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Non-destructive Quantitative Phase Analysis and Microstructural Characterization of Zirconium Coated U-10Mo Fuel Foils via Neutron Diffraction

This report uses neutron diffraction to investigate the crystal phase composition of uranium-molybdenum alloy foils (U-10Mo) for the CONVERT MP-1 Reactor Conversion Project, and determines the effect on alpha-uranium contamination following the deposition of a Zr metal diffusion layer by various methods: plasma spray deposition of Zr powders at LANL and hot co-rolling with Zr foils at BWXT. In summary, there is minimal decomposition of the gamma phase U-10Mo foil to alpha phase contamination following both plasma spraying and hot co-rolling. The average unit cell volume, i.e. lattice spacing, of the Zr layer can be mathematically extracted from the diffraction data; co-rolled Zr matches well with literature values of bulk Zr, while plasma sprayed Zr shows a slight increase in the lattice spacing, indicative of interstitial oxygen in the lattice. Neutron diffraction is a beneficial alternative to conventional methods of phase composition, i.e. x ray diffraction (XRD) and destructive metallography. XRD has minimal penetration depth in high atomic number materials, particularly uranium, and can only probe the first few microns of the fuel plate; neutrons pass completely through the foil, allowing for bulk analysis of the foil composition and no issues with addition of cladding layers, as in the final, aluminum-clad reactor fuel plates. Destructive metallography requires skilled technicians, cutting of the foil into small sections, hazardous etching conditions, long polishing and microscopy times, etc.; the neutron diffraction system has an automated sample loader and can fit larger foils, so there is minimal analysis preparation; the total spectrum acquisition time is ~ 1 hour per sample. The neutron diffraction results are limited by spectra refinement/calculation times and the availability of the neutron beam source. In the case of LANSCE at Los Alamos, the beam operates ~50% of the year. Following the lessons learned from these preliminary results, optimizations to the process and analysis can be made, and neutron diffraction can become a viable and efficient technique for gamma/alpha phase composition determination for nuclear fuels.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Delayed Gamma-Ray Spectroscopy for Non-Destructive Assay of Nuclear Materials

High-­energy, beta-delayed gamma-­ray spectroscopy is a potential, non-­destructive assay techniques for the independent verification of declared quantities of special nuclear materials at key stages of the fuel cycle and for directly assaying nuclear material inventories for spent fuel handling, interim storage, reprocessing facilities, repository sites, and final disposal. Other potential applications include determination of MOX fuel composition, characterization of nuclear waste packages, and challenges in homeland security and arms control verification. Experimental measurements were performed to evaluate fission fragment yields, to test methods for determining isotopic fractions, and to benchmark the modeling code package. Experimental measurement campaigns were carried out at the IAC using a photo-­neutron source and at OSU using a thermal neutron beam from the TRIGA reactor to characterize the emission of high-­energy delayed gamma rays from 235 U, 239 Pu, and 241 Pu targets following neutron induced fission. Data were collected for pure and combined targets for several irradiation/spectroscopy cycle times ranging from 10/10 seconds to 15/30 minutes.The delayed gamma-ray signature of 241 Pu, a significant fissile constituent in spent fuel, was measured and compared to 239 Pu. The 241 Pu/ 239 Pu ratios varied between 0.5 and 1.2 for ten prominent lines in the 2700-­3600 keV energy range. Such significant differences in relative peak intensities make it possible to determine relative fractions of these isotopes in a mixed sample. A method for determining fission product yields by fitting the energy and time dependence of the delayed gamma-­ray emission was developed and demonstrated on a limited 235 U data set. De-­convolution methods for determining fissile fractions were developed and tested on the experimental data. The use of high count-­rate LaBr 3 detectors was investigated as a potential alternative to HPGe detectors. Modeling capabilities were added to an existing framework and codes were adapted as needed for analyzing experiments and assessing application-­specific assay concepts. A de-­convolution analysis of the delayed gamma-­ray response spectra modeled for spent fuel assemblies was performed using the same method that was applied to the experimental spectra.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Preliminary critical experiments validation of a lattice physic code LATC - 14415

Core and System Integrated Engine for design and analysis (COSINE) is an integrated nuclear engineering code package, which is being developed by State Nuclear Power Software Development Center (SNPSDC) in China. A lattice physics code named LATC is included in COSINE.LATC is a 2D, steady-state code for modeling PWR fuel. A WIMS-D 69 group micro library based on ENDF/B-VI is used and there are two transportation methods in LATC, such as two steps method (collision probability method for cell homogenization, discrete coordinate method for assembly homogenization) and one step method (MOC). The UO{sub 2} fuel assembly, which may contain guide tubes, burnable poisons such as Integral Fuel Burnable Absorbers (IFBA) / Wet Annular Burnable Absorbers (WABA)/ Pyrexes or control rods etc, can be calculated in LATC. LATC provides the required cross-section data for the core physics simulator analysis code in COSINE. In order to evaluate the quality of the LATC, a strategy of validation is researched and applied to the LATC. Firstly, a validation requirement analysis is performed, and the corresponding critical experiments are collected, and then a critical experimental matrix considering the variety of fuel enrichments, fuel pitch and water to uranium ratio is generated. Finally, a comparison of results between LATC using collision probability and discrete coordinate method and critical experiments are made to make sure that the code works well. According to the validation strategy discussed above, the preliminary validation is carried out and critical experiments are calculated according to the critical experimental matrix and results from LATC code are compared with reference results. The result shows that the calculated results agree well with critical experiments, and do not indicate any significant trends with respect to the various conditions considered. (authors)

42 ENGINEERING↗

Evaluation of mineral reactive surface area estimates for prediction of reactivity of a multi-mineral sediment

Our limited understanding of mineral reactive surface area contributes to significant uncertainties in quantitative simulations of reactive chemical transport in subsurface processes. Continuum formulations for reactive transport typically use a number of different approximations for reactive surface area, including geometric, specific, and effective surface area. In this work, reactive surface area estimates are developed and evaluated for their ability to predict dissolution rates in a well-stirred flow-through reactor experiment using disaggregated samples from the Nagaoka pilot CO 2 injection site (Japan). The disaggregated samples are reacted with CO 2 acidified synthetic brine under conditions approximating the field conditions and the evolution of solute concentrations in the reactor effluent is tracked over time. The experiments, carried out in fluid-dominated conditions at a pH of 3.2 for 650 h, resulted in substantial dissolution of the sample and release of a disproportionately large fraction of the divalent cations. Traditional reactive surface area estimation methods, including an adjusted geometric surface area and a BET-based surface area, are compared to a newly developed image-based method. Continuum reactive transport modeling is used to determine which of the reactive surface area models provides the best match with the effluent chemistry from the well-stirred reactor. The modeling incorporates laboratory derived mineral dissolution rates reported in the literature and the initial modal mineralogy of the Nagaoka sediment was determined from scanning electron microscopy (SEM) characterization. The closest match with the observed steady-state effluent concentrations was obtained using specific surface area estimates from the image-based approach supplemented by literature-derived BET measurements. To capture the evolving effluent chemistry, particularly over the first 300 h of the experiment, it was also necessary to account for the grain size distribution in the sediment and the presence of a highly reactive volcanic glass phase that shows preferential cation leaching.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deuterium Permeation Through a Self-Supported Palladium-Silver Membrane in Helium Gas Mixtures

Palladium membranes and membrane reactors can separate and purify tritium from impurities in the plasma exhaust processing system for the fusion energy fuel cycle. Membranes can also act as a continuous separation method to remove tritium from helium streams in the breeder blanket tritium extraction system, such as from the purge gas of solid breeders. To investigate the potential of these membranes for these applications, we performed a deuterium permeation campaign with a self-supported palladium-silver (Pd-25Ag wt%) tube of 0.15 m length, 76 µ m wall thickness, and 3.0 mm inner diameter. A gas mixture of 3.95% D 2 and a balance of He was delivered to the inside of the tube and D permeated radially outwards through the membrane into a vacuum chamber. Permeation experiments were conducted at 300 ° C, 350 ° C, 400° C, and 450°C, from 100 to 1000 sccm total flow rate, and with total pressures of 90, 150, 190, and 250 kPa. Further, deuterium permeation was consistently lower than predicted from diffusion-limited permeation models, thus we developed a transport model that included gas-phase mass transfer and surface reactions to model experimental results. The dissociation constant was optimized to fit the developed model to experimental data.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Acoustic Monitoring of Pyroprocessing Equipment

This paper provides an introduction to using acoustic monitoring to advance detection techniques for pyroprocessing in support of nuclear safeguards and non-proliferation. The usage of free air acoustic monitoring has been previously demonstrated at Idaho National Laboratory (INL) facilities such as the Advanced Test Reactor and the National Security Test Range. However, the proposed work revolves around a new deployment environment, the Fuel Conditioning Facility, that brings forward several questions regarding the performance of the technology in non-free air media. The confinement of the pyroprocessing equipment to a heavily shielded hot cell, the atmosphere of the hot cell containing argon gas, and the radiation dose inside the hot cell are all new environments for acoustic monitoring. To our knowledge, acoustic measurements have not been completed in such an environment before. This offers a new opportunity to study not only the acoustic signatures of the equipment inside of the hot cell, but also the propagation of the signals through the hot cell and at distances away from their origination. The objective of this paper is to explain the planned instruments to monitor the Fuel Conditioning Facility in order to evaluate acoustic signals emitted from equipment during various stages of operation. Identifying these signals can potentially enable the identification of specific pieces of equipment used in pyroprocessing and produce information of their operational status. If successful, this type of monitoring could offer a new method to aid in safeguards and proliferation detection of pyroprocessing activities.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

Prediction of the energetic particle redistribution by an improved critical gradient model and analysis of the transport threshold

Based on the theory of critical gradient model (CGM) and following the simulation method proposed by Waltz et al., a combination of TGLFEP and EPtran code is employed to predict the energetic particle (EP) transport induced by Alfvén eigenmodes (AEs). To be consistent with the experiment, recent improvements to the simulation method include consideration of threshold evolution and orbit loss due to finite orbit width. The revised CGM is applied to simulate two DIII-D experimental discharges (#142111 and #153071). It well reproduces the experimental profiles with multiple unstable AEs and large-scale EP transport. Discharge #142111 had previously been simulated using a nonlinear MHD-kinetic code MEGA with a transport mechanism based on stochasticity induced by overlapping AE. By comparing the simulated EP profiles, we find that the AE transport threshold is approximated by both the MEGA nonlinear stability threshold and the proposed CGM threshold (error <5% for single n and <17% for multiple n simulation). Both of them are larger than the linear stability threshold of the most unstable AE mode by a quantity of the order of the flux needed to sustain EP transport by the background turbulence. Additionally, we have also applied the improved CGM to simulate the α particle redistribution for a China Fusion Engineering Test Reactor steady state scenario. Because of the clear separation between the AE unstable region and the loss cone, only a moderate α particle loss of ~9.6% is predicted.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Design Rules for Carboborothermic Reduction Synthesis of High Uranium Density UB 4 –UBC Composites

Uranium borides are promising candidate fuel forms for use in advanced nuclear reactors due to their high thermal conductivity and potential for dual use as both fuel and burnable absorber. In this work, uranium tetraboride () and uranium monoboroncarbide (UBC) composite were synthesized by using industrially scalable carboborothermic reduction method. The final uranium boride phase composition is sensitive to the sample holding crucibles ( and graphite) such that graphite supply excess carbon, promoting the formation of a predominant UBC phase. The high‐temperature in situ synchrotron X‐ray diffraction of pristine –UBC show persistence , UBC, and phases while preoxidized –UBC leads to predominant and formation due to progressive oxidation and boron loss at high temperature. The oxidation behavior was further characterized using thermogravimetric analysis, allowing direct comparison with other potential accident tolerant fuels such as , , UC, and UN. The –UBC shows higher uranium loading than monolithic and demonstrates promising oxidation behavior at high temperature, pointing to its potential as an improved uranium boride‐based fuel form.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Assessment of Activation on Level L3 of the Tokamak Building due to the ITER Tokamak Cooling Water System

The ITER fusion reactor is being built to demonstrate the feasibility of fusion power and will be the largest tokamak in the world. The tokamak cooling water system (TCWS) will extract the heat generated during operations and includes large amounts of piping and equipment such as pumps and heat exchangers (HXs) that are located in a large shielded region on level L3 of the tokamak building. During operation, water in the TCWS will be activated by plasma neutrons and then flow into this shielded region. The activated coolant will in turn activate the steel in the TCWS during operation and result in an activation gamma source and radiation responses that must be assessed to inform equipment selection and maintenance schedules.The activation of materials in the shielded region of level L3 was assessed at several decay times and for different equipment options using the Oak Ridge National Laboratory (ORNL) shutdown dose rate (SDDR) code suite. The ORNL SDDR code suite implements the rigorous two-step method using the Multi-Step Consistent Adjoint-Driven Importance Sampling (MS-CADIS) method to create effective neutron variance reduction parameters for the photon response of interest. In conclusion, two different HX designs, shell and tube and shell and plate, were considered, as well as the impact of cobalt impurities in steel equipment.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Mesh Adaptive Search Optimization in SERPENT2 Stereolithography Geometry

SERPENT2 Monte Carlo program has the capability to model reactor cores by stereolithography (STL) geometry. In this geometry, volumes are defined by the union of triangulated surfaces. Using the STL geometry offers unique benefits, including: 1) the model can be printed on 3D printers; 2) the possibility to use directly geometrical models from Computer-Aided Design (CAD); 3) the capability to perform multi-physics simulations coupling neutronics, thermal-hydraulics, and material science computations. In this work the STL geometry has been created by the CUBIT software, which is designed for finite elements mesh generation. The materials in the STL geometry have been assigned by a simple C program using the colors of the volumes in the CUBIT model. The goal of this work is to minimize the SERPENT2 computing time using mesh adaptive search algorithms. The basic idea is to split the geometry of the core into two zones: one zone containing the fuel elements (including the moderator and the coolant) and the other containing the reflector (and the target zone of the core, if it is driven by an external neutron source). By performing this splitting, two separate meshes are used, which results in a considerable computing time saving. (authors)

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

The influence of electron discharge and magnetic field on calcium carbonate (CaCO{sub 3}) precipitation

The influences of electron discharge and magnetic field on calcium carbonate (CaCO{sub 3}) precipitation in water have been successfully investigated. The study used three pairs of magnetic field 0.1 T whilst the electron discharge was generated from television flyback transformer type BW00607 and stainless steel SUS 304 as an electrode. The water sample with an initial condition of 230 mg/L placed in the reactor with flow rate 375 mL/minutes, result showed that the electron discharge can be reduced contain of calcium carbonate the water sample around 17.39% within 2 hours. Meanwhile for the same long period of treatment and flow rate, around 56.69% from initial condition of 520 mg/L of calcium carbonate in the water sample can be achieved by three pairs of magnetic field 0.1 T. When the combination of three pairs of magnetic field 0.1 T and the electron discharge used for treatment, the result showed that the combination of electron discharge and magnetic field methods can be used to precipitate calcium carbonate in the water sample 300 mg/L around 76.66% for 2 hours of treatment. The study then investigated the influence of the polar position of the magnetic field on calcium carbonate precipitation. Two positions of magnetic field were tested namely the system with alternated polar magnetics and the system without inversion of the polar magnetics. The influence of the polar position showed that the percentage reduction in levels of calcium carbonate in the water sample (360 mg/L) is significant different. Result showed that the system without inversion of the polar magnetics is generally lower than the system with alternated polar magnetics, with reduction level at 30.55 and 57.69%, respectively.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Dry Storage of Encapsulated Defective Fuel Rods at Doel 1 and 2 in Belgium - 17581

The project of removing all fissile and non-fissile material out of the spent fuel ponds of Belgian Doel power plant is on-going and in that framework, a solution was needed for evacuating all used fuel elements from Doel 1 and 2 storage pool, including Defective Fuel Assemblies (DFA) and Defective Fuel Rods (DFR). Following the moving out of storage pool, all used fuel elements are intended to be loaded in dry storage casks, this used fuel management option being the one implemented today in Belgium while waiting for final management. Synatom, in charge of all fuel cycle related activities for the nuclear power plants of Belgium and Engie-Electrabel, the operator of both Belgium power plants (Doel and Tihange), had then to find an industrial solution for emptying Doel 1 and 2 used fuel pool and loading DFR in dry storage casks. After having thoroughly reviewed the possible options for implementing dry storage of DFR, Synatom selected AREVA technology. It consists in: - encapsulating each DFR by loading the fuel rod in a capsule, drying the fuel rod using a process which allows to physically verify with high accuracy the residual water content inside the DFR, and welding the capsule, - assembling the capsules in a capsule canister (a skeleton with external dimensions similar to fuel assembly's) and - transferring this capsule canister along with intact fuel assemblies in an associated dry transport and storage (dual purpose) cask, as already used for interim storage of used fuel at Doel site. The French as well as the Belgian competent authorities are parties to the licensing process project. The purpose of the paper is to present the on-going industrial project related to dry storage of dried and encapsulated DFR - along with intact used fuel in dual purpose casks - at Doel 1 and 2 in Belgium, its challenges and progress. The paper presents: - why the drying method, welded capsule and associated cask is the best available technology for dry storage of DFR; - a focus on fuel assembly repair operations (initial step before encapsulation) per-formed in 2015 which consisted in successful extraction of four DFR from their original fuel assembly, using proven and experienced methods and tools; - in conclusion, an update of Doel 1 and 2 DFR dry storage project: reaching of major qualifications and licensing milestones and overview of the project perspectives. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Demonstration of transient CHI startup using a floating biased electrode configuration

Abstract Results from the successful solenoid-free plasma startup using the method of transient coaxial helicity injection (transient CHI) in the QUEST spherical tokamak (ST) are reported. Unlike previous applications of CHI on HIT-II and on NSTX which required two toroidal insulating breaks to the vacuum vessel, QUEST uses a first of its kind, floating single biased electrode configuration, which does not use such a vacuum break. Instead, the CHI electrode is simply insulated from the outer lower divertor plate support structure. This configuration is much more suitable for implementation in a fusion reactor than the previous configurations. Transient CHI generated toroidal currents of 135 kA were obtained. The toroidal current during the formation of a closed flux configuration was over 50 kA. These results bode well for the application of transient CHI in a new generation of compact high-field STs and tokamaks in which the space for the central solenoid is very restricted.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Solar Thermochemical Ammonia Production (STAP) (Final Report)

Ammonia (NH 3 ) is an energy-dense chemical and a vital component of fertilizer. In addition, it is a carbon-neutral liquid fuel and a potential candidate for thermochemical energy storage for high-temperature concentrating solar power (CSP). Currently, NH 3 synthesis occurs via the Haber-Bosch process, which requires high pressures (15-25 MPa) and medium to high temperatures (400-500 °C). N 2 and H 2 are essential feedstocks for this NH 3 production process. H 2 is generally derived from methane via steam reforming; N 2 is sourced from air, after oxygen removal via combustion of hydrocarbons. Both processes consume hydrocarbons, resulting in the release of CO 2 . In addition, hydrocarbon fuels are burned to produce the heat and mechanical energy required to perform the NH 3 reaction, further increasing CO 2 emissions. Overall, the production of ammonia via the Haber-Bosch (H-B) process is responsible for up to 1.4% of the world’s carbon emissions. The development of a renewable pathway to NH 3 synthesis, which utilizes concentrated solar irradiation as a process heat instead of fossil fuels and operates under low or ambient pressure, will result in a decrease (or elimination) of greenhouse gas emissions as well as avoid the cost, complexity, and safety issues inherent in high-pressure processes. Most current efforts to “green” ammonia production involve either electrolysis or simply replacing the energy source for H-B with renewable electricity, but otherwise leaving the process intact. The effort proposed here would create a new paradigm for the synthesis of NH 3 utilizing solar-thermal heat, water, and air as feedstocks, providing a truly green method of production. The overall objective of the STAP (Solar Thermal Ammonia Production) project was to develop a solar thermochemical looping technology to produce and store nitrogen (N 2 ) from air for the subsequent production of ammonia (NH 3 ) via an advanced two-stage process. The goal is a cost-effective and energy efficient technology for the renewable N 2 production and synthesis of NH 3 from H 2 (produced from H 2 O) and air using solar-thermal energy from concentrating sunlight, under pressures an order of magnitude lower than H-B NH 3 production. Our process involves two looping cycles, which do not require catalysts and can be recycled. Over the course of the STAP project, we (1) developed and deeply characterized oxide materials for N 2 separation; (2) developed a method for the synthesis of metal nitrides, producing a series of quaternary compounds that have been heretofore unreported; (3) modeled, designed, and fabricated bench-scale tube and on-sun reactors for the N 2 production step and demonstrated the ability to separate N 2 over multiple cycles in the tube reactor; (4) designed and fabricated a bench-scale Ammonia Synthesis Reactor (ASR) and demonstrated the proof of concept of NH 3 synthesis via a novel looping process using metal nitrides over multiple cycles; and (5) completed a systems- and technoeconomic analysis showing the feasibility of ammonia production on a larger scale via the STAP process. The development of renewable, low-cost NH 3 will be of great interest to the chemicals industry, particularly agricultural sectors. The CSP industry should be both an important customer and potential end-user of this technology, as it affords the capability of synthesizing a promising thermochemical storage material on-site. Since the NH 3 synthesis step also requires H 2 , there will exist a symbiotic relationship between this technology and solar-thermochemical water-splitting applications. Green ammonia synthesis will result in the decarbonization of a hydrocarbon-intensive industry, helping to meet the Administration goal of industrial decarbonization by 2050. The resulting decrease in CO 2 and related pollutants will improve health and well-being of society, particularly for those living in the vicinity of commercial production plants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

50-kWth methane/air chemical looping combustion tests with commercially prepared CuO-Fe 2 O 3 -alumina oxygen carrier with two different techniques

CuO-Fe 2 O 3 /alumina oxygen carriers were manufactured using two different techniques (i.e., spray drying and wet granulation). The spray drying method produced porous, spherical particles in the range of 100–200 µm. The wet granulation, or tumbling method, produced particles in the range of 200–600 µm. Both batches of material showed good gas conversion and particle durability during tests in NETL’s 50-kWth chemical looping circulating fluidized bed combustor unit at 700–900 °C. No agglomeration was observed, even though the oxygen carrier had a high CuO concentration (30%). The particle losses with 200–600 µm batch were significantly lower than that with the 100–200 µm batch. The oxygen carrier materials in the 200–600 µm range were circulated for approximately 3.1 days in the target temperature range (700–850 °C) and a total of approximately 40 h of chemical looping combustion testing was conducted during that time. The average fuel reactor temperatures ranged from 760 to 815 °C for the chemical looping combustion test periods, and the average air reactor temperature ranged from 840 to 915 °C. The fuel conversion from natural gas to CO 2 ranged from 50 to 80%. Approximately 1.6 h of continuous operation was achieved with no gas preheat and no natural gas augmented heating. During this test period, the average fuel reactor temperature ranged from 780 to 825 °C, the air reactor temperature ranged from 930 to 960 °C, and the natural gas to CO 2 conversion ranged from 50 to 65%. Finally, analysis of the oxygen carrier after the test indicated that there were no significant changes in the particle size or the surface morphology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Machined phononic crystals to block high-order Lamb waves and crosstalk in through-metal ultrasonic communication systems

For systems that require complete metallic enclosures (e.g., containment buildings for nuclear reactors), it is impossible to access interior sensors and equipment using standard electromagnetic techniques. A viable way to communicate and supply power through metallic barriers is the use of elastic waves and ultrasonic transducers, introducing several design challenges that must be addressed. Specifically, the use of multiple communication channels on the same enclosure introduces an additional mechanism for signal crosstalk between channels: guided waves propagating in the barrier between channels. This work numerically and experimentally investigates a machined phononic crystal to block MHz Lamb wave propagation between ultrasonic communication channels, greatly reducing wave propagation and the resulting crosstalk voltage. Blind grooves are machined into one or both sides of a metallic barrier to introduce a periodic unit cell, greatly altering the guided wave dispersion in the barrier. Numerical simulations are used to determine a set of groove geometries for testing, and experiments were performed to characterize the wave-blocking performance of each design. The best-performing design was tested using piezoelectric transducers bonded to the barrier, showing a 14.4 dB reduction in crosstalk voltage. Overall, the proposed periodic grooving method is a promising technique for completely isolating ultrasonic power/data transfer systems operating in a narrow frequency range.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Non-Boltzmann Effects in Chain Branching and Pathway Branching for Diethyl Ether Oxidation

Low-temperature (LT) engine applications have several potential benefits, including reduced emissions and increased efficiency. Attaining these benefits requires accurate kinetic modeling of LT chain branching, which depends heavily on ketohydroperoxide (KHP) decomposition. For diethyl ether (DEE), a promising biofuel, current estimates of the KHP decomposition rate constant are largely based on empirical fits to data. In this study, we investigate the most important KHP isomer in DEE LT oxidation by applying variable reaction coordinate transition state theory to the main pathway for KHP decomposition: OO bond fission to produce •OH and a keto-alkoxy radical, •OQ'O. We also use ab initio kinetics methods to investigate the decomposition of •OQ'O, where we find dominant branching to acetic acid, with the remaining flux going to CH 3 C(O)OCHO. Additionally, new time-resolved measurements of DEE and acetic acid concentrations during LT (450–600 K) DEE oxidation are obtained in a laser photolysis flow reactor coupled with multiplexed photoionization mass spectrometry. These new experimental data, along with jet-stirred reactor data in the literature, are compared with the predictions of a recent DEE mechanism (Tran et al. Proc. Comb. Inst. 2019, 37, 511-519) that was modified with the newly calculated ab initio rate constants for KHP and •OQ'O decomposition. The predictions of the modified mechanism are quite poor when compared to the experimental data; this is primarily due to the new KHP ⇌ •OQ'O + •OH rate constant, which is 1–2 orders of magnitude slower than empirical values employed in recent mechanisms. To reconcile the new KHP rate constant and the experimental data, we explore and quantify the possible role of non-Boltzmann (nB) reaction sequences. The nB reactions have a substantial effect on both the overall mechanism reactivity and the •OQ'O branching to acetic acid. We also provide guidance on the proper implementation of nB reactions in kinetic mechanisms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pathways to Electrochemical Ironmaking at Scale Via the Direct Reduction of Fe 2 O 3

Electrochemical ironmaking can provide an energy efficient, zero-emissions alternative to traditional methods of ironmaking, but the scalability of low-temperature electrochemical cells may be constrained by reactor throughput and the availability of acceptable feedstocks. Electrodes directly converting solid iron-oxide particles to metal circumvent traditional mass-transport limitations but are sensitive to both the particle size and nanoscale morphology of reactants. Furthermore, the effect of these properties on reactor throughput has not been systematically studied at model electrowinning surfaces. Here, we have used size-controlled, homologous α-Fe 2 O 3 particles to study how the nanoscale morphology of oxides influences the obtainable current density toward Fe metal and integrated these results in a technoeconomic model for alkaline iron electrowinning systems. Micron-scale α-Fe 2 O 3 with nanoscale porosity can be used to form Fe at current densities commensurate with industrial water electrolysis (>0.6 A cm –2 ) in the absence of external convection, providing a path to cost-competitive and scalable ironmaking using electrochemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗