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At least 415 records · Page 23

In situ detection and characterization of alkali-silica reaction damage in concrete using contactless ultrasonic wavefield imaging

Here we present work to characterize cracking damage in concrete caused by alkali-silica reactivity distress. We apply contactless ultrasonic scan inspection, exploiting Rayleigh wave scattering from concrete inhomogeneities. The scanning system utilizes a multi-channel MEMS sensor array to collect ultrasonic wavefield data from concrete subjected to ASR-promoting environments. The location and extent of ASR damage are established by internal expansion measurements from embedded strain gauges, scanning electron microscope images of cored samples, and expansion measurements from companion samples. A wavefield data processing method extracts oscillatory fields from the ultrasonic wavefield data to detect distinct zones of ASR damage. A damage index is proposed to further characterize the extent of ASR damage. The results confirm the feasibility and accuracy of the approach to characterize ASR damage in concrete. The fully contactless ultrasonic scanning measurement system does not require separate material samples and enables in situ characterization of ASR damage within concrete structures.

36 MATERIALS SCIENCE↗

Reactive transport modeling of organic carbon degradation in marine methane hydrate systems

Abstract Natural methane hydrate has often been observed in sand layers that contain no particulate organic carbon (POC), but are surrounded by organic-rich, fine-grained marine muds. In this paper, we develop a reactive transport model (RTM) of a microbially-mediated set of POC degradation reactions, including hydrolysis of POC driven by extracellular enzymes, fermentation of the resulting high-molecular weight dissolved organic carbon (HMW-DOC), and methanogenesis that consumes low-molecular weight dissolved organic carbon (LMW-DOC). These processes are mediated by two groups of microbes, fermenters and methanogens that are heterogeneously distributed in different lithologies, with the largest numbers of microbes in the large pores of coarse-grained layers. We find that the RTM can reproduce methane hydrate occurrences observed in two different geological environments, at Walker Ridge Site 313-H (Gulf of Mexico) and IODP Site U1325 (Cascadia Margin). We also find that microbes can degrade POC even if they are physically separated, as extracellular enzymes and DOC can diffuse away from where they are produced by microbes. Microbial activity is highest at relatively early times after burial at shallow depths and near lithological boundaries, where concentration gradients transport solutes to intervals that contain the most microbes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Group extraction of organic compounds present in liquid samples

An extraction device is disclosed comprising a tube containing a substantially inert, chemically non-reactive packing material with a large surface area to volume ratio. A sample which consists of organic compounds dissolved in a liquid, is introduced into the tube. As the sample passes through the packing material it spreads over the material's large surface area to form a thin liquid film which is held on the packing material in a stationary state. A particular group or family of compounds is extractable from the sample by passing a particular solvent system consisting of a solvent and selected reagents through the packing material. The reagents cause optimum conditions to exist for the compounds of the particular family to pass through the phase boundary between the sample liquid and the solvent of the solvent system. Thus, the compounds of the particular family are separated from the sample liquid and become dissolved in the solvent of the solvent system. The particular family of compounds dissolved in the solvent, representing an extract, exits the tube together with the solvent through the tube's nozzle, while the rest of the sample remains on the packing material in a stationary state. Subsequently, a different solvent system may be passed through the packing material to extract another family of compounds from the remaining sample on the packing material.

Jahnsen, Vilhelm J.↗

Development of Integrated Thermal Fluids Modeling Capability for MSRs

The DOE Nuclear Energy Advanced Modeling and Simulation (NEAMS) program supports a full range of computational thermal fluids analysis capabilities and code developments for a broad class of light-water and advanced reactor concepts. The research and development approach under thermal fluids technical area synergistically combines three length and time scales in a hierarchal multi-scale approach. To demonstrate the feasibility and capabilities of a multi-scale thermal fluids capability using these codes, a key joint effort has been pursued to develop an integrated system-and engineering-scale thermal fluids analysis capability with the MOOSE-based codes, through integration of SAM and Pronghorn, both based on the MOOSE framework. This report summarizes the progress in developing an integrated system- and engineering-scale thermal fluids analysis capability based on SAM and Pronghorn for molten salt reactors (MSRs), which gained significant interest in recently years. Two coupling approaches were studied, i.e. separate domain or domain-segregated coupling approach and the domain-overlapping approach. A series of coupled multi-physics models have been developed for a common reference molten salt fast reactor (MSFR) concept, ranging from standalone SAM system model to integrated SAM-Pronghorn-Griffin models. Both the steady state and the transient simulations are performed to the state-of-the-art simulation capabilities of NEAMS software suite in MSFR system applications. This report also covers further development and testing of the gas transport model in SAM for MSR modeling support. The presence of noncondensable gas in MSR systems would have strong impacts on fission gas removal and transport of noble metals throughout the system. Fission products removed through the off-gas system can also impact reactivity and can act as an additional point of heat removal. To ensure that the gas transport model is adequately tested, the supported modeling capabilities and features of SAM were identified, and a suite of tests were developed to test the model for each identified feature. Validation and UQ testing were also performed for the model and demonstrated that the buoyancy term, which was originally developed using non-salt/helium gas experimental data, can capture the experimental gas bubble velocity and diameter to within experimental and code uncertainty. An existing MSRE model was also modified in this work to include the gas transport model and to demonstrate the gas model behavior for realistic conditions of interest.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes (BNNTs) for Structural Applications

Boron nitride nanotubes (BNNTs) are more thermally and chemically compatible with metal- and ceramic-matrix composites than carbon nanotubes (CNTs). The lack of an abundant supply of defect-free, high-aspect-ratio BNNTs has hindered development as reinforcing agents in structural materials. Recent activities at the National Research Council - Canada (NRC-C) and the University of California - Berkeley (UC-B) have resulted in bulk synthesis of few-walled, small diameter BNNTs. Both processes employ induction plasma technology to create boron vapor and highly reactive nitrogen species at temperatures in excess of 8000 K. Subsequent recombination under controlled cooling conditions results in the formation of BNNTs at a rate of 20 g/hr and 35 g/hr, respectively. The end product tends to consist of tangled masses of fibril-, sheet-, and cotton candy-like materials, which accumulate within the processing equipment. The radio frequency plasma spray (RFPS) facility at NASA Langley (LaRC), developed for metallic materials deposition, has been re-tooled for in-situ synthesis of BNNTs. The NRC-C and UC-B facilities comprise a 60 kW RF torch, a reactor with a stove pipe geometry, and a filtration system. In contrast, the LaRC facility has a 100 kW torch mounted atop an expansive reaction chamber coupled with a cyclone separator. The intent is to take advantage of both the extra power and the equipment configuration to simultaneously produce and gather BNNTs in a macroscopic form amenable to structural material applications.

Hales, Stephen J.↗

Reactive Sequencing for Autonomous Navigation Evolving from Phoenix Entry, Descent, and Landing

Virtual Machine Language (VML) is an award-winning advanced procedural sequencing language in use on NASA deep-space missions since 1997, and was used for the successful entry, descent, and landing (EDL) of the Phoenix spacecraft onto the surface of Mars. Phoenix EDL utilized a state-oriented operations architecture which executed within the constraints of the existing VML 2.0 flight capability, compatible with the linear "land or die" nature of the mission. The intricacies of Phoenix EDL included the planned discarding of portions of the vehicle, the complex communications management for relay through on-orbit assets, the presence of temporally indeterminate physical events, and the need to rapidly catch up four days of sequencing should a reboot of the spacecraft flight computer occur shortly before atmospheric entry. These formidable operational challenges led to new techniques for packaging and coordinating reusable sequences called blocks using one-way synchronization via VML sequencing global variable events. The coordinated blocks acted as an ensemble to land the spacecraft, while individually managing various elements in as simple a fashion as possible. This paper outlines prototype VML 2.1 flight capabilities that have evolved from the one-way synchronization techniques in order to implement even more ambitious autonomous mission capabilities. Target missions for these new capabilities include autonomous touch-and-go sampling of cometary and asteroidal bodies, lunar landing of robotic missions, and ultimately landing of crewed lunar vehicles. Close proximity guidance, navigation, and control operations, on-orbit rendezvous, and descent and landing events featured in these missions require elaborate abort capability, manifesting highly non-linear scenarios that are so complex as to overtax traditional sequencing, or even the sort of one-way coordinated sequencing used during EDL. Foreseeing advanced command and control needs for small body and lunar landing guidance, navigation and control scenarios, work began three years ago on substantial upgrades to VML that are now being exercised in scenarios for lunar landing and comet/asteroid rendezvous. The advanced state-based approach includes coordinated state transition machines with distributed decision-making logic. These state machines are not merely sequences - they are reactive logic constructs capable of autonomous decision making within a well-defined domain. Combined with the JPL's AutoNav software used on Deep Space 1 and Deep Impact, the system allows spacecraft to autonomously navigate to an unmapped surface, soft-contact, and either land or ascend. The state machine architecture enabled by VML 2.1 has successfully performed sampling missions and lunar descent missions in a simulated environment, and is progressing toward flight capability. The authors are also investigating using the VML 2.1 flight director architecture to perform autonomous activities like rendezvous with a passive hypothetical Mars sample return capsule. The approach being pursued is similar to the touch-and-go sampling state machines, with the added complications associated with the search for, physical capture of, and securing of a separate spacecraft. Complications include optically finding and tracking the Orbiting Sample Capsule (OSC), keeping the OSC illuminated, making orbital adjustments, and physically capturing the OSC. Other applications could include autonomous science collection and fault compensation.

asteroid↗

RECLAIM: Electrochemical Lithium and Nickel Extraction with Concurrent Carbon Dioxide Mineralization

This project aims to develop technologies toward the production of Li and Ni from CO 2 -reactive minerals and rocks that contain Ca and Mg, while sequestering CO 2 . The technologies include acoustic stimulation and electrolytic proton production, which use electricity to liberate valuable metal ions from the surrounding mineral matrix at sub-boiling temperatures (~20-80°C). Feedstocks include Li/Ni/Ca/Mg-rich igneous and sedimentary rocks and minerals such as holmquistite, hectorite, lateritic Ni ores enriched in Mg-rich serpentine. Other examples of feedstocks that could be used include coarse grained orthocumulate, mine tailings, etc. In the first step, the electrolytic breakdown of water to H + and OH – (as well as O 2 and H 2 ) will be induced by applying an electric potential to simultaneously produce acidity and alkalinity. The solid feedstocks will be dissolved in the acidic anolyte under acoustic stimulation. Solubilized species will then undergo separation using our unique Li + -selective membranes driven by electrodialysis, leading to concentration of Li as soluble lithium silicate, from which Li 2 CO 3 can be derived by reaction with CO 2(g) while supplying cathode alkalinity. Also at the cathode, stepwise electrolytic precipitation of metal hydroxides, including Ni(OH) 2 , Ca(OH) 2 , and Mg(OH) 2 is performed along a cascade reactor in which both the applied potential and pH increase downstream, thereby simultaneously extracting and separating the metals. Finally, exposure of Ca(OH) 2 and Mg(OH) 2 to dilute CO 2 will result in CO 2 uptake in the form of Ca and Mg carbonates. The primary accomplishments include sample procurement and characterization. Progress has been made on precursor identification and mapping, establishing protocols for assessing metal extractability under sonication, and preliminary technoeconomic analysis (TEA) and life cycle analysis (LCA).

36 MATERIALS SCIENCE↗

Long‐Range Confinement‐Driven Enrichment of Surface Oxygen‐Relevant Species Promotes C−C Electrocoupling in CO 2 Reduction

Abstract CO 2 reduction is a highly attractive route to transform CO 2 into useful feedstocks, of which C 2 products are more desired than C 1 , yet face high kinetic barriers of C−C electrocoupling. Here, the engineering of pore‐enabled local confinement reaction environments is reported for tuning the enrichment of surface‐adsorbed oxygen‐relevant species and the establishment of their pronounced benefits in promoting C−C coupling over oxide‐derived Cu‐based catalysts. A new approach of utilizing the microphase separation of a block copolymer is developed to fabricate bicontinuous mesoporous CuO nanofibers (CuO‐BPNF). The enhanced confinement from long‐range mesochannels enables the adsorption of OH ad /O ad on the Cu surface at a wide negative potential range of −0.7 – −1.3 V in CO 2 reduction, which cannot be achieved over conventional deficient and short‐range pores. Constant‐potential DFT calculations reveal that the surface‐bound oxygen species weakens *CO affinity with the Cu (111) surface and lowers the kinetic barriers for both *CO−CO dimerization and *CO hydrogenation to enable *CO−CHO coupling. Accordingly, a CO 2 ‐to‐C 2 Faradaic efficiency of 74.7% over CuO‐BPNF is shown, significantly larger than counterparts with conventional pores. This work offers a general design principle of confinement engineering to manage the adsorption of reactive species for steering reaction pathways in interfacial catalysis.

Chemistry↗

Role of shell composition and morphology in achieving single-emitter photostability for green-emitting “giant” quantum dots

The use of the varied chemical reactivity of precursors to drive the production of a desired nanocrystal architecture has become a common method to grow thick-shell graded alloy quantum dots (QDs) with robust optical properties. Conclusions on their behavior assume the ideal chemical gradation and uniform particle composition. In this work, advanced analytical electron microscopy (high-resolution scanning transmission electron microscopy coupled with energy dispersive spectroscopy) is used to confirm the nature and extent of compositional gradation and these data are compared with performance behavior obtained from single-nanocrystal spectroscopy to elucidate structure, chemical-composition, and optical-property correlations. In particular, the evolution of the chemical structure and single-nanocrystal luminescence was determined for a time-series of graded-alloy “CdZnSSe/ZnS” core/shell QDs prepared in a single-pot reaction. In a separate step, thick (~6 monolayers) to giant (>14 monolayers) shells of ZnS were added to the alloyed QDs via a successive ionic layer adsorption and reaction (SILAR) process, and the impact of this shell on the optical performance was also assessed. By determining the degree of alloying for each component element on a per-particle basis, we observe that the actual product from the single-pot reaction is less “graded” in Cd and more so in Se than anticipated, with Se extending throughout the structure. The latter suggests much slower Se reaction kinetics than expected or an ability of Se to diffuse away from the initially nucleated core. It was also found that the subsequent growth of thick phase-pure ZnS shells by the SILAR method was required to significantly reduce blinking and photobleaching. However, correlated single-nanocrystal optical characterization and electron microscopy further revealed that these beneficial properties are only achieved if the thick ZnS shell is complete and without large lattice discontinuities. Thus, we identify the necessary structural design features that are required for ideal light emission properties in these green-visible emitting QDs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Compatibilization Strategy and Mechanism for Co-stabilizing Commingled Plastics and Pyrolyzed Rubber in Asphalt

Hot mix asphalt mixture is considered the ideal approach to reuse waste plastics in high-value applications because of its very high amount of usage in highway construction. However, the differences in polarity and density between polymers and asphalt lead to polymer coalescence and therefore the poor storage stability of modified asphalt. These challenges are exalted when recycling commingled plastics. This study introduced an innovative compatibilization strategy and mechanism for co-stabilizing commingled plastics and pyrolyzed rubber in asphalt. Commingled plastics were first grafted with maleic anhydride for surface activation, followed by reactive kneading with pyrolyzed rubber and crosslinking agent to form an integrated thermoplastic elastomer (ITPE) for asphalt modification. The mechanical, thermal, and interfacial behaviors of the ITPE were evaluated through tensile testing, thermogravimetric analysis, and scanning electron microscopy. The storage stability and rheological properties of the modified binder blends were evaluated through the cigar tube test and dynamic shear rheometer testing. Results demonstrated a successful formation of imide bonds in the ITPE, which can improve the strength, ductility, and thermal stability of rubber–plastic composites. Appropriate utilization of crosslinking agents can improve both rutting and fatigue resistance of ITPE-modified asphalt with good storage stability because of the co-existence of rigid plastic and soft rubbery regimes and the formation of a crosslink network. Furthermore, excessive content of crosslinker led to severe phase separation and reduced storage stability of modified binder blends. Extra crosslinker tended to float in asphalt because of its low density and caused an excessive formation of the crosslink network in the top section of the asphalt.

asphalt binder modifiers↗

An Overview of Experiments and Modeling of Polysiloxane-Coated Thermal Protection Systems for Missions to Mars, Titan, and Beyond.

Phenolic Impregnated Carbon Ablator (PICA) gained heritage during the historic Stardust mission, where it successfully returned samples from a comet’s tail and has since been instrumental in delivering payloads to the surface of Mars [1-3]. Most recently, PICA enabled the safe return of samples collected from asteroid Bennu as part of the OSIRIS-REx mission. This rich legacy underscores PICA’s critical role in allowing NASA’s most ambitious exploration missions. However, the friable nature of its phenolic phase presents challenges during handling and pre-launch activities. To mitigate this issue, PICA is coated with a polysiloxane resin system, which serves to suppress particulate dispersion and thereby safeguard spacecraft components. A comprehensive understanding of the polysiloxane resin’s behavior is imperative, as it profoundly shapes the material response of PICA during atmospheric entry by influencing its thermal and oxidative stability. This influence extends to thermocouple plugs embedded within thermal protection systems. These plugs have demonstrated their significance in missions such as Mars Science Laboratory (MSL) and Mars 2020, where the MEDLI and MEDLI2 instrumentation suites delivered in-valuable insights into the performance of thermal protection systems during entry into the Martian atmosphere [4]. Looking ahead, missions such as Dragonfly, set to descend into Titan’s dense atmosphere, aim to leverage advanced sensor technologies to further refine our understanding of thermal protection response [5]. Moreover, thermocouple plugs play an essential role in validating cutting-edge material response models, such as those pioneered under NASA’s Entry Systems Modeling Project (ESM), designed, in-part, to predict the operational integrity of thermal protection systems under the extreme stresses of atmospheric entry. To achieve these modeling goals, ground-based experiments are crucial to provide the foundational data necessary for developing and refining these predictive tools. To this end, an extensive test campaign was conducted at the Hypersonic Materials Environmental Test System (HyMETS) to investigate the high-temperature behavior of the polysiloxane resin in an air environment [6]. These experiments revealed critical phenomena, including the formation of a silicon oxycarbide layer that enhances oxidation resistance, moderates surface temperatures, and alters in-depth thermal response. Building on these findings, subsequent tests were designed to simulate atmospheric entry conditions in reactive gases, such as CO2 and N2, to mimic the environments of Mars and Titan, respectively, as well as non-reactive gases representing the atmospheres of the Ice Giants (Neptune and Uranus). A heating rate dependent decomposition mechanism has been identified for the polysiloxane resin under oxidizing conditions (Fig. 1). In the initial stage, the resin and the underlying thermal protection system undergo pyrolysis, rapidly generating a thin amorphous silicon oxycarbide interwoven with carbonaceous char and residual fibers from PICA. During the second stage, the nascent oxide layer establishes a robust, oxidation-resistant thermal barrier coating, which significantly impedes heat transfer to the underlying carbonaceous char, resulting in a stagnation of the surface temperature. A key factor contributing to this thermal resistance is the low recombination efficiency of atomic oxygen (γ), which further diminishes the heat load on the material’s interior layers [7]. Moreover, as the surface temperature stagnates, the silicon oxycarbide phase separates into distinct regions of silica and free graphite. Ultimately, when the heat flux reaches a critical threshold, a third stage is triggered, leading to the breakdown of the coating through carbothermal reduction, exposing the underlying char layer. This exposure leads to a dramatic surface temperature spike, driven by highly exothermic reactions between atomic oxygen and the char layer, further accelerating material degradation. A detailed mass and heat transfer model of PICA coated with polysiloxane resin was implemented in the Porous material Analysis Toolbox based on OpenFOAM, PATO [8]. The initial stage was considered negligible in this model because the resin decomposition occurs rapidly within a thin surface layer. Instead, the coating was directly considered as an oxygen-resistant thermal barrier coating. For the second stage, the thin amorphous silicon oxycarbide was treated as a pure silica surface to simplify the thermochemical behavior. The model ac-counts for surface equilibrium processes using representative elements of the coating-environment system. For the third stage, specific boundary conditions were developed to estimate the onset and progression of the coating removal. Two-dimensional material response simulations were conducted to compare uncoated and coated PICA using boundary conditions calibrated with HyMETS data. Fig. 2 illustrates that the simulations closely align with experimental data, successfully reproducing measured temperature profiles. This work will include the latest advancements in the coating model, including the calibration of recombination of atomic oxygen at the surface during the second phase. These simulated results will be further validated against additional CO2 data points from HyMETS, reinforcing the models’ predictive capabilities. These mechanisms and their effects on thermal protection systems, including thermochemical behavior and thermocouple probe performance in extreme environments, provide crucial insights for optimizing spacecraft designs that safeguard scientific payload and ensure mission success in future planetary exploration endeavors.

Active Oxidation↗

Tuning Surface, Phase, and Magnetization of Superparamagnetic Magnetite by Ionic Liquids: Single-Step Microwave-Assisted Synthesis

Achieving colloidal and chemical stability in ferrofluids by surface modification requires multiple steps, including purification, ex situ modification steps, and operation at high temperatures. In this study, a single-step microwave-assisted methodology is developed for iron oxide nanoparticle (IONP) synthesis utilizing a series of imidazolium-based ionic liquids (ILs) with chloride, bis(trifluoromethylsulfonyl)imide, and pyrrolide anions as the reaction media, thus eliminating the use of volatile organics while enabling rapid synthesis at 80 °C as well as in situ surface functionalization. The characterized surface functionality, hydrodynamic particle size, magnetization, and colloidal stability of the IONPs demonstrate a strong dependence on the IL structure, ion coordination strength, reactivity, and hydrophilicity. The IONPs present primarily a magnetite (Fe 3 O 4 ) phase with superparamagnetism with the highest saturation magnetization at 81 and 73 emu/g at 10 and 300 K, respectively. Depending on the IL coating, magnetization and exchange anisotropy decrease by 20 and 2–3 emu/g (at 35 wt % IL), respectively, but still represent the highest magnetization achieved for coated IONPs by a coprecipitation method. Further, the surface-functionalized superparamagnetic magnetite nanoparticles show good dispersibility and colloidal stability in water and dimethyl sulfoxide at 0.1 mg/mL concentration over the examined 3 month period. This study reports on the intermolecular and chemical interactions between the particle surface and the ILs under synthetic conditions as they relate to the magnetic and thermal properties of the resulting IONPs that are well suited for a variety of applications, including separation and catalysis.

36 MATERIALS SCIENCE↗

Probabilistic effects of porosity and chemical kinetics on the shock initiation of an octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) based explosive

In this work, we investigate the effects of porosity and chemical reactivity on the shock initiation of an HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine)-based polymer bonded explosive due to thin flyer impact using two-dimensional mesoscale simulations. Microstructural samples are computationally generated, and the calculated shock response is compared to experiments. The sample dimensions are 0.1×1.05 mm 2 , and each sample accounts for grain scale heterogeneities, including randomized grain morphology and pore spacing. Simulations are performed using the Lawrence Livermore National Laboratory (LLNL) arbitrary Lagrangian–Eulerian multi-physics code ALE3D. Chemistry and equation of states are handled with LLNL's thermochemical code Cheetah. We employ a modified Arrhenius-based chemical kinetics model that scales the temperature exponent fitting parameter with flyer shock conditions. This new model is calibrated to the mean response of experimental shock initiation thresholds for three separate Kapton flyer thicknesses. A simplified shock initiation criterion is proposed, which classifies the macroscale initiation response based on cross-sectional temperature profiles of the shocked sample. This criterion is used to further investigate the probabilistic response of the sample to variations in the mean porosity and chemical kinetics rate, and we find an inverse correlation between the shock pressure and the confidence interval of the experimental threshold velocity. Furthermore, the methodology presented in this work for quantifying the probabilistic nature of shock initiation is material agnostic. These mesoscale studies may be used to inform continuum scale models and expedite the development of future, tailored energetic formulations.

36 MATERIALS SCIENCE↗

Low impedance printed circuit radiating element

A printed circuit radiating element comprises a geometrically symmetric planar area of a conducting material separated from a ground plane by a dielectric medium. The driving point of the radiating element is at the base of a notch in one side thereof so that the driving impedance is reduced from that obtained when the element is driven at its edge. Symmetrically disposed on opposite sides of an axis of symmetry of the element along which the driving point lies are two notches which restore the electrical symmetry of the radiating element thereby to suppress higher order modes. The suppression of these higher order modes results in a radiation pattern with minimal cross-polarized energy in the principal planes and high port-to-port isolation which could not be achieved with an asymmetrical element. Two driving points may be employed with the radiating element to produce a dual linearly polarized antenna and a reactive combiner or hybrid may be employed to obtain circularly-polarized radiations. The shape of the radiating element may be square, rectangular or circular, for example, in accordance with the desired characteristics. A plurality of radiating elements may be interconnected via appropriate transmission paths to form an antenna array.

Rahm, James K.↗

Radiolytic evaluation of a new technetium redox control reagent for advanced used nuclear fuel separations

Technetium is a problematic radioisotope for used nuclear fuel (UNF) and subsequent waste management owing to its high environmental mobility and coextraction in reprocessing technologies as the pertechnetate anion (TcO 4 - ). Consequently, several strategies are under development to control the transport of this radioisotope. A proposed approach is to use diaminoguanidine (DAG) for TcO 4 - and transuranic ion redox control. Although the initial DAG molecule is ultimately consumed in the redox process, its susceptibility to radiolysis is currently unknown under envisioned UNF reprocessing conditions, which is a critical knowledge gap for evaluating its overall suitability for this role. To this end, we report the impacts of steady-state gamma irradiation on the rate of DAG radiolysis in water, aqueous 2.0 M nitric acid (HNO 3 ), and in a biphasic solvent system composed of aqueous 2.0 M HNO 3 in contact with 1.5 M N,N-di-(2-ethylhexyl)isobutyramide (DEHiBA) dissolved in n-dodecane. In addition, we report chemical kinetics for the reaction of DAG with key transients arising from electron pulse radiolysis, specifically the hydrated electron (e aq - ), hydrogen atom (H ˙ ), and hydroxyl ( ˙ OH) and nitrate (NO 3 ˙ ) radicals. The DAG molecule exhibited significant reactivity with the ˙ OH and NO 3 ˙ radicals, indicating that oxidation would be the predominant degradation pathway in radiation environments. This is consistent with its role as a reducing agent. Steady-state gamma irradiations demonstrated that DAG is readily degraded within a few hundred kilogray, the rate of which was found to increase upon going from water to HNO 3 containing solutions and solvents systems. This was attributed to a thermal reaction between DAG and the predominant HNO 3 radiolysis product, nitrous acid (HNO 2 ), k(DAG + HNO 2 ) = 5480 ± 85 M -1 s -1 . Although no evidence was found for the radiolysis of DAG altering the radiation chemistry of the contacted DEHiBA/n-dodecane phase in the investigated biphasic system, the utility of DAG as a redox control reagent will likely be limited by significant competition with its degradation by HNO 2 .

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Diverse organic carbon dynamics captured by radiocarbon analysis of distinct compound classes in a grassland soil

Soil organic carbon (SOC) is a large, dynamic reservoir composed of a complex mixture of plant- and microbe-derived compounds with a wide distribution of cycling timescales and mechanisms. The distinct residence times of individual carbon components within this reservoir depend on a combination of factors, including compound reactivity, mineral association, and climate conditions. To better constrain SOC dynamics, bulk radiocarbon measurements are commonly used to trace biosphere inputs into soils and to estimate timescales of SOC cycling. However, understanding the mechanisms driving the persistence of organic compounds in bulk soil requires analyses of SOC pools that can be linked to plant sources and microbial transformation processes. Here, we adapt approaches, previously developed for marine sediments, to isolate organic compound classes from soils for radiocarbon ( 14 C) analysis. We apply these methods to a soil profile from an annual grassland in Hopland, California (USA), to assess changes in SOC persistence with depth (down to 1 m). We measured the radiocarbon values of water-extractable organic carbon (WEOC), total lipid extracts (TLEs), total hydrolyzable amino acids (AAs), and an acid-insoluble (AI) fraction from bulk and physically separated size fractions (< 2 mm, 2 mm–63 µm, and < 63 µm). Our results show that Δ 14 C values of bulk soil, size fractions, and extracted compound classes became more depleted with depth, and individual SOC components have distinct age–depth distributions that suggest distinguishable cycling rates. We found that AAs and TLEs cycle faster than the bulk soils and the AI fraction. The AI was the most 14 C-depleted fraction, indicating that it is the most chemically inert in this soil. Our approach enables the isolation and measurement of SOC fractions that separate functionally distinct SOC pools that can cycle relatively quickly (e.g., plant and microbial residues) from more passive or inert SOC pools (associated with minerals or petrogenic) from bulk soils and soil physical fractions. With the effort to move beyond SOC bulk analysis, we find that compound class 14 C analysis can improve our understanding of SOC cycling and disentangle the physical and chemical factors driving OC cycling rates and persistence.

58 GEOSCIENCES↗

Mercury Speciation During Vitrification of LAW

n this work, laboratory and engineering-scale tests were conducted that mimic the reactive environment of the Hanford Tank Waste Treatment and Immobilization Plant (WTP) low activity waste (LAW) melter and off-gas system in order to assess the speciation of mercury at select points in the processing system. The experimental protocols, test equipment, feed materials used, and rationale for testing are detailed in the Test Plan for this work. Particular attention was paid to the amount and speciation of mercury in submerged bed scrubber (SBS) solutions, which are intended to be recycled back to the melter feed at the WTP. Results are presented from detailed mercury analysis of these solutions using Environmental Protection Agency (EPA) Method 1630 and modifications to this method for dimethyl mercury and methyl mercury as well as EPA Method 1631 and modifications to this method for total, dissolved, elemental, suspended, and ionic mercury. Testing was conducted in two separate sets of experiments: (1) One set of tests (crucible-scale furnace tests) that involved heating small batches of mercury-spiked melter feed in crucibles to determine the amount of mercury retained in the glass and the species of mercury in the exhaust gases; (2) A second set of tests (DM10 melter tests) was planned that involved creating LAW melter plenum gas compositions using the DM10 melter system, injecting mercury into the off-gas stream, and passing that stream though a reactor that simulates various plenum gas conditions. Operational issues led to the need to use one of the VSL DM100 melters in place of the planned DM10 melter for these tests. The speciation of mercury after exposure to those conditions was monitored. In both sets of tests, the exhaust gases were run through a scrubber that was intended to mimic the LAW SBS in order to determine how much of the mercury exiting the melter would be retained in the primary off-gas system fluids and in what form. After passing through the SBS, the exhaust stream was analyzed to determine particulate, ionic, elemental, and total mercury passing downstream of the SBS. In tests employing gases derived from the DM100 melter that were spiked with elemental mercury, the processing system provided gas temperatures and residence times that are representative of the WTP LAW vitrification system in order to assess the effect of those conditions on mercury speciation. The Decontamination Factor (DF) across the system in the tests with mercury-spiked DM100 melter exhaust was determined using the analytical data from EPA Method 30B (Fluegas Adsorption Mercury Speciation (FAMS TM )) exhaust samples and the amount of mercury detected in the SBS solutions. Mercury species used in melter feed crucible scale tests were divalent (chloride and iodide), monovalent (chloride and fluoride), and elemental mercury. Individual tests included only a single form of mercury in the feed. The results for total mercury mass balances in the crucible tests are also presented.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

How Does Water Dissociation Work in Bipolar Membranes?

Bipolar membranes (BPMs) create counteracting spatial gradients of pH and electrostatic potential in electrochemical systems, enabling applications in pH regulation, electrocatalysis, and separations. At the polarized junction of a BPM the water dissociation (WD, 2H2O ⇌ H3O+ + OH-) reaction can be driven, but it remains poorly understood. In this Perspective, we integrate molecular insights from bulk-water autoionization and the associated field effects with continuum descriptions of BPM electrostatics and experimental WD kinetic analyses to describe possible mechanisms of voltage-driven WD. Pristine BPM junctions highlight both the limits of primarily electric-field-driven WD and the practical challenges of junction stability at extreme reverse bias. Introducing heterogeneous catalyst layers, commonly metal oxides and graphene oxides, accelerates WD by orders of magnitude through hypothesized coupled effects in which surface acid-base functionality and high-density hydroxyl sites mediate proton-transfer steps, and catalyst mobile electronic/ionic charges redistribute the junction electric potential drop to shape the local electric fields and reactive microenvironments. Kinetic analyses suggest two regimes of heterogeneous WD mechanism, including field-driven ordering of interfacial water and a Second-Wien-Effect dissociation-barrier lowering. We conclude by defining the key unknown variables (local pH, electrostatic potential, catalyst charge state and relationships among mechanisms) and outlining experimental and multiscale modeling strategies needed for predictive WD catalysis and for controlling related ion-transfer reactions.

Wu, Yifan↗