of thickness. We herein present the results of these transverse resistance measurements. Results show a stronger dependence on pressure for smaller pressure vs. larger ones. Also, of the two components of contact resistance, i.e. contact and bulk, the latter was negligible.

Tamagnini, E. [Turin Polytechnic]↗

NASA NTRS2001

Vapor/Mist Used to Lubricate Gears After Loss of Primary Lubrication System

Loss of lubrication in rotorcraft drive systems is a demanding requirement placed on drive system manufacturers. The drive system must operate for at least 30 minutes once the primary lubrication system has failed. This test is a military requirement that must be passed prior to certification of the aircraft. As new aircraft engines, operating at higher speeds, are fielded, the requirements for the drive system become increasingly more difficult. Also, the drive system must be lightweight, which minimizes the opportunity to use the gear bodies to absorb the tremendous amount of heating that takes place. In many cases, the amount of heat generated because of the high speed and load requires an emergency lubrication system that negatively impacts the aircraft's weight, complexity, and cost. A single mesh spur gear test rig is being used at the NASA Glenn Research Center to investigate possible emergency lubrication system improvements that will minimize the impact of having these systems onboard rotorcraft. A technique currently being investigated uses a vapor/mist system to lubricate the contacting surfaces after the primary lubrication system has been shut down. A number of tests were conducted in which the vapor/mist used the same lubricant as the primary system, but at a greatly reduced flow rate. Each test was initiated with the primary lubrication system operational and at steady-state conditions for a given speed and load. Then the primary lubrication system was shut down, and the vapor/mist lubrication system was initiated. An example of the tests conducted is shown in the figures. These preliminary tests have uncovered a mechanism that provides a lubricious, carbonaceous solid on the surface that actually reduces the surface temperature of the meshing gear teeth during operation. Surface analysis of the carbonaceous solid revealed it was graphitic. This mechanism is the synthetic lubricant "coking" on the active profile of the gears, which reduces the friction between the contacting gear surfaces. The level of load affects the onset of this mechanism: the higher the load, the sooner coking takes place. Future work will investigate several other factors that could improve the already promising results that have been attained.

Handschuh, Robert F.↗

DOE OSTI2026

Microstructure and Composition of Passivating Interfaces in Silicon Heterojunction Solar Modules Weathered in Different Climates

Sanyo/Panasonic patented silicon heterojunction with intrinsic thin layer (HIT) solar cells in the 1990's, which demonstrated world record photovoltaic (PV) efficiency around 2014 and inspired the newer generations of silicon heterojunction technology (SHJ) as well as the current world record back-contact PV cell designs. The high-quality passivation strategy, utilizing ultra-thin layers of hydrogenated amorphous silicon (a-Si:H), leads to high voltages and long carrier lifetimes, but these qualities may degrade over time as the modules operate outdoors. Here, we investigate local microstructure and composition at the interface layers of cells from HIT modules weathered in a hot, humid climate (Florida, USA) and temperate climate (Colorado, USA) for 10 years. We employ a comprehensive set of high-resolution electron microscopy imaging and spectroscopy to directly resolve structure and composition in these cells down to the nanoscale. We show features such as alignment of the In2O3 transparent conducting oxide and a-Si:H layers on the textured c-Si facets, interfacial oxidation at the a-Si:H/c-Si and In2O3/a-Si:H interfaces, and twinned c-Si resulting from epitaxial growth into the a-Si:H layer. Our results raise potential degradation mechanisms in these outdoor-weathered modules, but the root cause of electrical loss remains uncertain due to the very small changes in aged samples. This study shows that many atomic scale features at the In2O3/a-Si:H/c-Si interfaces are surprisingly robust, and the electrical losses with aging may either be attributed to other pathways or be very sensitive to the subtle chemical and microstructural features observed here.

14 SOLAR ENERGY↗

DOE OSTI2020

An Investigation of Liquefaction in Irradiated TRIGA Fuel Exposed to Relatively High Temperatures

This report presents the findings of an investigation into high temperature fuel cladding chemical interactions (FCCI) in Training, Research, Isotopes, General Atomics (TRIGA) fuel rods. A TRIGA fuel-rod core or meat is principally composed of uranium (U) particles dispersed in a zirconium hydride (Zr H) matrix. The fuel is clad in sealed 304SS or Incoloy 800 tubes. At high temperatures, the fuel will interact with the cladding, resulting in FCCI. To investigate the FCCI (in this case, liquefaction), irradiated TRIGA fuel rods were exposed to relatively high temperatures in furnace tests. The tests were performed at different temperatures using segments from an irradiated TRIGA fuel rod at the Hot Fuel Examination Facility located at Idaho National Laboratory (INL). The data from this study is important for developing a better understanding of the performance of U-ZrH fuel type during transient events (e.g., a Loss of Coolant Accident (LOCA) event) that may result in high temperatures while operating a TRIGA reactor. Furnace tests were run for 6 hours at 730, 800, 900, 950, and 1,000°C. One test was run for 12 hours at 950°C. Post-test microstructural characterization was performed on the heat-treated samples using optical metallography to look for evidence of liquefaction. Additionally, microstructural characterization was performed using scanning electron microscopy to investigate the microstructure of the as-irradiated fuel before heat treatment and the microstructural changes that occurred after heat treating for the 730 and 950°C heat treatments for 6 hours. Results of the analysis were compared to those produced during diffusion studies performed using unirradiated TRIGA fuel meat and type 304 stainless steel. A gap is typically present in as-irradiated fuel that limits any possibility for chemical interaction between the fuel and cladding. Optical metallography (OM) was used to identify areas in the specimens heat treated at 950 and 1000°C where fuel and cladding contact was satisfactory for the FCCI to transpire. The bulk of the interaction zones that form due to FCCI developed in the fuel meat and not as much in the cladding. Even in the sample tested at 1,000°C, no evidence was found that gross fuel meat or cladding melting had occurred. Only limited porosity was found in the fuel meat that possibly could have been due to melting of a particular precipitate phase or phases that had formed during FCCI. These results agreed with those reported for the unirradiated diffusion couple studies.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

NASA NTRS2003

Guide for Hydrogen Hazards Analysis on Components and Systems

The physical and combustion properties of hydrogen give rise to hazards that must be considered when designing and operating a hydrogen system. One of the major concerns in the use of hydrogen is that of fire or detonation because of hydrogen's wide flammability range, low ignition energy, and flame speed. Other concerns include the contact and interaction of hydrogen with materials, such as the hydrogen embrittlement of materials and the formation of hydrogen hydrides. The low temperature of liquid and slush hydrogen bring other concerns related to material compatibility and pressure control; this is especially important when dissimilar, adjoining materials are involved. The potential hazards arising from these properties and design features necessitate a proper hydrogen hazards analysis before introducing a material, component, or system into hydrogen service. The objective of this guide is to describe the NASA Johnson Space Center White Sands Test Facility hydrogen hazards analysis method that should be performed before hydrogen is used in components and/or systems. The method is consistent with standard practices for analyzing hazards. It is recommended that this analysis be made before implementing a hydrogen component qualification procedure. A hydrogen hazards analysis is a useful tool for hydrogen-system designers, system and safety engineers, and facility managers. A hydrogen hazards analysis can identify problem areas before hydrogen is introduced into a system-preventing damage to hardware, delay or loss of mission or objective, and possible injury or loss of life.

Beeson, Harold↗

NASA NTRS2004

New Hydrophilic, Composite Membranes for Air Removal from Water Coolant Systems

Liquid coolants are commonly used as thermal transport media to increase efficiency and flexibility in aerospace vehicle design. The introduction of gas bubbles into the coolant can have negative consequences, including: loss of centrifugal pump prime, irregular sensor readings, and blockage of coolant flow to remote systems. One solution to mitigate these problems is the development of a passive gas removal device, or gas trap, installed in the flight cooling system. In this study, a new hydrophilic, composite membrane has been developed for passage of the coolant fluid and retention of gas bubbles. The trapped bubbles are subsequently vented from the system by a thin, hydrophobic, microporous membrane. The original design for this work employed a homogeneous membrane that was susceptible to fouling and pore plugging. Spare gas traps of this variety have degraded during storage, and recreation of the membranes has been complicated due to problems with polymer duplication and property variations in the final membranes. In this work, replacements have been developed based on deposition of a hydrophilic polymer on the bore-side of a porous polyethylene (PE) tube. The tube provides excellent chemical and mechanical stability, and the hydrophilic layer provides retention of gas bubbles. Preliminary results have shown that intimate contact is required between the deposited layer and the substrate to overcome material differences. This has been accomplished by presoaking the membrane tube in the solvent to raise its surface energy. Polymer solutions of various concentrations have been used to promote penetration of the polymer layer into the porous substrate and to control separation layer thickness. The resulting composite membranes have shown repeatable decrease in nitrogen permeability, which is indicative of a decrease in membrane pore size. Studies with water permeation have yielded similar results. We have observed some swelling of the added polymer layer, which causes a slight decrease in membrane pore size, and should result in improved bubble retention. Preliminary studies have also been performed on gas retention in flowing systems. Initial results have been promising, with negligible gas permeation for the coated membranes compared to 100% gas permeation in the uncoated tube.

Ritchie, Stephen M. C.↗

DOE OSTI2021

Labile Fe(III) supersaturation controls nucleation and properties of product phases from Fe(II)-catalyzed ferrihydrite transformation

We report Fe(II)-catalyzed ferrihydrite (Fh) transformation to more crystalline iron (oxyhydr)oxide phases is a widely occurring geochemical process which has been extensively studied as a function of Fe(II)/Fh ratios at fixed Fh loadings. However, recent isolation of an intermediate Fe(III) species resulting from Fe(II)-Fh contact that facilitates transformation by dissolution/reprecipitation suggests that the kinetics and properties of product phases will instead depend mostly on its rate of accumulation to a critical concentration, consistent with principles in the classical nucleation theory (CNT). This suggests a dependence both on the loading of Fe(II) on the surface, which controls the rate of labile Fe(III) formation, as well as the available volume of solution, which also impacts how fast it can achieve its critical concentration to nucleate product phases. To specifically examine the latter effect, here we studied transformation of 15 mg Fh in 1 mM FeSO 4 solutions at pH 7.2 in batch suspensions of 30 mL, 150 mL, and 450 mL volumes. Time-dependent concentrations of aqueous Fe(II), surface-associated Fe(II), and resulting labile Fe(III) were monitored along with bulk solids characterization as a function of time. Transmission electron microscopy (TEM) was used to visualize the evolution of phases at identical locations on TEM grids. The collective results show that the rates of Fh loss and emergence of product lepidocrocite (Lp) and goethite (Gt) as well as their phase proportions, nucleation mode and morphological properties depend directly on the rate of accumulation of the labile Fe(III) precursor to its critical concentration, which in our experiments was controlled simply by varying the available volume of solution into which it enters. Statistical analyses of TEM image data suggest that while both heterogeneous and homogeneous nucleation occurred in all experiments, the former was increasingly favored at lower Fh/solution ratio due to its lower nucleation barrier being more favorable at attendant lower supersaturations of Fe(III).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Magnetic braking saturates: evidence from the orbital period distribution of low-mass detached eclipsing binaries from ZTF

ABSTRACT We constrain the orbital period (Porb) distribution of low-mass detached main-sequence eclipsing binaries (EBs) with light-curves from the Zwicky Transient Facility (ZTF), which provides a well-understood selection function and sensitivity to faint stars. At short periods (Porb ≲ 2 d), binaries are predicted to evolve significantly due to magnetic braking (MB), which shrinks orbits and ultimately brings detached binaries into contact. The period distribution is thus a sensitive probe of MB. We find that the intrinsic period distribution of low-mass (0.1 ≲ M1/M⊙ < 0.9) binaries is basically flat (${\rm d}N/{\rm d}P_{\rm orb} \propto P_{\rm orb}^0$) from Porb = 10 d down to the contact limit. This is strongly inconsistent with predictions of classical MB models based on the Skumanich relation, which are widely used in binary evolution calculations and predict ${\rm d}N/{\rm d}P_{\rm orb} \propto P_{\rm orb}^{7/3}$ at short periods. The observed distributions are best reproduced by models in which the magnetic field saturates at short periods with a MB torque that scales roughly as $\dot{J}\propto P_{\rm orb}^{-1}$, as opposed to $\dot{J} \propto P_{\rm orb}^{-3}$ in the standard Skumanich law. We also find no significant difference between the period distributions of binaries containing fully and partially convective stars. Our results confirm that a saturated MB law, which was previously found to describe the spin-down of rapidly rotating isolated M dwarfs, also operates in tidally locked binaries. We advocate using saturated MB models in binary evolution calculations. Our work supports previous suggestions that MB in cataclysmic variables (CVs) is much weaker than assumed in the standard evolutionary model, unless mass transfer leads to significant additional angular momentum loss in CVs.

El-Badry, Kareem (ORCID:0000000268711752)↗