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FY 2016 Progress Report on the ANL Sodium Draining and Refilling Experiments

The main incentive for utilization of compact diffusion-bonded sodium-to-CO 2 heat exchangers for a Sodium-Cooled Fast Reactor (SFR) with a supercritical carbon dioxide (sCO 2 ) Brayton cycle power converter is the potential for reduction in heat exchanger size and cost relative to traditional shell-and-tube technology. There is an incentive for the designer to reduce the width of the sodium and CO 2 channels as much as possible to realize the greatest size and cost reductions. However, there are practical limits on minimum channel size due to fundamental phenomena particular to sodium and CO 2 . One is that the channel size must be large enough to enable the rapid draining of sodium from the heat exchanger sodium channels in the event that a sodium leak is detected in an intermediate sodium heat transport system loop, in order to rapidly drain the sodium into the loop sodium storage vessel/tank and thereby limit the sodium mass released that could potentially burn if exposed to air. Information about the minimum sodium channel size can only be obtained by actually draining sodium from representative stainless steel sodium channels under prototypical conditions. It is not possible to obtain such information through modeling and simulation or through simulant experiments. The ANL Sodium Draining and Refilling experiment facility has been designed and is being assembled to obtain data on the draining of sodium from compact diffusion bonded sodium-to-carbon dioxide heat exchanger sodium channels including the mass of sodium drained versus time, the mass of sodium retained inside of the channels, and the potential for sodium to bridge the channel, freeze, and form a plug inside the channel versus the channel size. This information is needed to determine the minimum sodium channel size required to meet the requirements for sodium draining without bridges being left inside of the channels. Initial shakedown testing has been initiated using water and glass tubes before transitioning to sodium and stainless steel test sections. For the latter, the test sections will be heated to promote rapid sodium wetting of the stainless steel prior to draining. Testing with sodium will be initiated in FY 2017.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Development of High-efficiency and Cost-effective Forged Ingot Niobium Technology for Science Frontiers and Accelerator Applications

Development of Forged Ingot Niobium Technology: Worlds science frontier programs and SRF accelerator applications demand high performance and cost-effective SRF accelerator technology [1-8]. Fine-grain (FG) and Large-grain (LG) ingot niobium technologies have been very well developed and implemented in all the present-day accelerator projects. However, forged ingot niobium technology which is the focus of this development proposal will be much more cost-effective and expected to have several technical advantages. FG niobium sheet production is very complex involving more than ten processing steps making them prone to contamination. As a result, they are very expensive to produce and require stringent QA procedure to be ready for SRF cavity production. The accelerating cavity process steps are also numerous and require strict procedures in order to achieve high accelerating gradients and quality factors needed for science frontier programs. LG niobium disc production, directly sliced from the ingot, is relatively simple and straight forward to keep surface cleanness. The disc production cost is significantly low compared to FG niobium sheet production. However, there are (some) draw backs due to non-homogeneity of the grain boundary distribution, resulting in non-uniform mechanical properties and complex cavity fabrication, although the LG cavities achieve the expected high-gradient performance goals with lower cost. Medium-grain (MG) niobium disk production may be realized with a new approach/process, the disc directly sliced from the forged ingot, involves a simpler process steps contributing major production cost reduction [9]. These discs are expected to be superior as they tend to be homogenous with uniform sub millimeter grains and mechanical properties. We are eagerly looking forward to developing the forged ingot niobium SRF accelerator technology for the benefit of the world-wide science frontier programs, green energy subcritical nuclear energy systems and a wide variety of industrial applications including the production of radio isotopes and nuclear transmutation applications. Measurement of thermal characteristics of the forged ingot niobium: Measurement of the thermal diffusivity, D, of superconducting MG niobium is important to be understood in comparison with FG sheet and LG disc, as well as that of advanced composite material of Nb3Sn film sputtered on forged ingot Nb, which will be determined using transient pump-probe thermo-modulation [10,11]. Transient thermo-modulation is based on using an ultrafast laser pulse to heat the superconducting materials by a few K, then a synchronized laser pulse probes the reflectance of the heated material. For thin films on a substrate (e.g, 100-nm Nb3Sn on Nb), it takes <100 ps for the heat to reach the substrate by diffusion. Therefore, an ultrafast method is needed to probe D of the studied material. D will be measured from room temperature to liquid helium temperatures. Fundamental Research: The increase of rf loss in SRF cavities is related to trapping of residual magnetic field during the cavity cool-down. The study suggested that the micro structure plays the role in flux trapping sensitivity. The research includes the flux trapping and expulsion study as forged ingot niobium goes through several mechanical deformations, crystallization leading to the optimal SRF cavity performance. Furthermore, the cavity made from FG, MG, and LG sheet/disc will be compared to understand the optimal re-crystallization temperature that cavity needed to be heat treated which minimize the flux trapping and increase SRF cavity performance. References: 1. S. Belomestnykh, Overview of recent SRF developments for ERLs, presented at the SRF 2015, Whistler, BC, Canada (2015). 2. A. Yamamoto, M. Yamanaka and G. Myneni, Ingot Nb based SRF Technology for the International Linear Collider, in Science and Technology of Ingot Niobium for Superconducting Radio Frequency Applications, AIP Conf. Proc. 1687, 030005-1 ? 03005-6, 2015 3. Report of the Workshop on Energy and Environmental Applications of Accelerators, DOE Workshop Report. https://science.osti.gov/-/media/hep/pdf/Reports/2020/CASM_WorkshopReport.pdf? la=en&hash=AEB0B318ED0436B1C5FF4EE0FDD6DEB84C2F15B2 4. G. Ciovati, et al., Design of a cw, low-energy, high-power superconducting linac for environmental applications, Phys. Rev. Accel. Beams 21, 091601 (2018). 5. P. Dhakal, et al., Effect of high temperature heat treatments on the quality factor of a large-grain superconducting radio-frequency niobium cavity, Phys. Rev. ST Accel. Beams 16, 042001 (2013). 6. P. Kneisel et al., Review of ingot niobium as a material for superconducting radio frequency accelerating cavities, Nuclear Instruments and Methods in Physics Research A 774, 133 (2015). 7. G. Ciovati, P. Dhakal, and G. R, Myneni, Superconducting radio-frequency cavities made from medium and low-purity niobium ingots, Supercond. Sci. Technol. 29, 064002 (2016). 8. M. Drury et al., commissioning of the prototype C75 cavities in a CEBAF cryomodule, in Proc. of IPAC 2018, Vancouver, BC, Canada (2018) 9. Feasibility of forged-ingot niobium disc and SRF cavity fabrication technology recently demonstrated in cooperation of ATI, BSCE, and KEK (2020). 10. Hani E. Elsayed-Ali, ?Measurements of heat transport in thin films by ultrafast laser-based techniques,? 3rd International Conference on Thermal Issues in Emerging Technologies Theory and Applications, Cairo, Egypt, pp. 347 ? 350 (2010). DOI: 10.1109/ThETA17616.2010 11. W. M. G. Ibrahim, H. E. Elsayed-Ali, M. Schinn, and C. A. Bonner, Jr., ?Ultrafast investigation of electron dynamics in multilayer metals,? Int. J. Heat and Mass Transfer, 47(10?11), 2261?2268 (2004).

Myneni, G.↗

Investigation of long-term light stability of negative charge injected into oxide-nitride-oxide passivation stack of crystalline silicon solar cells

A negatively charged oxide-nitride-oxide stack for field-effect passivation of crystalline silicon solar cells is discussed. The negative charge was injected into the stack by a plasma charge injection technology. Charge stability was studied by exposing samples to AM1.5 simulation visible light and full-spectrum light at temperatures ranging from 55 to 78 °C for up to 300 h. Charge injection and loss were quantified based on shifts in the flatband voltage of capacitance–voltage curves measured with a mercury probe. The most probable mechanism of charge loss was found to be diffusion of negative charged hydrogen atoms through nitride and bottom oxide. The optimum recipe for each layer of the stack was investigated to minimize the loss of injected charge. The flatband voltage decay of the optimized stack was found to fit a power-law trend, suggesting the dispersive transport of hydrogen atoms with a dispersion parameter of ~0.06–0.07. The optimized stack is projected to maintain a negative charge density of about 3.6 × 10 12 cm –2 or more after 25 years of field operation in an environment such as Arizona, which would be sufficient for field-effect passivation under one-sun illumination. Furthermore, the high stability of the negative injected charge makes the plasma charging technology a safer and lower cost alternative to Al 2 O 3 -passivation technology commonly used to passivate p-type surfaces.

14 SOLAR ENERGY↗

Innovative Method for Reliable Measurement of PEM Water Electrolyzer Component Resistances

Understanding the sheet resistance of porous electrodes is essential for improving the performance of polymer electrolyte membrane (PEM) water electrolyzers and related technologies. Despite its importance, existing methods often fail to provide reliable and comprehensive data, especially for porous materials with complex morphologies and non‐uniform thicknesses. This study introduces a robust and straightforward method for determining the sheet resistance of porous electrodes using a novel probe concept based on industrial printed circuit board (PCB) technology. This probe measures resistance across ten distances, ranging from 250 µm to 2500 µm, enabling local mapping of resistance. The study focuses on the sheet resistance of key components in PEM water electrolyzers, including the gas diffusion layer (GDL), porous transport layer (PTL), and catalyst layers deposited on a membrane. Additionally, an image‐processing‐based method is presented to obtain the thickness distribution of the studied catalyst layers, facilitating a detailed analysis of the electrical in‐plane resistivity with thickness variations. Overall, this methodology has the potential to expedite material integration and bridge the gap between electrode engineering and single‐cell testing, thereby advancing the development of PEM water electrolyzers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deep Generative Models in Energy System Applications: Review, Challenges, and Future Directions

In recent years, with the advent of mature machine learning products like ChatGPT, Stable Diffusion, and Sora, the world has witnessed tremendous changes driven by the rapid development of generative artificial intelligence (GAI). Beyond applications in text, speech, image, and video creation, deep generative models (DGMs) underpinning these cutting-edge technologies have also been employed by domain researchers to address scientific and engineering challenges. This paper aims to fill a gap in the research community by providing a systematic review of how DGMs have been utilized in energy system applications. After introducing four most popular DGMs, we review and categorize 196 research articles into five focus areas: data generation, forecasting, situational awareness, modeling, and optimal decision-making. Through this classification, we uncover trends in how DGMs are employed for each type of problem, highlighting GAI techniques that contribute to breakthroughs over traditional methods. We discuss limitations in existing literature, engineering challenges, and propose future directions, all tailored to the unique nature of problems in energy system engineering. Our goal is to offer insights for energy system domain researchers, providing a comprehensive view of existing studies and potential future opportunities.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Underlying mechanism of structural transformation between GaSb and GaAs response to intense electronic excitation

Ion irradiation of semiconductors has emerged as a promising approach for fabricating self-organized nanosystems with high atomic precision, despite often being accompanied by undesirable phenomena. Exploring the mechanisms underlying structural transformations is crucial for assessing nanostructure array types under complex irradiation environments. By quantitatively calculating the thermodynamically driven processes and analyzing the impact of intrinsic structural parameters, distinct structural transformations in response to intense electronic excitation are systematically investigated in gallium antimonide (GaSb) and gallium arsenide (GaAs) systems. In high-energy regimes, the nanofibers layer of GaSb exhibits intriguing structural discrepancy, characterized by partial nanofibers with coherent boundaries, interspersed nanopores accompanied by antisite defects and Ga precipitates, distinguishing to a series of discontinuous latent tracks that emerged within cylindrical trajectories in GaAs. Furthermore, significant diffusion behaviors of the nanohillocks are discovered in GaAs, with higher average roughness than GaSb, driven by the gradient stress distribution influenced by the free-surface effects. The deposition energy for melting phase formation, Gibbs free energy, and Ga diffusion coefficients contribute to the distinctive structural features, evidencing relatively stable morphological configurations and higher irradiation resistance in GaAs. Consequently, special optoelectronic properties associated with structural discrepancies facilitate the design and optimization of material functionalities by irradiation technologies.

36 MATERIALS SCIENCE↗

The persistence of memory in ionic conduction probed by nonlinear optics

Predicting practical rates of transport in condensed phases enables the rational design of materials, devices and processes. This is especially critical to developing low-carbon energy technologies such as rechargeable batteries. For ionic conduction, the collective mechanisms, variation of conductivity with timescales and confinement, and ambiguity in the phononic origin of translation, call for a direct probe of the fundamental steps of ionic diffusion: ion hops. However, such hops are rare-event large-amplitude translations, and are challenging to excite and detect. Here we use single-cycle terahertz pumps to impulsively trigger ionic hopping in battery solid electrolytes. This is visualized by an induced transient birefringence, enabling direct probing of anisotropy in ionic hopping on the picosecond timescale. The relaxation of the transient signal measures the decay of orientational memory, and the production of entropy in diffusion. We extend experimental results using in silico transient birefringence to identify vibrational attempt frequencies for ion hopping. Using nonlinear optical methods, we probe ion transport at its fastest limit, distinguish correlated conduction mechanisms from a true random walk at the atomic scale, and demonstrate the connection between activated transport and the thermodynamics of information.

25 ENERGY STORAGE↗

PET based nanocomposite films for microwave packaging applications

In recent years, changes in life standards have promoted the diffusion of Ready to Cook (RTC) and Ready to Eat (RTE) products for microwave ovens. However, the main limits in microwave (MW) ovens usage are often related to the proper choice of packaging materials suitable for such technology. In fact, packages for microwaveable RTC and RTE foods should ensure adequate preservation of the product before cooking/heating such as high barriers to gases and aromas and adequate control of water vapor transmission. In addition, microwaveable packaging material must be transparent to MW, thermally stable and resistant to the mechanical stress induced by the accumulation in the head space of volatile substances produced during the cooking. Polymeric materials are good candidates for microwaveable packaging thanks to their transparency to MW. In the last years a great interest is devoted to developing innovative solution based on the use of additives or systems that act as susceptors or heating enhancers for improving the characteristics of polymers in cooking/heating in MW ovens. The present work was focused on the production and characterization of nanocomposite copolyester based films suitable for microwaveable food packaging applications. The matrices selected consist in two PET copolymers modified with carbon black (ULTRA STD) and with titanium oxide (ULTRA NA). Nanocomposite co-extruded multilayer films were produced using different percentages (0%, 2% and 4%wt/wt) of Cloisite 20A (C20A). Films were analyzed for evaluating the effect of nanofiller on the morphology and barrier properties. Moreover, to verify the effectiveness of the designed systems in reducing the cooking times of meat products, MW heating tests were carried out on pork meat hamburgers in MW oven at varying supplied powers. The cooking tests have pointed out that the selected matrices are efficient in reducing cooking times and that even low concentration of C20A acts as heating enhancers of PET.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Generalized Fourier's law for nondiffusive thermal transport: Theory and experiment

Phonon heat conduction over length scales comparable to their mean free paths is a topic of considerable interest for basic science and thermal management technologies. However, debate exists over the appropriate constitutive law that defines thermal conductivity in the nondiffusive regime. Here, we derive a generalized Fourier's law that links the heat flux and temperature fields, valid from ballistic to diffusive regimes and for general geometries, using the Peierls-Boltzmann transport equation within the relaxation time approximation. Here, this generalized Fourier's law predicts that thermal conductivity not only becomes nonlocal at length scales smaller than phonon mean free paths but also requires the inclusion of an inhomogeneous nonlocal source term that has been previously neglected. We provide evidence for the validity of this generalized Fourier's law through direct comparison with time-domain thermoreflectance measurements in the nondiffusive regime without adjustable parameters. Furthermore, we show that interpreting experimental data without the generalized Fourier's law can lead to inaccurate measurement of thermal transport properties.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Probing the Structure and Dynamics of Fluid Mixtures in Porous Materials Through Ultrafast Vibrational Spectro-Microscopy and Many-Body Molecular Dynamics

This research program focused on the characterization of both molecular structure and dynamics of aqueous solutions in various metal-organic frameworks (MOFs) and organic polymers that have recently been proposed for applications in water treatment technologies. This was accomplished by integrating ultrafast vibrational spectroscopy and microscopy, which are sensitive to local environments, molecular orientation, and dynamical couplings, with many-body molecular dynamics (MB-MD) simulations, which enable realistic modeling of aqueous systems and porous materials under different thermodynamic conditions. Our studies allowed for identifying the physical mechanisms and characterizing the underlying molecular interactions between water and host materials that determine the adsorption and transport processes of water in various MOFs and β-cyclodextrin polymers – prototypical examples of porous materials and polymers, that have recently been proposed for technological applications in water purification. By combining bulk- and surface-sensitive, spatially resolved ultrafast vibrational spectroscopy with MB-MD simulations, it was possible to gain broad insight into the structure and mobility of water under heterogeneous confinement at various length scales. In particular, measurements of surface- and bulk-sensitive vibrational spectra at single crystal level, integrated with MB-MD simulations were used to characterize domain-specific, structure–binding affinity relationships. Besides providing specific information about the behavior of aqueous solutions in prototypical MOFs and organic polymers for potential applications in water treatment technologies, our studies also provided fundamental insights into the properties of aqueous solutions in confined heterogeneous environments, which have broad implications in many areas, ranging from heterogeneous catalysis to oil recovery, ion transport processes, and reaction-diffusion processes in crowded systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

ADVANCED TEST REACTOR (ATR) CONVERSION TO LOW ENRICHED URANIUM (LEU) FUEL

The United States Department of Energy (DOE), National Nuclear Security Administration (NNSA), Office of Material Management and Minimization (MMM) is working to convert research reactors globally from highly enriched uranium (HEU) fuel to low-enriched uranium (LEU) fuel. MMM and its predecessor programs have converted or verified the shutdown of 88 HEU research reactors and isotope production facilities, using LEU fuel developed in the 1980s. However, there is a small set of high performance research reactors which require a new high density LEU fuel for conversion, including six U.S. high performance research reactors (USHPRRs), which include the Advanced Test Reactor (ATR) and the ATR Critical (ATRC) Facility at the Idaho National Laboratory (INL) near Idaho Falls, ID; University of Missouri Research Reactor (MURR) at Columbia, MO; Massachusetts Institute of Technology Reactor (MITR) at MIT in Cambridge, MA; High Flux Isotope Reactor (HFIR) at Oak Ridge National Laboratory (ORNL) near Oak Ridge, TN; and National Bureau of Standards Reactor (NBSR) at the National Institute of Standards and Technology (NIST) Center for Neutron Research (NCNR) in Gaithersburg, MA. These reactors will share the same uranium-molybdenum (U-Mo) fuel plate design. The U-Mo fuel meat foil will have a zirconium (Zr) diffusion barrier with aluminum cladding. Three different application methods for the Zr diffusion barrier layer are being pursued – co-rolled, electroplating and plasma spraying. Fabrication of the higher density LEU U-Mo fuel has presented several challenges. Because the U-Mo fuel fabrication process uses the existing stockpile of 93% highly enriched uranium (HEU) to be blended with molybdenum and depleted uranium (DU) to form 19.75% LEU, cost benefits of enriching to 19.75% will not be realized. Homogeneity of the U-235 and molybdenum in the metal foil is a challenge due to U-Mo casting process results in variations between adjacent cast U-Mo plates. LEU will not require less U-235 as previously believed due to self-shielding properties of U-238 requiring additional U-235 to be loaded in each fuel element. Although the overall dimensions of the ATR fuel element remain unchanged, the weight of the LEU ATR fuel element is 72% greater than a HEU ATR fuel element. During waste recovery and recycling efforts, separation of aluminum cladding from the HEU fuel meat is a relatively simple chemical dissolution, however, separation of the Zr diffusion barrier from the U-Mo fuel meat is significantly more challenging.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Achieving the Vision: An Update on Cleanup, Closure, and Reindustrialization of the East Tennessee Technology Park - 18401

URS-CH2M Oak Ridge LLC (UCOR) is responsible for cleanup of the U.S. Department of Energy's (DOE) East Tennessee Technology Park (ETTP) in Oak Ridge, Tennessee. Formerly known as the K-25 site, the facility enriched uranium for major defense nd energy programs for more than 40 years. The site's industrial processes - largely the gaseous diffusion method used for enriching uranium - left behind radioactive, chemical and industrial contaminants in soils and structures. Cleanup of the environmental legacies enables DOE's goal for converting ETTP into a private sector industrial park. Return of the restored site to the community will attract new industries to the region, creating jobs and growing the economy. The central elements to achieve DOE's vision for the site are 1) Cleanup, 2) Closure, and 3) Reindustrialization. Cleanup entails completion of all demolition activities and remedial actions consistent with the Comprehensive Environmental Response, Compensation and Liability Act of 1980 (CERCLA) agreements. Closure leaves facilities and infrastructure in a condition that enables transfer of the site to non-federal entities and reduces DOE's long-term stewardship costs. Closure activities include: - Infrastructure stabilization (site utilities, roads, stormwater, etc.); - Disposal or transfer of government property; - Relocation of most DOE contractors and support functions offsite; - Transfer of the majority of the site property to non-federal entities for redevelopment. Reindustrialization enables DOE's vision for the site as a multi-use private sector industrial park, reducing DOE's costs and enhancing the local economy. Transfer to the private sector will be accomplished through the Community Reuse Organization of East Tennessee (CROET), which will serve as the Park Manager. (author)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Python codes for the paper - "Trade-offs in the latent representation of microstructure evolution"

SAND2024-00946O Python codes used in "Trade-offs in the latent representation of microstructure evolution," a manuscript accepted for publication in Acta Materialia, are part of a repository. The code was developed to perform analysis of microstructure evolution. The repository consists of two main directories: models, which train and test models such as autoencoders and diffusion maps, and analysis, which analyzes microstructures. Source code is used to perform dimensionality reduction of microstructure data for analysis of its evolution in time. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.

Dingreville, Remi↗

Advancing Enhanced Raman Spectroscopy to Detect and Measure NOW Pheromones (CPRB 2022 proposal)

Insect sex pheromones are chemical compounds that insects release to attract their partners over distances of hundreds of meters or even kilometers, in complete darkness and without any audible signals. Use of synthetic forms of key compounds have in some cases become an essential component of monitoring and/or managing key pests of agricultural crops, including navel orangeworm (Amyelois transitella) (NOW) in California tree nuts. These pheromone-based strategies can include monitoring, mating disruption, mass trapping, attract-and-kill and push-pull. There are currently multiple commercially available mating disruption products available for NOW and recent studies have demonstrated that they can be effectively used to reduce crop damage by this pest. Just how mating disruption works is not fully established and likely varies across products and target species. For instance, the extent to which synthetic pheromones compete with natural pheromone is not well understood, or in the case of monitoring, how efficaciously the insect follows the diffusing plumes, especially across large blocks and at plot borders. Furthermore, there may be specific conditions under which poor or impeded diffusion of synthetic pheromone diminishes the disruption effect, which could result in some males effectively locating females for reproduction. At the same time, many commercially available synthetic lures are also available, and growers have been effectively using them to track population development – although the attractive range of these lures remains unclear. That is, while pheromone lures can attract many moths, the relationship between trap capture and local populations, much less crop damage, remains unclear. Regardless of the emission source (aerosol puffers, meso emitters, lures etc.), we currently lack the ability to fully understand how these synthetic pheromone compounds diffuse away from their point-source of emission – and subsequently how this might affect the efficacy of mating disruption and/or the accuracy of monitoring efforts. Raman spectroscopy (RS) may offer a means to detect synthetic pheromone because of its analytical properties and recent technological advancements. In combination with nanostructured probes, RS has a demonstrated capability to detect volatiles at extremely low concentrations. While other methods for detecting pheromones have proven to be successful, such analytical methods like mass spectrometry (MS) gas chromatography (GC) require sampling in the fields and are not real-time. Other methods such as EAG/ EAD are also invasive (use antennas) but are of course valuable. Opto-electronic, micro and nano sensors just recently enticed interest. We fall in this latter category, proposing the use of optical spectroscopy (Raman) in a fiber aided by nanostructures to provide a chemical fingerprint without transductions and in real-time (i.e. no sampling). To date, we have been able to generate Raman signatures for the main chemicals in synthetic pheromones (a first for science, to the best of our knowledge), observe their trends at different concentrations, and also provide a clear distinction of such signatures in mixed samples via Principal Component Analysis (PCA) – all of which strengthens our conclusions on the ability of RS to detect emissions in more realistic conditions. We also established processes to enhance the detection sensitivity via preconcentration with Solid Phase Micro Extraction (SPME) fibers and Surface Enhanced Raman Spectroscopy (SERS) to increase the overall optical signals. Furthermore, we explored limitations and requirements for detecting from dispensers, lures, or live moths, including Dept. of Energy and CA State regulatory approvals. Finally, we setup some of our first “orchard in a box” experiments to measure pheromone diffusion along with developing appropriate models.

42 ENGINEERING↗

Facilitating Screening of MOFs for Mixed Matrix Membranes Using Machine Learning and the Maxwell Model

Metal organic framework (MOF)-based mixedmatrix membranes (MMMs), which embed MOF particles in polymer matrices, combine the advantages of polymeric and inorganic membranes. Multiple previous studies have used the Maxwell model together with molecular simulations and machine learning (ML) to predict the performance of MOF/polymer MMMs. However, the assumption of rigid MOF frameworks in molecular simulations limited the accuracy of the data used in the predictions, particularly in predicting molecular diffusivities. We developed a novel workflow integrating ML models with consideration of MOF flexibility to predict the permeability and selectivity of 131,722 MMMs for CO 2 /CH 4 , O 2 /N 2 and He/H 2 separations. The full range of achievable MMM performance within the Maxwell model was analyzed, and several promising MOFs were identified using this workflow. This approach offers an efficient tool for screening any polymer and MOF combination in gas separation applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

FY 2017 Progress Report on the Argonne Sodium Draining and Refilling Experiments

The main incentive for utilization of compact diffusion-bonded sodium-to-CO 2 heat exchangers for a Sodium-Cooled Fast Reactor (SFR) with a supercritical carbon dioxide ( s CO 2 ) Brayton cycle power converter is the potential for reduction in heat exchanger size and cost relative to traditional shell-and-tube technology. There is an incentive for the designer to reduce the width of the sodium and CO 2 channels as much as possible to realize the greatest size and cost reductions. However, there are practical limits on minimum channel size due to fundamental phenomena particular to sodium and CO 2 . One is that the channel size must be large enough to enable the rapid draining of sodium from the heat exchanger sodium channels in the event that a sodium leak is detected in an intermediate sodium heat transport system loop, in order to rapidly drain the sodium into the loop sodium storage vessel/tank and thereby limit the sodium mass released that could potentially burn if exposed to air. Information about the minimum sodium channel size can only be obtained by actually draining sodium from representative wetted stainless steel sodium channels under prototypical conditions. It is not possible to obtain such information through modeling and simulation or through simulant experiments. The ANL Sodium Draining and Refilling experiment facility has been designed and is being assembled to obtain data on the draining of sodium from compact diffusion-bonded sodium-to-carbon dioxide heat exchanger sodium channels including the mass of sodium drained versus time, the mass of sodium retained inside of the channels, and the potential for sodium to bridge the channel, freeze, and form a plug inside the channel versus the channel size. This information is needed to determine the minimum sodium channel size required to meet the requirements for sodium draining without bridges being left inside of the channels. Initial shakedown testing has been initiated using water and glass and plastic tubes before transitioning to sodium and stainless steel test sections. For the latter, the test sections will be heated to high temperature to promote rapid sodium wetting of the stainless steel prior to draining. Testing with sodium will be initiated in FY 2018.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Finite Larmor radius effects on E x B weak turbulence transport

Transport of test particles in two-dimensional weak turbulence with waves propagating along the poloidal direction is studied using a reduced model. Finite Larmor radius (FLR) effects are included by gyroaveraging over one particle orbit. For low wave amplitudes the motion is mostly regular with particles trapped in the potential wells. As the amplitude increases the trajectories become chaotic and the Larmor radius modifies the orbits. For a thermal distribution of Finite Larmor radii the particle distribution function (PDF) is Gaussian for small $\unicode[STIX]{x1D70C}_{th}$ (thermal gyroradius) but becomes non-Gaussian for large $\unicode[STIX]{x1D70C}_{th}$ . Furthermore, the time scaling of transport is diffusive, as characterized by a linear dependence of the variance of the PDF with time. An explanation for this behaviour is presented that provides an expression for an effective diffusion coefficient and reproduces the numerical results for large wave amplitudes which implies generalized chaos. When a shear flow is added in the direction of wave propagation, a modified model is obtained that produces free-streaming particle trajectories in addition to trapped ones; these contribute to ballistic transport for low wave amplitude but produce super-ballistic transport in the chaotic regime. As in the previous case, the PDF is Gaussian for low $\unicode[STIX]{x1D70C}_{th}$ becoming non-Gaussian as it increases. The perpendicular transport presents the same behaviour as in the case with no flow but the diffusion is faster in the presence of the flow.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

In situ stable crack growth at the micron scale

Grain boundaries typically dominate fracture toughness, strength and slow crack growth in ceramics. To improve these properties through mechanistically informed grain boundary engineering, precise measurement of the mechanical properties of individual boundaries is essential, although it is rarely achieved due to the complexity of the task. Here we present an approach to characterize fracture energy at the lengthscale of individual grain boundaries and demonstrate this capability with measurement of the surface energy of silicon carbide single crystals. We perform experiments using an in situ scanning electron microscopy-based double cantilever beam test, thus enabling viewing and measurement of stable crack growth directly. These experiments correlate well with our density functional theory calculations of the surface energy of the same silicon carbide plane. Subsequently, we measure the fracture energy for a bi-crystal of silicon carbide, diffusion bonded with a thin glassy layer.

Science & Technology - Other Topics↗